CN114695857A - Monoatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material - Google Patents

Monoatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material Download PDF

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CN114695857A
CN114695857A CN202210424739.XA CN202210424739A CN114695857A CN 114695857 A CN114695857 A CN 114695857A CN 202210424739 A CN202210424739 A CN 202210424739A CN 114695857 A CN114695857 A CN 114695857A
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antimony
nitrogen
oxygen
porous carbon
carbon sheet
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CN114695857B (en
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张桥保
肖本胜
陈慧鑫
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Xiamen University
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Xiamen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The present disclosure provides a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material, comprising: the porous carbon sheet matrix material comprises a plurality of porous carbon sheets to form a layered material, and the porous carbon sheets are tightly connected with one another; and a monatomic antimony modified and nitrogen and oxygen co-doped structure, wherein the monatomic antimony, nitrogen and oxygen atoms form an oxygen-antimony-nitrogen (O-Sb-N) bond and are combined in the porous carbon sheet substrate material to form the monatomic antimony and nitrogen and oxygen co-doped structure. The disclosure also provides a preparation method of the porous carbon sheet composite material modified by the monoatomic antimony and co-doped with nitrogen and oxygen, a battery cathode material and a battery.

Description

Monoatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material
Technical Field
The disclosure relates to the field of two-dimensional carbon atom/carbon materials, in particular to a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material and a preparation method thereof.
Background
Sodium/potassium ion batteries have attracted considerable attention in recent years because of the wide availability and low cost of sodium/potassium resources and the low redox voltage of sodium/potassium.
In the aspect of electrode materials of sodium/potassium ion batteries, more positive electrode materials are available at present, but the selection of negative electrode materials in practical application is relatively limited. Based on this, it is important to develop a suitable sodium/potassium ion battery negative electrode material.
Most of carbon sheet composite materials in the prior art inhibit huge volume expansion in the alloying process of antimony particles in a mode of coating the antimony particles with a carbon material, so that the electrochemical performance of the carbon sheet composite materials is improved, and the researched active electrode material takes the antimony particles as a main body and takes the carbon material as an auxiliary body.
Compared with an antimony material based on a sodium/potassium alloying reaction mechanism, the carbon material has the advantages of long cycle stability, low cost, good electrochemistry and safety performance, controllable structure and the like, and meets the requirement of large-scale energy storage.
However, when the carbon material is applied to the sodium/potassium ion battery electrode material, the carbon material is limited by a corresponding intercalation and deintercalation reaction mechanism, the capacity is low, modification of the carbon material is a problem worthy of intensive research, and the current modification strategy is basically to introduce F, O, P, N and other non-metal heteroatom doping into the carbon material, but the improvement of the capacity of the carbon material is limited.
Disclosure of Invention
In order to solve at least one of the above technical problems, the present disclosure provides a monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material and a preparation method thereof.
According to one aspect of the present disclosure, there is provided a monatomic antimony-modified and nitrogen-and-oxygen-co-doped porous carbon sheet composite material, comprising:
the carbon sheet comprises a porous carbon sheet matrix material, wherein the porous carbon sheet matrix material comprises a plurality of porous carbon sheets to form a layered material, and the porous carbon sheets are tightly connected with one another;
the single atom antimony is modified and is doped with nitrogen and oxygen, the single atom antimony, nitrogen and oxygen atoms form oxygen antimony nitrogen (O-Sb-N) bonds and are combined in the porous carbon sheet substrate material to form the single atom antimony and nitrogen and oxygen doped structure.
Monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheets according to at least one embodiment of the present disclosureA composite material in which the monoatomic antimony forms O with nitrogen atoms and oxygen atoms2-Sb-N4A bond of said monoatomic antimony with O2-Sb-N4The bonding form is coated in the matrix material of the porous carbon piece.
According to the monatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material of at least one embodiment of the present disclosure, a plurality of monatomic antimony is uniformly embedded in the porous carbon sheet matrix material.
The monoatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material according to at least one embodiment of the present disclosure has bonds of O-Sb-N-C between the monoatomic antimony, nitrogen, oxygen, and carbon.
The monoatomic antimony-modified and nitrogen-and-oxygen-co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure is amorphous carbon.
