CN114695857B - Monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material - Google Patents
Monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material Download PDFInfo
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- CN114695857B CN114695857B CN202210424739.XA CN202210424739A CN114695857B CN 114695857 B CN114695857 B CN 114695857B CN 202210424739 A CN202210424739 A CN 202210424739A CN 114695857 B CN114695857 B CN 114695857B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 200
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 155
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 104
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 95
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000001301 oxygen Substances 0.000 title claims abstract description 94
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- CBHXNHKHSWDLJG-UHFFFAOYSA-N [Sb].[N].[O] Chemical compound [Sb].[N].[O] CBHXNHKHSWDLJG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 229910001414 potassium ion Inorganic materials 0.000 description 18
- 229910001415 sodium ion Inorganic materials 0.000 description 18
- 239000003575 carbonaceous material Substances 0.000 description 14
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 239000012456 homogeneous solution Substances 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000441 X-ray spectroscopy Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000001385 aberration-corrected high resolution transmission electron microscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical group [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present disclosure provides a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material comprising: a porous carbon sheet matrix material comprising a plurality of porous carbon sheets to form a layered material, the porous carbon sheets being closely connected to each other; and the monoatomic antimony is modified and is in a nitrogen and oxygen co-doped structure, and the monoatomic antimony forms an oxygen-antimony-nitrogen (O-Sb-N) bond with nitrogen and oxygen atoms and is combined into the porous carbon sheet matrix material to form the monoatomic antimony and nitrogen and oxygen co-doped structure. The disclosure also provides a preparation method of the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material, a battery anode material and a battery.
Description
Technical Field
The present disclosure relates to the field of two-dimensional carbon atoms/carbon materials, and in particular, to a single-atom antimony-modified and nitrogen and 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 sodium/potassium resources have wide availability and low cost, and sodium/potassium has a low redox voltage.
In the aspect of sodium/potassium ion battery electrode materials, more positive electrode materials are available at present, but the selection of negative electrode materials is relatively limited in practical application. Based on the above, it is important to develop a suitable negative electrode material for sodium/potassium ion batteries.
In the carbon sheet composite material in the prior art, the huge volume expansion in the alloying process of the antimony particles is restrained in a mode of coating the antimony particles by the carbon material, so that the electrochemical performance of the carbon sheet composite material is improved, and the active electrode material is researched by taking the antimony particles as a main body and taking the carbon material as an auxiliary body.
Compared with an antimony material based on an alloying reaction sodium/potassium storage mechanism, the carbon material has the advantages of long-cycle stability, low cost, good electrochemistry, 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 electrode material of the sodium/potassium ion battery, the carbon material is limited by a corresponding intercalation and deintercalation reaction mechanism, the capacity is low, the modification of the carbon material is a problem worthy of intensive study, and the current modification strategy basically introduces F, O, P, N and other nonmetallic heteroatom doping into the carbon material, but has limited capacity improvement.
Disclosure of Invention
In order to solve at least one of the technical problems, the present disclosure provides a single-atom antimony-modified and nitrogen and 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 monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material comprising:
a porous carbon sheet matrix material comprising a plurality of porous carbon sheets to form a layered material, each of the porous carbon sheets being intimately connected;
and the monoatomic antimony is modified and is in a nitrogen and oxygen co-doping structure, and the monoatomic antimony forms an oxygen-antimony-nitrogen (O-Sb-N) bond with nitrogen and oxygen atoms and is combined into the porous carbon sheet matrix material to form the monoatomic antimony and nitrogen and oxygen co-doping structure.
A monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the monatomic antimony forming O with nitrogen atoms, oxygen atoms 2 -Sb-N 4 Bond of monoatomic antimony in O 2 -Sb-N 4 The bond-forming form is encapsulated within the porous carbon sheet matrix material.
A porous carbon sheet composite material modified with monoatomic antimony and co-doped with nitrogen and oxygen according to at least one embodiment of the present disclosure, a plurality of the monoatomic antimony being uniformly embedded in the porous carbon sheet matrix material.
A monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the bond of the monoatomic antimony, nitrogen atom, oxygen atom and carbon being O-Sb-N-C.
A monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the carbon sheet being amorphous carbon.
A monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the porous carbon sheet having a length of 2 μm to 15 μm and a width of 2 μm to 15 μm.
A monoatomic 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 of monoatomic antimony that is lower than the molar content of elemental nitrogen, and both have orders of magnitude differences.
A monatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the ratio of the molar content of monatomic antimony to the molar content of nitrogen element is about 1:12.
according to another aspect of the present disclosure, there is provided a method for preparing a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material, comprising:
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 which is named as Sb/C/N-1;
drying the mixed solution Sb/C/N-1 to obtain a solid matter which is named as Sb/C/N-2;
and heating and carbonizing the solid Sb/C/N-2 in a protective atmosphere to obtain the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
A method for preparing a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the carbon/oxygen source being a feedstock comprising both elemental carbon and elemental oxygen.
According to 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 monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material in at least one embodiment of the present disclosure, the continuous magnetic stirring time is 12 to 24 hours.
A method of preparing a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the temperature of the drying process being from 60 ℃ to 80 ℃.
According to the preparation method of the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material in at least one embodiment of the present disclosure, the drying treatment time is 12 to 24 hours.
A method of preparing a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to at least one embodiment of the present disclosure, the heating temperature being 600 ℃ to 800 ℃.
According to the preparation method of the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material, the heating temperature rising rate is 5 ℃/min to 10 ℃/min.
According to yet another aspect of the present disclosure, there is provided a battery anode material comprising the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material of any of the embodiments of the present disclosure.
According to yet another aspect of the present disclosure, there is provided a battery, the battery anode material of which comprises the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material of any 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 chart of a method of preparing a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to one embodiment of the disclosure.
FIG. 2 is an X-ray diffraction pattern (XRD) of a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material made by a method of making an embodiment of the present disclosure.
Fig. 3 is a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) of a monoatomic 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 spectroscopy analysis (EDS) of a single-atom antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure. Wherein the content of Sb is 12.9wt%, the content of C is 63.5wt%, the content of N is 17.8wt%, and the content of O is 5.8wt%.
Fig. 5 is a CV graph of a monoatomic 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 for a potassium ion battery.
FIG. 6 is a graph showing the small current of 0.1Ag when the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure and the pure nitrogen-oxygen co-doped two-dimensional carbon sheets prepared in comparative example 1 and comparative example 2 are used as the negative electrode material of the potassium ion battery -1 Is a graph comparing cycle performance of (c).
Fig. 7 is a graph comparing the cycle performance of the battery rate when the monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure and the pure nitrogen and oxygen co-doped two-dimensional carbon sheets 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 graph of a monoatomic 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 for a sodium ion battery.
FIG. 9 is a graph showing the small current of 0.1Ag when the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure and the pure nitrogen-oxygen co-doped two-dimensional carbon sheets prepared in comparative example 1 and comparative example 2 are used as the negative electrode material of sodium ion battery -1 Is a graph comparing cycle performance of (c).
Fig. 10 is a graph comparing the cycle performance of the battery rate when the monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure and the pure nitrogen and oxygen co-doped two-dimensional carbon sheets prepared in comparative example 1 and comparative example 2 are used as the negative electrode material of the sodium ion battery.
Fig. 11 is an aberration corrected HRTEM image of a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material made in example 1 of the present disclosure.
FIG. 12 is an XPS-N1S plot of a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure.
Fig. 13 is a schematic structural view of a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to one embodiment of the disclosure.
Fig. 14 is an X-ray near-edge spectrum, R-space, and fitting results thereof of a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to one embodiment of the disclosure.
FIG. 15 is an XPS-O1s+Sb3d graph of a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material prepared in example 1 of the present disclosure.
Detailed Description
The present disclosure is described in further detail below with reference to the drawings and the embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant content and not limiting of the present disclosure. It should be further noted that, for convenience of description, only a portion relevant to the present disclosure is shown in the drawings.
