CN114628669A - Carbon-carrier nitrogen-doped Fe2O3@ NC and preparation and application thereof - Google Patents
Carbon-carrier nitrogen-doped Fe2O3@ NC and preparation and application thereof Download PDFInfo
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 17
- 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 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- -1 ferric iron ions Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses carbon carrier nitrogen-doped Fe2O3The patent refers to the field of 'processes or means for the direct conversion of chemical energy into electrical energy'. Firstly, taking a surfactant as a template and a carbon source, taking ethanol and water as solvents, taking dopamine hydrochloride (DA) as a nitrogen source and a carbon source of a precursor, sequentially adding an iron source and an organic ligand, and carrying out self-polymerization to form Fe2O3A precursor of @ NC complex; then heating the synthesized precursor to 600-800 ℃ in Ar atmosphere, calcining for a period of time, cooling to room temperature, and placing in air for a period of time to obtain Fe2O3@ NC. The carbon carrier prepared by the invention is nitrogen-doped Fe2O3The @ NC particle is capable of inhibiting Fe2O3The growth of the nano particles shortens the transmission path of ions, improves the reaction rate, shows higher electrochemical activity, and has better rate performance and high rate cycling stability.
Description
Technical Field
The invention belongs to the technical field of alkali metal batteries, and particularly relates to carbon carrier nitrogen-doped Fe synthesized by a natural oxidation method2O3@ NC and its preparation and use.
Background
Recently, sodium ion batteries have attracted extensive attention of various scholars as potential substitutes for lithium ion batteries in large-scale energy storage systems, mainly due to the abundant resource and low cost of sodium. Sodium (Na) belongs to the same main group as lithium (Li) in the periodic table of elements, and exhibits similar physicochemical properties as lithium, which is advantageous for the development of sodium ion battery technology. However, most electrode materials of lithium ion batteries have difficulty carrying sodium ions because the radius of sodium ions (about 0.102nm) is greater than the radius of lithium ions (about 0.076 nm). Therefore, the development of sodium ion batteries has not left the search for suitable host materials to accommodate the larger Na+. Over the past few years, a number of positive and negative electrode materials have been investigated for use in sodium ion batteries and have evolved significantly, such as prussian blue-based materials, sodium layered oxides and phosphate materials. However, the small distance between graphite layers (0.34nm) is not favorable for sodium ion intercalation in commercial graphite anodes, and therefore, the development of high-performance anode materials is currently a major challenge in the research process of sodium ion batteries.
Transition metal oxides have received much attention due to their high theoretical capacity, abundant resources and environmental friendliness. In which Fe2O3Due to the high theoretical capacity (1007mA h g)-1) Rich resources, low cost and environmental friendliness, and is considered to be a promising candidate anode material in the sodium-ion battery. However, Fe2O3Subject to the inherent low conductivity and volume of the sodium ion insertion/extraction processThe variation is greatly hindered. In addition, since the radius of sodium ion is large, Fe2O3The volume change of the negative electrode material of the sodium ion battery is larger than that of the lithium ion battery. The large volume change can lead to pulverization of active material particles, loss of electrical contact between the active material and the electrode frame, and continued growth of a very thick Solid Electrolyte Interface (SEI) film, all of which can lead to rapid capacity fade during cycling.
In order to solve the above problems, although the prior art has adopted the method including manufacturing Fe having different nanostructures2O3Or by addition of Fe2O3The nanoparticles are dispersed into different carbon matrices, such as carbon nanotubes, carbon nanofibers and graphene. However, most of the reported Fe for sodium ion batteries2O3Is based on Fe2O3Constructed by reacting Fe2O3Relevant research on the anchoring and dispersing of the nanoparticles in the nitrogen-doped three-dimensional carbon skeleton for developing a high-performance anode material is not reported.
Disclosure of Invention
In view of the above, the invention aims to provide carbon-carrier nitrogen-doped Fe2O3Preparation method and application of @ NC.