The monoatomic antimony-modified and nitrogen-and-oxygen-co-doped porous carbon sheet composite according to at least one embodiment of the present disclosure has a length of 2 to 15 μm and a width of 2 to 15 μm.
The monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure has a molar content that is lower than the molar content of elemental nitrogen, and the two have an order of magnitude difference.
The monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure has a ratio of the molar content of monatomic antimony to the molar content of elemental nitrogen of about 1: 12.
according to another aspect of the disclosure, a preparation method of a monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material is provided, which comprises the following steps:
sequentially adding an antimony source, a nitrogen source and a carbon/oxygen source into an absolute ethyl alcohol solvent to form a mixed solution;
carrying out ultrasonic treatment on the mixed solution within a preset time range;
continuously magnetically stirring the mixed solution subjected to ultrasonic treatment at a preset temperature to obtain a uniform mixed solution, and recording the uniform mixed solution as Sb/C/N-1;
drying the mixed solution Sb/C/N-1 to obtain a solid substance, and marking as Sb/C/N-2;
and heating and carbonizing the solid Sb/C/N-2 under a protective atmosphere to obtain the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
According to the preparation method of the monoatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material, the carbon/oxygen source is a raw material simultaneously comprising a carbon element and an oxygen element.
According to the preparation method of the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material of at least one embodiment of the present disclosure, the mass ratio of the antimony source, the nitrogen source and the carbon/oxygen source is preferably (0.05-0.3):2: 0.2.
According to the preparation method of the monatomic antimony-modified and nitrogen and oxygen-codoped porous carbon sheet composite material, the continuous magnetic stirring time is 12-24 h.
According to the preparation method of the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material, the temperature of the drying treatment is 60-80 ℃.
According to the preparation method of the monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material, the drying treatment time is 12-24 h.
According to the preparation method of the monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material of at least one embodiment of the present disclosure, the heating temperature is 600 ℃ to 800 ℃.
According to the preparation method of the monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material, the heating rate is 5-10 ℃/min.
According to yet another aspect of the present disclosure, there is provided a battery anode material comprising the monatomic antimony-modified and nitrogen-and-oxygen-co-doped porous carbon sheet composite according to any one of the embodiments of the present disclosure.
According to still another aspect of the present disclosure, there is provided a battery having a battery anode material including the monatomic antimony-modified and nitrogen-and-oxygen-co-doped porous carbon sheet composite according to any one of the embodiments of the present disclosure.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 is a schematic flow diagram of a preparation method of a monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite according to an embodiment of the present disclosure.
Fig. 2 is an X-ray diffraction pattern (XRD) of the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared by the preparation method according to one embodiment of the present disclosure.
Fig. 3 is a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) of the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure.
Fig. 4 is an X-ray energy spectrum analysis (EDS) of the monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite prepared in example 1 of the present disclosure. Wherein, the content of Sb is 12.9 wt%, the content of C is 63.5 wt%, the content of N is 17.8 wt%, and the content of O is 5.8 wt%.
Fig. 5 is a CV curve graph of the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure as a negative electrode material of a potassium ion battery.
FIG. 6 shows that the current is 0.1Ag for the monatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material prepared in example 1 and the pure nitrogen-oxygen-codoped two-dimensional carbon sheet prepared in comparative example 1 and comparative example 2 are used as the negative electrode material of the potassium ion battery-1Comparative cycle performance of (c).
Fig. 7 is a graph comparing the rate cycle performance of the battery when the monatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material prepared in example 1 and the pure nitrogen-oxygen-codoped two-dimensional carbon sheet prepared in comparative example 1 and comparative example 2 are used as the negative electrode material of the potassium ion battery.
Fig. 8 is a CV curve graph of the monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure as an anode material of a sodium ion battery.
FIG. 9 shows that the current is 0.1Ag for the monatomic antimony-modified and nitrogen-oxygen-codoped porous carbon sheet composite material prepared in example 1 and the pure nitrogen-oxygen-codoped two-dimensional carbon sheet prepared in comparative examples 1 and 2 of the disclosure when the two-dimensional carbon sheet is used as the negative electrode material of the sodium ion battery-1Comparative cycle performance of (c).