In addition, embodiments of the present disclosure and features of the embodiments may be combined with each other without conflict. The technical aspects of the present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
Unless otherwise indicated, the exemplary implementations/embodiments shown 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. Thus, unless otherwise indicated, features of the various implementations/embodiments may be additionally combined, separated, interchanged, and/or rearranged without departing from the technical concepts of the present disclosure.
The use of cross-hatching and/or shading in the drawings is typically used to clarify the boundaries between adjacent components. As such, the presence or absence of cross-hatching or shading does not convey or represent any preference or requirement for a particular material, material property, dimension, proportion, commonality between illustrated components, and/or any other characteristic, attribute, property, etc. of a component, unless indicated. In addition, in the drawings, the size and relative sizes of elements may be exaggerated for clarity and/or descriptive purposes. While the exemplary embodiments may be variously implemented, the specific process sequences may be performed in a different order than that described. For example, two consecutively described processes may be performed substantially simultaneously or in reverse order from that described. Moreover, like reference numerals designate like parts.
When an element is referred to as being "on" or "over", "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 this reason, the term "connected" may refer to physical connections, electrical connections, and the like, with or without 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 the present specification, the presence of stated features, integers, steps, operations, elements, components, and/or groups thereof is described, but the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof is not precluded. It is also noted that, as used herein, the terms "substantially," "about," and other similar terms are used as approximation terms and not as degree terms, and as such, are used to explain the inherent deviations of measured, calculated, and/or provided values that would be recognized by one of ordinary skill in the art.
The monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite materials of the present disclosure and methods of making the same are described in detail below in conjunction with fig. 1-15.
FIG. 1 is a schematic flow chart of a method of preparing a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to one embodiment of the disclosure.
Referring to fig. 1, a method S100 for preparing a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to one 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, continuously magnetically stirring the mixed solution subjected to ultrasonic treatment at a preset temperature to obtain a uniform mixed solution which is named as Sb/C/N-1;
s108, drying the mixed solution Sb/C/N-1 to obtain a solid matter which is named as Sb/C/N-2;
and S110, heating and carbonizing the solid Sb/C/N-2 in a protective atmosphere to obtain the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
The monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material comprises: a porous carbon sheet matrix material comprising a plurality of porous carbon sheets to form a layered material, the porous carbon sheets being closely connected to each other; and the monoatomic antimony is modified and is in a nitrogen and oxygen co-doped structure, and the monoatomic antimony forms an oxygen-antimony-nitrogen bond with nitrogen and oxygen atoms and is combined in the porous carbon sheet matrix material to form the monoatomic antimony and nitrogen and oxygen co-doped structure.
Fig. 13 is a schematic structural view of a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to one embodiment of the disclosure, and the monoatomic antimony modified and nitrogen and oxygen co-doped structure is shown in fig. 13.
FIG. 14 shows the X-ray absorption spectrum and R-space of the monatomic Sb-modified and nitrogen-oxygen co-doped porous carbon sheet composite material of example 1 and the fitting result thereof, wherein the coordination number of the monatomic Sb obtained by fitting is 6, which proves that the monatomic Sb is O 2 -Sb-N 4 A 6-coordinate structure of (2). ICP measurement shows that the single-atom antimony content is 14.3wt% and is similar to EDS analysis result.
TABLE 1
Antimony (Sb) is a high theoretical capacity alloying negative electrode material with higher hot spots in the battery material, but the alloying process is accompanied by several times of volume expansion, resulting in poor cycle performance.
The present disclosure forms O with N/O atoms through monoatomic antimony 2 -Sb-N 4 The 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 comprising both elemental carbon and elemental oxygen.
In step S102, the antimony source, the nitrogen source and the carbon/oxygen source are sequentially added into the 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 implementation, 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.
The adjustment of the antimony source, nitrogen source, carbon/oxygen source by those skilled in the art in light of the technical proposal of the disclosure falls within the protection scope of the disclosure.