The invention is realized by the following modes:
fe was synthesized by in-situ carbonization of the polymer, followed by natural oxidation in air2O3Fe with nanoparticles anchored and dispersed in nitrogen-doped three-dimensional carbon skeleton2O3Composite (Fe)2O3@NC)。
Firstly, taking a surfactant as a template and a carbon source, taking ethanol and water as solvents, taking dopamine hydrochloride (DA) as a nitrogen source and a carbon source of a precursor, sequentially adding an iron source and an organic ligand, and carrying out self-polymerization to form Fe2O3A precursor of @ NC complex; then heating the synthesized precursor to 600-800 ℃ in Ar atmosphere, calcining for a period of time, cooling to room temperature, and placing in air for a period of time to obtain Fe2O3@NC。
Further, the surfactant is an addition polymer (F127) of polypropylene glycol and ethylene oxide, polyvinylpyrrolidone (PVP) or hexadecylsulfonic acid.
Further, the concentration of the surfactant is 5-15 (mg/ml).
Further, the concentration of the dopamine hydrochloride is 0-15 (mg/ml).
Further, the iron source is Fe (NO)3)3·9H2O、Fe(NO3)3、FeCl3、Fe2(SO4)3、FeSO4，Fe(NO3)2、FeCl2One or more than two of them.
Further, the organic ligand is one or more than two of 1,3, 5-benzene tricarboxylic acid, terephthalic acid and dimethyl imidazole.
Further, the organic ligand is 1,3, 5-benzene tricarboxylic acid and Fe (NO)3)3·9H2The preferred molar weight ratio of O is 2: 1-1: 2.
Further, the heating rate is 0.1-3 ℃ min-1。
Further, the calcining temperature is 600-800 ℃.
Furthermore, the calcination time is 2-6 h.
Another object of the present invention is to provide a carbon carrier nitrogen-doped Fe prepared by the above method2O3Application of @ NC in alkali metal ion batteries.
Further, the carbon carrier is nitrogen-doped Fe2O3@ NC as an alkali metal ion battery negative active material.
Further, the alkali metal ion battery is a sodium ion battery, a lithium ion battery and a potassium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. most of the currently available Fe2O3The size of the composite material is relatively large, while the Fe of the invention2O3The nanoparticles anchored and dispersed on a carbon substrate of several hundred nanometers can inhibit Fe2O3Growth of nanoparticles to shorten ion transport pathThe reaction rate is improved, and the electrochemical activity is higher.
2. The hard carbon material with the widest application in the sodium ion battery has low specific capacity and poor multiplying power and cycle performance, and the carbon carrier of the invention is Fe doped with nitrogen2O3The rate capability and the cycling stability of the @ NC composite material are both obviously improved.
3. The method of the invention obtains Fe/C compound by stirring and calcining at normal temperature, and then obtains Fe by natural oxidation in air2O3The @ NC compound has simple process and easy operation, and can realize large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
FIG. 1: fe synthesized in examples 1 and 42O3XRD pattern of @ NC.
FIG. 2: example 1 synthesized Fe2O3Scanning electron microscope image of @ NC.
FIG. 3: fe synthesized in examples 1 and 42O3Magnification expression graph of @ NC.
FIG. 4: example 1 synthesized Fe2O3@ NC at 5 A.g-1Cycling plot at current density.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
Example 1
1) Synthesis of Polymer particles:
1.0g of an addition polymer of polypropylene glycol and ethylene oxide (F127) and 1.0g of DA (dopamine hydrochloride) were dissolved in 100mL of ethanol water having a volume concentration of 50%, and stirred at room temperature to obtain a clear solution. 5.8083g of Fe (NO)3)3·9H2O and 3.0212g of 1,3, 5-benzenetricarboxylic acid are sequentially added to the mixture, the mixture is continuously stirred and reacted for 30 minutes, and after centrifugation, a separated substance is obtained, and after washing 3 times with ethanol water with the volume concentration of 50%, and drying is carried out, the polymer can be obtained.
2.Fe2O3Synthesis of @ NC composite Material (Fe)2O3@NC)：
The synthesized polymer was heated at 1 ℃ for min in Ar atmosphere-1Heating to 600 ℃ at a heating rate, calcining for 3h, cooling to room temperature, taking out, placing in air, and standing for 30 min to obtain Fe2O3@NC。
Through detection, the mass content of N in the polymer carrier NC is 1.06%, and the particle size of the carrier NC is 100-300 nm;
active ingredient Fe2O3Is distributed on the inner and outer surfaces of the porous carrier NC, and is particles with the particle size of 10-30 nm.