Fig. 10 is a graph comparing the rate cycle performance of the battery when the monatomic antimony-modified and nitrogen-oxygen-co-doped porous carbon sheet composite material prepared in example 1 and the pure nitrogen-oxygen-co-doped two-dimensional carbon sheets prepared in comparative examples 1 and 2 are used as the negative electrode material of the sodium ion battery.
Figure 11 is an aberration corrected HRTEM image of a monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite made in example 1 of the present disclosure.
Fig. 12 is an XPS-N1S diagram of a monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite prepared in example 1 of the present disclosure.
Fig. 13 is a schematic structural diagram of a monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite according to one embodiment of the present disclosure.
Fig. 14 is an X-ray near-edge spectrum, R-space, and fit thereof for a monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite according to one embodiment of the present disclosure.
FIG. 15 is an XPS-O1 s + Sb3d graph of a monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure.
Detailed Description
The present disclosure will be described in further detail with reference to the drawings and embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure. It should be further noted that, for the convenience of description, only the portions relevant to the present disclosure are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. Technical solutions of the present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
Unless otherwise indicated, the illustrated exemplary embodiments/examples are to be understood as providing exemplary features of various details of some ways in which the technical concepts of the present disclosure may be practiced. Accordingly, unless otherwise indicated, features of the various embodiments may be additionally combined, separated, interchanged, and/or rearranged without departing from the technical concept of the present disclosure.
The use of cross-hatching and/or shading in the drawings is generally used to clarify the boundaries between adjacent components. As such, unless otherwise noted, the presence or absence of cross-hatching or shading does not convey or indicate any preference or requirement for a particular material, material property, size, proportion, commonality between the illustrated components and/or any other characteristic, attribute, property, etc., of a component. Further, in the drawings, the size and relative sizes of components may be exaggerated for clarity and/or descriptive purposes. While example embodiments may be practiced differently, the specific process sequence may be performed in a different order than that described. For example, two processes described consecutively may be performed substantially simultaneously or in reverse order to that described. In addition, like reference numerals denote like parts.
When an element is referred to as being "on" or "on," "connected to" or "coupled to" another element, it can be directly on, connected or coupled to the other element or intervening elements may be present. However, when an element is referred to as being "directly on," "directly connected to" or "directly coupled to" another element, there are no intervening elements present. For purposes of this disclosure, the term "connected" may refer to physically, electrically, etc., and may or may not have intermediate components.
The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Furthermore, when the terms "comprises" and/or "comprising" and variations thereof are used in this specification, the presence of stated features, integers, steps, operations, elements, components and/or groups thereof are stated but does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and/or groups thereof. It is also noted that, as used herein, the terms "substantially," "about," and other similar terms are used as approximate terms and not as degree terms, and as such, are used to interpret inherent deviations in measured values, calculated values, and/or provided values that would be recognized by one of ordinary skill in the art.
The monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material and the preparation method thereof according to the present disclosure will be described in detail below with reference to fig. 1 to 15.
Fig. 1 is a schematic flow diagram of a preparation method of a monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite according to an embodiment of the present disclosure.
Referring to fig. 1, a preparation method S100 of a monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to an embodiment of the present disclosure includes the steps of:
s102, sequentially adding an antimony source, a nitrogen source and a carbon/oxygen source into an absolute ethyl alcohol solvent to form a mixed solution;
s104, carrying out ultrasonic treatment on the mixed solution;
s106, carrying out continuous magnetic stirring on the mixed solution subjected to ultrasonic treatment at a preset temperature to obtain a uniform mixed solution, and recording the uniform mixed solution as Sb/C/N-1;
s108, drying the mixed solution Sb/C/N-1 to obtain a solid substance Sb/C/N-2;
s110, heating and carbonizing the solid Sb/C/N-2 under a protective atmosphere to obtain the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material.
The disclosed porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen comprises: the porous carbon sheet substrate material comprises a plurality of porous carbon sheets to form a layered material, and the porous carbon sheets are tightly connected with one another; and the monatomic antimony modifies and nitrogen and oxygen codope structure, and the monatomic antimony, nitrogen and oxygen atoms form an oxygen-antimony-nitrogen bond and are combined in the porous carbon sheet substrate material to form the monatomic antimony and nitrogen and oxygen codope structure.