In step S104, the mixed solution is subjected to ultrasound for a preset time range, which may be 20 minutes to 50 minutes, preferably, for 30 minutes.
In step S106, the above mixed solution is subjected to continuous magnetic stirring (for example, at room temperature) to obtain a homogeneous mixed solution Sb/C/N-1. The magnetic stirring time can be 12 to 24 hours, preferably 12 to 24 hours. It should be noted that the magnetic stirring time is not limited to 12h to 24h, and can be properly adjusted to other time ranges, which fall within the protection 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, so that a white solid precursor Sb/C/N-2 is obtained. Wherein the drying temperature of the electric oven is 60-80 ℃. The drying working time of the electric oven is 12 to 24 hours, preferably 12 to 24 hours. It should be noted that, the drying temperature is not limited to 60 ℃ to 80 ℃, and can be properly adjusted to other temperature ranges, which fall within the protection scope of the present disclosure.
In step S110, the porcelain boat with the white solid precursor Sb/C/N-2 is placed in a heating device, and carbonized under the constant temperature condition of nitrogen protection atmosphere to obtain the monoatomic antimony modified and nitrogen and 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 ℃, the heating rate of the tube furnace is 5-10 ℃ per minute, preferably 5-10 ℃ per minute, and the protective atmosphere is N 2 Or Ar. It should be noted that, the carbonization temperature range is not limited to 600 to 800 ℃, and may be appropriately adjusted to other temperature ranges, which fall within the protection scope of the present disclosure.
Other examples are set forth below to further illustrate the preparation of the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composites of the present disclosure, including examples 1 through 10, and comparative examples 1 and 2 thereof.
Example 1:
the preparation method of the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material comprises the following steps.
Step one: to 10ml of absolute ethanol solvent was added 0.1g of antimony trichloride (SbCl 3 I.e. antimony source), 2g dicyandiamide (nitrogen source) and 0.2g trimesic acid (carbon/oxygen source), and after ultrasonic treatment for 30min, magnetically stirring for 24h to obtain precursor homogeneous solution Sb/C/N-1.
Step two: and (3) putting the precursor homogeneous solution Sb/C/N-1 obtained in the step one into 80 ℃ constant temperature equipment for heat preservation for 24 hours. After 24 hours, a white solid was obtained after the completion of the reaction, and the white solid was pulverized into powder with a mortar, and the obtained product was designated 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 placed in a beaker, and then the beaker filled with the precursor homogeneous solution Sb/C/N-1 is placed in a constant temperature electric oven.
Step three: placing the white solid product Sb/C/N-2 obtained in the second step into a porcelain boat, placing the porcelain boat filled with the white solid Sb/C/N-2 into a heating device, and heating the porcelain boat at 800 ℃ by the heating device under the protection of N 2 Heating for 2 hours at constant temperature in the environment of (1) to obtain a black solid product Sb/C/N-3, namely the porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen. In the step, the heating device can be a tube furnace, and the heating 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:
sequentially adding 2g of dicyandiamide and 0.2g of trimesic acid into 10ml of absolute ethyl alcohol solvent, and magnetically stirring for 24 hours after ultrasonic treatment for 30min to obtain a precursor homogeneous solution.
And step two, placing the precursor homogeneous solution obtained in the step one into 80 ℃ constant temperature equipment for heat preservation for 24 hours. After 24 hours, a white solid was obtained after the completion of the reaction, and the white solid was pulverized into powder with a mortar. Wherein, the constant temperature equipment can be a constant temperature electric oven. The precursor homogeneous solution Sb/C/N-1 can be placed in a beaker, and then the beaker filled with the precursor homogeneous solution Sb/C/N-1 is placed in a constant temperature electric oven.
And thirdly, heating the product obtained in the second step for 2 hours at a constant temperature under the environment that the heating temperature is 800 ℃ and the protective atmosphere is N2 by a heating device to obtain a black solid product. In the step, the heating device can be a tube furnace, and the heating rate of the tube furnace is 5 ℃/min.