3.Fe2O3Testing the performance of the @ NC composite material:
fe prepared by the above method2O3The material is prepared by mixing @ NC as an electrode active substance, super P as a conductive agent and polyvinylidene fluoride (PVDF) as a binder, and the composition ratio of the material to the binder is 8:1: 1. And (3) taking copper foil as a current collector, coating an electrode with the thickness of 80 microns by blade coating, and drying at 60 ℃. The electrode supporting amount at this time was about 1mg cm-2. Using a sodium sheet with a diameter of 1.6mm as a counter electrode, a glass fiber membrane as a diaphragm, and 1M NaPF6Is an electrolyte, DGME is used as an electrolyte and is assembled into sodium | Fe2O3@ NC half cell. At 0.1A g-1(Fe2O3@NC)，0.2A g-1，0.5A g-1，1A g-1，2A g-1，5A g-1，10A g-1And 20A g-1The rate capability was tested by charging and discharging at 5A g-1The current density of (2) was measured.
Examples 2 to 15:
fe with the same carbon support nitrogen doping as in example 12O3Preparation process of @ NC composite material, battery assembling process and performance testing processExcept that the concentration of F127, the concentration of dopamine hydrochloride, the types of metal salts, the heating rate, the calcination temperature and the calcination time are shown in the table 1, and the performance test data of the prepared sodium-ion battery is shown in the table 3.
Comparative examples 1 to 5:
fe with the same carbon support nitrogen doping as in example 12O3The differences between the preparation process of the @ NC composite material and the battery assembling process and the performance testing process are the types of organic ligands, the heating rate and the material sequence, the related data are shown in table 2, and the performance testing data of the prepared sodium-ion battery are shown in table 3.
TABLE 1 preparation Process parameters for examples 1-18
TABLE 2 Process parameters for comparative examples 1-5
TABLE 3 results of Performance test of examples 1 to 15 and comparative examples 1 to 5
Fe synthesized when different amounts of dopamine hydrochloride (DA) are added2O3Example 1 Fe synthesized when electrochemical testing was carried out at @ NC2O3@ NC shows the best electrochemical activity. The prepared composite material is 20 A.g-1Has a current density of 122.3mAh g-1Specific capacity of 5 A.g-1After 5000 cycles of circulation at the current density, 63.1mAh g is also obtained-1The specific capacity of the high-power-factor lithium ion battery has good rate capability and high-current long-cycle stability.
By utilizing the characteristic that both ends of F127 are respectively provided with hydrophilic groups and hydrophobic groups, and the middle part is long-chain,the hydrophilic group shows electronegativity, is combined with ferric iron, and enables ferric iron ions to form micelle-shaped particles under the stirring condition; the micelle-like structure of the long chain and the hydrophobic group at the other end can prevent combination with other micelles, avoid agglomeration and has higher dispersity. The dopamine hydrochloride is mainly used as a nitrogen source, and a certain nitrogen element can be doped into the dopamine hydrochloride because the dopamine hydrochloride can be self-polymerized to form polydopamine and has certain viscosity; also, we have found that when the amount of dopamine hydrochloride is varied, Fe is present2O3The ratio of (A) is so small that it does not participate in the polymerization process of the whole reaction, mainly as a nitrogen source.
Fe(NO3)3·9H2O is used as an iron source, firstly forms micelle-like particles with F127 through electrostatic interaction, and then carries out coordination polymerization with 1,3, 5-benzene tricarboxylic acid. On one hand, 1,3, 5-benzene tricarboxylic acid can promote the assembly of the micelle through the action of van der Waals force and the hydrophobic end of the surfactant; on the other hand, the metal ions can enter the micelle to perform coordination and recombination with the metal ions, so that the size of the particles is effectively controlled.
From the experimental results, it can be seen that the change of the dosage of dopamine hydrochloride can affect Fe2O3Thereby affecting Fe2O3The preferable concentration of the dopamine hydrochloride in the invention is 0-15 (mg/ml); the preferable surfactant in the invention is F127, polyvinylpyrrolidone or sodium hexadecylsulfonate, and the preferable concentration is 5-15 (mg/ml); the iron source in the present invention is Fe (NO)3)3·9H2O、Fe(NO3)3、FeCl3、Fe2(SO4)3、FeSO4，Fe(NO3)2、FeCl2One or more than two of them.