Fig. 13 is a structural schematic diagram of a monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite according to an embodiment of the present disclosure, and a monatomic antimony-modified and nitrogen and oxygen co-doped structure is shown in fig. 13.
FIG. 14 shows the X-ray absorption spectrum and the R space of the porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen in example 1 and the fitting result thereof, and the coordination number of the monoatomic Sb is 6 obtained by fitting, which proves that the monoatomic Sb is O2-Sb-N4The 6-coordinate structure of (1). ICP analysis showed the results shown in Table 1, and the content of monoatomic antimony was 14.3 wt%, which is close to the EDS analysis result.
TABLE 1
Figure BDA0003608045150000071
Antimony (Sb) is a high theoretical capacity alloyed negative electrode material with a high hot spot in a battery material, but the alloying process is accompanied by volume expansion of several times, so that the cycle performance is poor.
The disclosure of O formation by monoatomic antimony and N/O atoms2-Sb-N4The bond is combined in the carbon material, so that more sodium/potassium storage reaction sites can be provided, and the capacity of the carbon material can be remarkably improved.
The carbon/oxygen source described in this disclosure is a feedstock that contains both elemental carbon and elemental oxygen.
In step S102, an antimony source, a nitrogen source, and a carbon/oxygen source are sequentially added to an absolute ethanol solvent to obtain a mixed solution, wherein the mass ratio of the antimony source, the nitrogen source, and the carbon/oxygen source is preferably (0.05-0.3):2:0.2, and in specific implementations, the ratio of the antimony source, the nitrogen source, and the carbon/oxygen source may be selected to be 0.05:2:0.2, 0.1:2:0.2, and 0.3:2: 0.2. The antimony source may be antimony trichloride (SbCl)3) The nitrogen source may be dicyandiamide and the carbon/oxygen source may be trimesic acid.
It is within the scope of the present disclosure for one skilled in the art to adjust the antimony source, the nitrogen source, and the carbon/oxygen source in light of the teachings of the present disclosure.
In step S104, the mixed solution is subjected to ultrasound within a preset time range, which may be 20 minutes to 50 minutes, and preferably, the preset time is 30 minutes.
In step S106, the above-mentioned mixed solution is subjected to continuous magnetic stirring (e.g., at room temperature) to obtain a homogeneous mixed solution Sb/C/N-1. Wherein, the magnetic stirring time can be 12h to 24h, and is preferably 12h and 24 h. It should be noted that the magnetic stirring time is not limited to 12h to 24h, and may be adjusted to other time ranges as appropriate, all falling within the scope of the present disclosure.
In step S108, the mixed solution is placed in a constant-temperature electric oven for drying, and the solvent is completely volatilized to obtain a white solid precursor Sb/C/N-2. Wherein the drying temperature of the electric oven is 60 ℃ to 80 ℃. The electric oven drying working time is 12h to 24h, preferably 12h and 24 h. It should be noted that the drying temperature is not limited to 60 ℃ to 80 ℃, and other temperature ranges can be properly adjusted, and all the temperature ranges fall within the protection scope of the present disclosure.
In step S110, the porcelain boat containing the white solid precursor Sb/C/N-2 is placed in a heating device, and carbonized under a nitrogen protective atmosphere at a constant temperature to obtain a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material. The heating device can be a tube furnace, the carbonization temperature of the tube furnace is 600-800 ℃, preferably 600 ℃, 700 ℃, 800 ℃, and the tube furnace is a tube furnaceThe temperature rise rate of the furnace is 5 ℃/min to 10 ℃/min, preferably 5 ℃/min and 10 ℃/min, and the protective atmosphere is N2Or Ar. It should be noted that the carbonization temperature range is not limited to 600 to 800 ℃, and other temperature ranges can be properly adjusted, all falling within the protection scope of the present disclosure.
Other examples are given below to further illustrate the preparation methods of the monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composites of the present disclosure, including examples 1-10, and comparative examples 1 and 2 thereof.
Example 1:
the preparation method of the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material of the embodiment includes the following steps.