Comparative example 1 differs from example 1 in that comparative example 1 was prepared without adding an antimony source, and in the same manner as in example 1, a pure nitrogen and oxygen co-doped porous carbon sheet composite material was obtained.
Comparative example 2:
sequentially adding 2g of dicyandiamide and 0.2g of trimesic acid into 10ml of absolute ethyl alcohol solvent, and magnetically stirring for 24 hours after ultrasonic treatment for 30min to obtain a precursor homogeneous solution.
And step two, adding 80mg of the pure nitrogen-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-oxygen doped carbon sheet.
Carrying out structural component test characterization on the monoatomic antimony modified and nitrogen and 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 binder were prepared into 12mm pole pieces in a ratio of 8:1:1, and potassium/sodium metal was used as counter electrodes respectively to assemble button half cells, and the electrochemical properties of the button half cells as cathode materials of potassium ion cells and sodium ion cells were tested as follows:
x-ray diffraction pattern (XRD) characterization: as a result, as shown in fig. 2, the XRD diffraction peak of the obtained composite material of the present disclosure is only a broad peak of carbon at about 2θ=26°, and no characteristic diffraction peak of Sb is shown to be an amorphous distribution.
Scanning electron microscope and transmission electron microscope characterization: as a result, see fig. 3, the obtained composite material of the present disclosure is 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.
X-ray spectroscopy (EDS) characterization: as a result, as shown in 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 12.9wt%, the content of C is 63.5wt%, the content of N is 17.8wt%, and the content of O is 5.8wt%.
Characterization as potassium ion battery negative electrode CV: at 0.1mV s -1 Is a scan rate bar of (2)A piece, a voltage window of 0.01V-3V, tested for 3 cycles of voltammetry, results see fig. 5, showing that during the first cycle, a broad cathode peak appears near 0.62V due to the formation of an irreversible SEI film; in the latter cycle, CV curves almost overlap, which shows that the composite material has good reversible cycle performance as a cathode material of a potassium ion battery.
As the characteristic of electrochemical cycle performance of the cathode of the potassium ion battery: at 0.1A g -1 Under the charge and discharge conditions, the voltage window was 0.01V-3V, and the initial discharge capacity was 1043.2mAh g as shown in FIG. 6 -1 After 100 cycles of charge and discharge, the capacity of the material is still kept at 593.3mAh g -1 Is a high reversible capacity of (a). The carbon sheet capacity in comparative example 1 was severely degraded, and the carbon sheet capacity in comparative example 2 was lower.
As a representation of the rate capability of the anode of the potassium ion battery: at 0.05, 0.1, 0.2, 0.5, 1, 2, 4A g -1 Under different current charge and discharge conditions, the voltage window was 0.01V-3V, and as a result, see fig. 7, the material prepared in example 1 had good capacity retention.
Characterization as sodium ion battery negative electrode CV: at 0.1mV s -1 A voltage window of 0.01V-3V, tested for 3 cycles of voltammograms, see fig. 8, with a broad cathode peak around 0.58V during the first cycle due to the formation of an irreversible SEI film; a set of peaks occurring near 0.1V or so are due to Na intercalation into the carbon layer, and during the subsequent cycles, the CV curves almost overlap, forming the NaCx. The composite material is shown to have good reversible cycle performance when being used as a negative electrode material of a sodium ion battery.
As a characterization of the electrochemical cycle performance of the negative electrode of the sodium ion battery: at 0.1A g -1 Under the charge and discharge conditions, the voltage window was 0.01V-3V, and as a result, as shown in FIG. 9, the initial discharge capacity was 513.3mAh g -1 After 50 cycles of charge and discharge, the capacity of the material is still kept to be 398.6mAh g -1 Is a high reversible capacity of (a). In comparative example 1, the battery capacity was severely degraded, and in comparative example 2, the battery capacity was exhibited lower.