The preferred ligand in the present invention is 1,3, 5-benzenetricarboxylic acid. And also can be one or more of terephthalic acid and dimethyl imidazole. From the experimental results, it can be seen that Fe is in the final composite2O3The ratio of (a) to (b) is mainly dependent on the molar amount of ferric ion.
When 1,3, 5-benzene tricarboxylic acid is replaced by terephthalic acid, the organic framework formed by the terephthalic acid and iron ions is enlarged due to the symmetrical structure of the terephthalic acid, and the formed Fe2O3The particles become larger and thus the performance is slightly inferior.
Because the formed colloidal particles are obtained by combining weak bond force, the structure of the colloidal particles can be damaged when the temperature rising rate is too high, the agglomeration of elementary substance iron is caused, and further Fe is caused2O3The particle size of (2) becomes large and the performance becomes poor, and the preferable heating rate in the invention is 0.1-3 ℃ min-1。
Due to the influence of the carbonization temperature of the surfactant, the organic ligand and the dopamine hydrochloride in the colloidal particles, the carbonization temperature needs to be higher than 600 ℃, when the calcination temperature is too high (such as 1200 ℃), the graphitization degree of the calcined carbon and the number of oxygen-containing groups on the surface of the calcined carbon are influenced, and Fe and C compounds are generated, so that the natural oxidation effect and the Fe are influenced2O3The specific gravity of the composite can further influence the overall performance of the material, and the preferred calcining temperature in the invention is 600-800 ℃.
When the calcination time is too long (such as 12 hours), the agglomeration of elementary iron particles may occur, and the natural oxidation effect and Fe are affected2O3The composite material occupies a specific gravity, so that the overall performance is deteriorated, and the calcination time is preferably 2-6 h.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Carbon-carrier nitrogen-doped Fe2O3A preparation method of @ NC, characterized in that the bagThe method comprises the following steps:
(1) taking a surfactant as a template and a carbon source, taking alcohol and water as solvents, taking dopamine hydrochloride as a nitrogen source and a carbon source of a precursor, sequentially adding an iron source and an organic ligand, and carrying out self-polymerization to form Fe2O3A precursor of @ NC complex;
(2) heating the precursor synthesized in the step (1) to 600-800 ℃ in an inert gas atmosphere, calcining for 2-6 h, cooling to room temperature, and standing in air for a period of time to obtain Fe2O3@NC。
2. The preparation method according to claim 1, wherein the alcohol in the step (1) is ethanol, and the volume ratio of the ethanol to the water is 1 (0.5-2).
3. The method according to claim 2, wherein the surfactant in the step (1) is an addition polymer of polypropylene glycol and ethylene oxide, polyvinylpyrrolidone or sodium hexadecyl sulfonate; the concentration of the surfactant is 5-15 (mg/ml); the concentration of the dopamine hydrochloride is 0-15 (mg/ml).
4. The method according to claim 3, wherein the iron source in the step (1) is Fe (NO)3)3·9H2O、Fe(NO3)3、FeCl3、Fe2(SO4)3、FeSO4，Fe(NO3)2、FeCl2One or more than two of them.
5. The method according to claim 4, wherein the organic ligand in step (1) is one or more selected from the group consisting of 1,3, 5-benzenetricarboxylic acid, terephthalic acid and dimethylimidazole; the molar weight ratio of the organic ligand to Fe in the iron source is 2: 1-1: 2.
6. The method according to any one of claims 1 to 5, wherein the heating rate in the step (2) is 0.1 to 3 ℃ for min-1(ii) a Inert gasThe body is Ar.
7. The method according to claim 6, wherein the standing time in the air in the step (2) is 20 to 40 min.
8. Carbon-carrier nitrogen-doped Fe2O3The @ NC particle is characterized by being produced by the production method according to any one of claims 1 to 7.
9. The carbon carrier nitrogen-doped Fe of claim 82O3Use of @ NC particles in alkali metal ion batteries.
10. Use according to claim 9, characterized in that the carbon support is nitrogen-doped Fe2O3The @ NC granules are used as an alkali metal ion battery negative electrode active material; the alkali metal ion battery is a sodium ion battery, a lithium ion battery or a potassium ion battery.
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