The method comprises the following steps: 0.1g of antimony trichloride (SbCl) was added to 10ml of an anhydrous ethanol solvent in this order3Namely antimony source), 2g dicyandiamide (nitrogen source) and 0.2g trimesic acid (carbon/oxygen source), and performing magnetic stirring for 24 hours after ultrasonic treatment for 30min to obtain a precursor homogeneous solution Sb/C/N-1.
Step two: and (4) putting the precursor homogeneous solution Sb/C/N-1 obtained in the step one into a constant temperature device with the temperature of 80 ℃ for heat preservation for 24 hours. After 24h, a white solid was obtained after the reaction was complete and ground to a powder in a mortar, and the resulting product was labeled as Sb/C/N-2. Wherein, the constant temperature equipment can be a constant temperature electric oven. The precursor homogeneous solution Sb/C/N-1 can be firstly put into a beaker, and then the beaker filled with the precursor homogeneous solution Sb/C/N-1 is put into a constant-temperature electric oven.
Step three: placing the white solid product Sb/C/N-2 obtained in the step two into a porcelain boat, placing the porcelain boat filled with the white solid Sb/C/N-2 into a heating device, and heating by the heating device at the temperature of 800 ℃ under the protective atmosphere of N2The temperature is constant and the heating is carried out for 2 hours in the environment to obtain a black solid product Sb/C/N-3, namely the porous carbon sheet composite material modified by the monoatomic antimony and co-doped with nitrogen and oxygen. In the step, the heating device can be a tube furnace, and the temperature rise rate of the tube furnace is 5 ℃/min. Wherein, the porcelain boat can be replaced by other containers with the same function.
Comparative example 1:
step one, sequentially adding 2g of dicyandiamide and 0.2g of trimesic acid into 10ml of absolute ethanol solvent, and performing ultrasonic stirring for 30min for 24h to obtain a precursor homogeneous solution.
And step two, putting the precursor homogeneous solution obtained in the step one into a constant temperature device with the temperature of 80 ℃ and preserving the temperature for 24 hours. After 24h, a white solid was obtained after the reaction was complete and ground into a powder using a mortar. Wherein, the constant temperature equipment can be a constant temperature electric oven. The precursor homogeneous solution Sb/C/N-1 can be firstly put into a beaker, and then the beaker filled with the precursor homogeneous solution Sb/C/N-1 is put into a constant-temperature electric oven.
And step three, heating the product obtained in the step two for 2 hours at the constant temperature of 800 ℃ in the environment of N2 in the protective atmosphere by a heating device to obtain a black solid product. In the step, the heating device can be a tube furnace, and the temperature rise rate of the tube furnace is 5 ℃/min.
Comparative example 1 is different from example 1 in that comparative example 1 does not add an antimony source during the preparation process, and other steps are the same as those of example 1, and a pure nitrogen and oxygen co-doped porous carbon sheet composite material is obtained.
Comparative example 2:
step one, sequentially adding 2g of dicyandiamide and 0.2g of trimesic acid into 10ml of absolute ethanol solvent, and performing ultrasonic stirring for 30min for 24h to obtain a precursor homogeneous solution.
And step two, adding 80mg of pure nitrogen-doped and oxygen-doped carbon sheet obtained in the step one and 30mg of antimony chloride into 80ml of ethanol solution, magnetically stirring for 2 hours, and performing suction filtration and drying to obtain the target product of the antimony particle nitrogen-doped and oxygen-doped carbon sheet.
Carrying out structural component test characterization on the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared in the embodiment 1; the materials prepared in example 1, comparative example 1 and comparative example 2, carbon black and a binder are prepared into 12mm pole pieces in a ratio of 8:1:1, potassium/sodium metal is respectively used as a counter electrode to assemble a button type half cell, and the electrochemical performance of the button type half cell as a negative electrode material of a potassium ion battery and a sodium ion battery is tested, and the specific characteristics are as follows:
x-ray diffraction pattern (XRD) characterization: as a result, referring to fig. 2, it can be seen that the XRD diffraction peak of the obtained composite material of the present disclosure has only a broad peak of carbon at about 2 θ ═ 26 °, and there is no characteristic diffraction peak of Sb, indicating that Sb is in an amorphous distribution.