Characterization of rate capability as negative electrode of sodium ion battery: at 0.05, 0.1, 0.2, 0.5, 1, 2, 4A g -1 Under different current charge and discharge conditions, the voltage window was 0.01V-3V, and as a result, see fig. 10, the material prepared in example 1 had good capacity retention.
The HRTEM image for aberration correction shows that the result is shown in fig. 11, in which the dispersed bright spots are single atoms of Sb, indicating that Sb exists in the form of single atoms.
The N1s of XPS and the Sb3d and O1s graphs of Sb show that the results are shown in FIG. 12 and FIG. 15, and that single-atom Sb forms O with nitrogen and oxygen in a nitrogen and oxygen co-doped carbon sheet 2 -Sb-N 4 A key.
Example 2:
the difference from example 1 is that the antimony trichloride of this example (SbCl 3 ): dicyandiamide: the mass ratio of the trimesic acid is 0.05:2:0.2, and the other steps are the same as those of the example 1, so that the single-atom antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material is obtained.
Example 3:
the difference from example 1 is that the antimony trichloride of this example (SbCl 3 ): dicyandiamide: the mass ratio of the trimesic acid is 0.3:2:0.2, and the other steps are the same as those of the example 1, so that the single-atom antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material is obtained.
Example 4:
the difference from example 1 is that the antimony source of this example is antimony nitrate (Sb (NO 3 ) 3 ) The other steps were the same as in example 1 to obtain a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material.
Example 5:
the difference from example 1 is that the heating temperature of this example is 600 ℃ and the ultrasonic time is 50 minutes, and the other steps are the same as those of example 1, so as to obtain the monoatomic 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 this example is 700 ℃ and the ultrasonic time is 20 minutes, and the other steps are the same as those of example 1, so as to obtain the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
Example 7:
the difference from example 1 is that the heating rate of the tube furnace of this example is 10 ℃/min, and the other steps are the same as those of example 1, so as to obtain the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
Example 8:
the difference from example 1 is that the protective atmosphere of this example is argon (Ar), and the other steps are the same as in example 1, to obtain a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material.
Example 9:
the difference from example 1 is that the magnetic stirring time of this example is 12h, and the other steps are the same as those of example 1, so as to obtain the monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
Example 10:
the difference from example 1 is that the working time of the constant temperature electric oven of this example is 12h, and the other steps are the same as those of example 1, so as to obtain the monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
Fig. 13 is a schematic structural view of a monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to one embodiment of the disclosure.
As shown in fig. 13, the monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material comprises the following components.
A porous carbon sheet matrix material comprising a plurality of porous carbon sheets to form a layered material, the porous carbon sheets being intimately connected to each other. Wherein the carbon sheet may be graphite phase carbon nitride (g-C3N 4).
The plurality of monoatomic stibium forms an oxygen-antimony-nitrogen bond with nitrogen and oxygen and is combined in the porous carbon sheet matrix material. Monoatomic antimony forms O with nitrogen 2 -Sb-N 4 Bond, monoatomic antimony as O 2 -Sb-N 4 The bond-forming form is encapsulated in a porous carbon sheet matrix material. The single-atom stibium is uniformly embedded in the porous carbon sheet matrix material. Single elementThe bonds of the antimonic, nitrogen, oxygen and carbon are O-Sb-N-C. In the porous carbon sheet composite material modified by monoatomic antimony and co-doped by nitrogen and oxygen, the content of monoatomic antimony is lower than the content (molar content) of nitrogen element, and the two are in order of magnitude difference.
The monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material provided in fig. 13 can be obtained by the method for preparing the monoatomic antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material, and the composite material can be used as a manufacturing material of 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 substitution made under the spirit and principles of the present disclosure will fall within the scope of the present disclosure.
According to yet another aspect of the present disclosure, there is provided a battery anode material comprising the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material of any of the embodiments of the present disclosure.