Characterization by scanning electron microscope and transmission electron microscope: as a result, as shown in fig. 3, the obtained composite material of the present disclosure has a two-dimensional layered structure, and the surface of the carbon sheet is wrinkled and porous. The carbon sheet is tightly connected with the carbon sheet.
Characterization of X-ray spectral analysis (EDS): as a result, referring to fig. 4 and 14, it can be seen that the composite material of the present disclosure contains carbon (C), nitrogen (N), and antimony (Sb), and each element is uniformly distributed. Wherein the content of Sb is 12.9 wt%, the content of C is 63.5 wt%, the content of N is 17.8 wt%, and the content of O is 5.8 wt%.
Characterization as negative electrode CV of potassium ion battery: at 0.1mV s-1Under the scan rate condition of (1), a voltage window of 0.01V to 3V, 3 voltammogram cycles were tested, and the results are shown in fig. 5, and it can be seen that during the first cycle, a broader cathodic peak occurs around 0.62V, which is attributed to the formation of an irreversible SEI film; in the subsequent cycle process, CV curves are almost overlapped, which shows that the composite material has good reversible cycle performance as a negative electrode material of the potassium-ion battery.
And (3) as the electrochemical cycle performance characterization of the potassium ion battery negative electrode: at 0.1A g-1Under the charging and discharging conditions of (1), the voltage window is 0.01V-3V, and the result is shown in FIG. 6, which indicates that the initial discharge capacity is 1043.2mAh g-1After 100 cycles of charge and discharge, the capacity of the capacitor is still maintained at 593.3mAh g-1High reversible capacity of (2). The capacity of the carbon sheet in comparative example 1 was severely degraded and the capacity of the carbon sheet in comparative example 2 was shown to be lower.
And (3) rate performance characterization as a potassium ion battery cathode: at 0.05, 0.1, 0.2, 0.5, 1, 2, 4A g-1Under different current charging and discharging conditions, the voltage window is 0.01V-3V, and the result is shown in FIG. 7, and the material prepared in example 1 has good capacity retention rate.
Characterization as sodium ion battery negative electrode CV: at 0.1mV s-1Under the condition of scan rate of (1), a voltage window of 0.01V to 3V, 3 voltammograms were tested, and the results are shown in FIG. 8, in the first round-tripIn the ring process, a broad cathodic peak appears around 0.58V, which is attributed to the formation of an irreversible SEI film; a set of spikes near around 0.1V is attributed to Na intercalation into the carbon layer, with CV curves nearly overlapping during later cycles, forming NaCx. The composite material has good reversible cycle performance as a negative electrode material of the sodium ion battery.
And (3) as the electrochemical cycle performance characterization of the negative electrode of the sodium-ion battery: at 0.1A g-1Under the charging and discharging conditions of (1), the voltage window is 0.01V-3V, and the result is shown in FIG. 9, which shows that the initial discharge capacity is 513.3mAh g-1After 50 cycles of charge and discharge, the capacity of the lithium ion battery is still kept at 398.6mAh g-1High reversible capacity of (2). In comparative example 1, the battery capacity was severely deteriorated, and in comparative example 2, the battery capacity was exhibited to be low.
And (3) representing the rate performance of the cathode of the sodium ion battery: at 0.05, 0.1, 0.2, 0.5, 1, 2, 4A g-1Under different current charging and discharging conditions, the voltage window is 0.01V-3V, and as a result, as shown in FIG. 10, the material prepared in example 1 has good capacity retention rate.
The aberration corrected HRTEM shows that the results are shown in fig. 11, where the scattered bright spots are Sb monoatomic, indicating that Sb is present as a monoatomic.
XPS diagrams of Sb3d and O1s for N1s and Sb show that, as shown in FIGS. 12 and 15, monatomic Sb forms O with nitrogen and oxygen in nitrogen and oxygen co-doped carbon sheets2-Sb-N4A key.
Example 2:
the difference from example 1 is that antimony trichloride (SbCl) in this example3): dicyandiamide: the mass ratio of trimesic acid is 0.05:2:0.2, and other steps are the same as those in example 1, so that the porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen is obtained.
Example 3:
the difference from example 1 is that antimony trichloride (SbCl) in this example3): dicyandiamide: the mass ratio of trimesic acid is 0.3:2:0.2, and other steps are the same as those in example 1, so that the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material is obtained.
Example 4:
the difference from example 1 is that the antimony source in this example is antimony nitrate (Sb (NO)3)3) And obtaining the porous carbon sheet composite material modified by the monoatomic antimony and co-doped with nitrogen and oxygen in the same way as in the example 1.
Example 5:
the difference from example 1 is that the heating temperature of the present example is 600 ℃, the ultrasonic time is 50 minutes, and other steps are the same as example 1, so as to obtain the monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
Example 6:
the difference from example 1 is that the heating temperature of the present example is 700 ℃, the ultrasonic time is 20 minutes, and other steps are the same as example 1, so as to obtain the monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
Example 7:
the difference from the example 1 is that the temperature rise rate of the tube furnace of the present example is 10 ℃/min, and other steps are the same as the example 1, so as to obtain the porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen.
Example 8:
the difference from example 1 is that the protective atmosphere in this example is argon (Ar), and the other steps are the same as example 1, so as to obtain a porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen.
Example 9:
the difference from the example 1 is that the magnetic stirring time of the example is 12h, and other steps are the same as the example 1, so that the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material is obtained.
Example 10:
the difference from the example 1 is that the working time of the constant-temperature electric oven in the embodiment is 12h, and other steps are the same as the example 1, so that the porous carbon sheet composite material modified by the monoatomic antimony and co-doped with nitrogen and oxygen is obtained.
Fig. 13 is a schematic structural diagram of a monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite according to one embodiment of the present disclosure.
As shown in fig. 13, the porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen comprises the following components.
The porous carbon sheet matrix material comprises a plurality of porous carbon sheets to form a layered material, and the porous carbon sheets are tightly connected with each other. Wherein the carbon sheet may be graphite phase carbon nitride (g-C3N 4).
The plurality of monoatomic antimones form oxygen-antimony-nitrogen bonds with nitrogen and oxygen and are combined in the porous carbon sheet matrix material. The monoatomic antimony forms O with nitrogen2-Sb-N4Bond, monoatomic antimony with O2-Sb-N4The bonding form is coated in the matrix material of the porous carbon sheet. The plurality of monoatomic stibium is uniformly embedded in the substrate material of the porous carbon sheet. The bond of the monoatomic antimony, nitrogen, oxygen and carbon is O-Sb-N-C. In the porous carbon sheet composite material modified by the monatomic antimony and co-doped with nitrogen and oxygen, the content of the monatomic antimony is lower than that of nitrogen element (molar content), and the monatomic antimony and the nitrogen element have order of magnitude difference.
The monatomic antimony-modified and nitrogen-and-oxygen-codoped porous carbon sheet composite material provided in fig. 13 can be obtained by the preparation method of the monatomic antimony-modified and nitrogen-and-oxygen-codoped porous carbon sheet composite material disclosed by the present disclosure, and the composite material can be used as a material for manufacturing a negative electrode of a sodium/potassium ion battery.
The present disclosure includes but is not limited to the above embodiments, and it should be understood by those skilled in the art that any equivalent or partial replacement made under the spirit and principle of the present disclosure will fall within the protection scope of the present disclosure.
According to yet another aspect of the present disclosure, there is provided a battery anode material comprising the monatomic antimony-modified and nitrogen-and-oxygen-co-doped porous carbon sheet composite according to any one of the embodiments of the present disclosure.
The monatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material provided by the disclosure is formed by distributing monatomic antimony in an atomic state in a porous carbon sheet substrate material, so that when the monatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material disclosed by the disclosure is applied to a negative electrode material of a potassium/sodium ion battery, the potassium/sodium ion diffusion dynamics can be enhanced, more alkali metal ion anchoring points can be provided, and a monatomic antimony modified and nitrogen and oxygen co-doped strategy can generate more delocalized electrons, the conductivity can be improved, and the electrochemical performance of the electrode material can be improved. The application of the two-dimensional carbon material in the potassium/sodium ion battery cathode material obviously improves the active site and material utilization rate of the carbon material, and further improves the theoretical capacity of the two-dimensional carbon material in the potassium/sodium ion battery cathode material. The application of the two-dimensional composite material in the cathode material of the potassium/sodium ion battery not only improves the charge and discharge capacity of the carbon material, but also solves the outstanding problems of serious volume expansion, short cycle life and the like of the antimony-based material, improves the structural stability of the material, and has excellent electrochemical performance.