According to the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material, monoatomic antimony is distributed in an atomic state in a porous carbon sheet matrix material to form the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material, when the monoatomic 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, potassium/sodium ion diffusion kinetics are enhanced, more alkali metal ion anchoring points are provided, and a strategy of monoatomic antimony modification and nitrogen and oxygen co-doping can generate more delocalized electrons, so that the conductivity is improved, and the electrochemical performance of the electrode material is improved. The application of the two-dimensional carbon material in the anode material of the potassium/sodium ion battery obviously improves the active site and the material utilization rate of the carbon material, and further improves the theoretical capacity of the two-dimensional carbon material in the anode material of the potassium/sodium ion battery. The application of the two-dimensional composite material in the anode material of the potassium/sodium ion battery not only improves the charge-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 monoatomic 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 of the present specification, reference to the terms "one embodiment/mode," "some embodiments/modes," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the present application. In this specification, the schematic representations of the above terms are not necessarily the same embodiments/modes or examples. 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/implementations or examples described in this specification and the features of the various embodiments/implementations or examples may be combined and combined by persons skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless explicitly defined otherwise.
It will be appreciated by those skilled in the art that the above-described 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 will be apparent to persons skilled in the art from the foregoing disclosure, and such variations or modifications are intended to be within the scope of the present disclosure.
Claims (13)
1. A monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material, comprising:
a porous carbon sheet matrix material comprising a plurality of porous carbon sheets to form a layered material, each of the porous carbon sheets being intimately connected; and
the single-atom antimony modification and nitrogen and oxygen co-doping structure is characterized in that the single-atom antimony forms an oxygen-antimony-nitrogen bond with nitrogen and oxygen atoms and is combined in the porous carbon sheet matrix material to form the single-atom antimony and nitrogen and oxygen co-doping structure;
wherein the monatomic antimony forms O with nitrogen atom and oxygen atom 2 -Sb-N 4 Bond of monoatomic antimony in O 2 -Sb-N 4 The bond-forming form is encapsulated in the porous carbon sheet matrix material;
the bond of the monatomic antimony, the nitrogen atom, the oxygen atom and the carbon is O-Sb-N-C.
2. The monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to claim 1, wherein a plurality of the monatomic antimony are uniformly embedded in the porous carbon sheet matrix material.
3. The monatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to claim 1, wherein the carbon sheet is amorphous carbon.
4. The monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to claim 1, wherein the porous carbon sheet has a length of 2 to 15 μm and a width of 2 to 15 μm.
5. The monatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to claim 1, wherein the molar content of monatomic antimony is lower than the molar content of nitrogen element and the two are orders of magnitude different.
6. The monatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to claim 5, wherein the ratio of the molar content of monatomic antimony to the molar content of nitrogen element is about 1:12.
7. a method for preparing a monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material, for preparing the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to claim 1, comprising:
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 which is named as Sb/C/N-1;
drying the mixed solution Sb/C/N-1 to obtain a solid matter which is denoted as Sb/C/N-2; and
and heating and carbonizing the solid Sb/C/N-2 in a protective atmosphere to obtain the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material.
8. The method for preparing a porous carbon sheet composite material modified by monoatomic antimony and co-doped with nitrogen and oxygen according to claim 7, wherein the carbon/oxygen source is a raw material comprising both carbon element and oxygen element.
9. The method for preparing the single-atom antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to claim 8, wherein the mass ratio of the antimony source, the nitrogen source and the carbon/oxygen source is (0.05-0.3) 2:0.2.
10. The method for preparing the single-atom antimony-modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to claim 7, wherein the continuous magnetic stirring time is 12-24 hours.
11. The method for preparing the monoatomic antimony modified and nitrogen and oxygen co-doped porous carbon sheet composite material according to claim 7, wherein the temperature of the drying treatment is 60-80 ℃; the drying treatment time is 12 to 24 hours; the heating temperature is 600 ℃ to 800 ℃; the heating rate of the heating is 5 ℃/min to 10 ℃/min.
12. A battery anode material comprising the monoatomic antimony-modified and nitrogen-oxygen co-doped porous carbon sheet composite material according to any one of claims 1 to 6.
13. A battery, characterized in that the battery anode 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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