The preparation method of the monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material has the advantages of low cost of raw materials, simple preparation operation, safety, strong controllability and the like, and is easy to popularize and use.
In the description herein, reference to the description of the terms "one embodiment/implementation," "some embodiments/implementations," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/implementation or example is included in at least one embodiment/implementation or example of the present application. In this specification, the schematic representations of the terms described above are not necessarily the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.

Claims (10)

1. The utility model provides a monatomic antimony modification and nitrogen, oxygen co-doped porous carbon sheet composite which characterized in that includes:
the carbon sheet comprises a porous carbon sheet matrix material, wherein the porous carbon sheet matrix material comprises a plurality of porous carbon sheets to form a layered material, and the porous carbon sheets are tightly connected with one another; and
the single atom antimony is modified and is doped with nitrogen and oxygen, the single atom antimony, nitrogen and oxygen atoms form oxygen antimony nitrogen (O-Sb-N) bonds and are combined in the porous carbon sheet substrate material to form the single atom antimony and nitrogen and oxygen doped structure.
2. The monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite material of claim 1, wherein the monatomic antimony forms O with nitrogen and oxygen atoms2-Sb-N4A bond of said monoatomic antimony with O2-Sb-N4The bonding form is coated in the matrix material of the porous carbon piece.
3. The monatomic antimony-modified and nitrogen-and-oxygen-co-doped porous carbon sheet composite material of claim 1 or 2, wherein a plurality of the monatomic antimony is uniformly embedded in the porous carbon sheet matrix material.
4. The monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite of claim 1, wherein the bond of the monatomic antimony, nitrogen, oxygen, and carbon is O-Sb-N-C.
5. The monatomic antimony-modified and nitrogen and oxygen-co-doped porous carbon sheet composite material of claim 1, wherein the carbon sheet is amorphous carbon.
6. The monatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite of claim 1, wherein the porous carbon sheet has a length of 2 to 15 μ ι η and a width of 2 to 15 μ ι η;
preferably, the molar content of the monoatomic antimony is lower than that of the nitrogen element, and the two have an order of magnitude difference;
preferably, the ratio of the molar content of said monatomic antimony to the molar content of said nitrogen element is about 1: 12.
7. a preparation method of a porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen is characterized by comprising the following steps:
sequentially adding an antimony source, a nitrogen source and a carbon/oxygen source into an absolute ethyl alcohol solvent to form a mixed solution;
carrying out ultrasonic treatment on the mixed solution;
continuously magnetically stirring the mixed solution subjected to ultrasonic treatment at a preset temperature to obtain a uniform mixed solution, and recording the uniform mixed solution as Sb/C/N-1;
drying the mixed solution Sb/C/N-1 to obtain a solid substance marked as Sb/C/N-2; and
and heating and carbonizing the solid Sb/C/N-2 under a protective atmosphere to obtain the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
8. The preparation method of the monatomic antimony-modified and nitrogen-and-oxygen-codoped porous carbon sheet composite material according to claim 7, wherein the carbon/oxygen source is a raw material simultaneously comprising a carbon element and an oxygen element;
preferably, the mass ratio of the antimony source, the nitrogen source and the carbon/oxygen source is (0.05-0.3) to 2: 0.2;
preferably, the continuous magnetic stirring time is 12h to 24 h;
preferably, the temperature of the drying treatment is 60 ℃ to 80 ℃;
preferably, the drying time is 12-24 h;
preferably, the temperature of the heating is 600 ℃ to 800 ℃;
preferably, the heating rate is 5 ℃/min to 10 ℃/min.
9. A battery negative electrode material, comprising the monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to any one of claims 1 to 6.
10. A battery, wherein a battery negative electrode material of the battery comprises the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to any one of claims 1 to 6.
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