CN114628668A - Nitrogen-doped carbon-supported FeP @ NC and preparation and application thereof - Google Patents
Nitrogen-doped carbon-supported FeP @ NC and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 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 20
- 229910052573 porcelain Inorganic materials 0.000 claims description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 12
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 230000008569 process Effects 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 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 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910000162 sodium phosphate 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
- 239000011261 inert gas Substances 0.000 claims 2
- 239000006183 anode active material Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
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- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract 5
- 239000000243 solution Substances 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- 239000000693 micelle Substances 0.000 description 5
- 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 4
- 230000008859 change Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
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- 239000003575 carbonaceous material Substances 0.000 description 1
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- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229920001690 polydopamine Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Images
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
- H01M4/58—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
- H01M4/5805—Phosphides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
Abstract
A nitrogen-doped carbon-supported FeP @ NC particle and a preparation method and application thereof are disclosed, wherein a coralliform FeP composite (FeP @ NC) with FeP nanoparticles anchored and dispersed on a nitrogen-doped three-dimensional carbon framework is synthesized by in-situ phosphorization/carbonization of polymer nanoparticles, firstly, a surfactant is used as a template and a carbon source, ethanol and water are used as solvents, dopamine hydrochloride (DA) is used as a nitrogen source and a carbon source of a precursor, an iron source and an organic ligand are sequentially added, and self-polymerization is carried out to form a coralliform precursor of the FeP @ NC composite; and then placing the synthesized precursor and the phosphorus source in two ceramic boats respectively, placing the ceramic boat with the phosphorus source at the upstream of the airflow of the tube furnace, placing the ceramic boat with the polymer particles at the downstream of the airflow of the tube furnace, enabling the Ar airflow to flow through the ceramic boat with the phosphorus source and then flow through the ceramic boat with the polymer particles, heating the tube furnace to 600-1200 ℃ from room temperature in Ar atmosphere, and calcining for a period of time to obtain FeP @ NC, wherein the FeP @ NC can shorten the transmission path of ions, realize rapid electron and ion transmission, improve the reaction rate, show higher electrochemical activity, and has better rate multiplying power performance and high multiplying power circulation stability.
Description
Technical Field
The invention belongs to the technical field of alkali metal batteries, and particularly relates to a sodium ion battery, a lithium ion battery and a potassium ion battery.
Background
Lithium ion batteries have been widely used in the fields of portable electronic devices, automobiles, and the like as one of the most important energy storage devices. However, due to the high cost of lithium and resource shortage on earth, the development of new lithium ion battery substitutes is imminent. Sodium ion batteries have attracted considerable attention because of the abundance of sodium sources and the low cost advantage. However, since the ionic radius of sodium ions is larger than that of lithium ions, a severe volume change occurs during repeated sodium ion insertion/extraction processes, showing a continuous decrease in reversible capacity and poor cycle stability. In addition, the larger radius of sodium ions (0.97nm), which is 55% larger than that of lithium ions, makes the rapid insertion/extraction of sodium ions in the host material more difficult. The development of novel electrode materials with stable microstructures, high reversible capacity and long cycle life is an urgent task for sodium ion batteries.
Transition Metal Phosphides (TMPs), e.g. FeP, CoP, Ni2P and Sn4P3And the like, which are widely concerned due to the characteristics of high theoretical capacity, abundant resources, environmental friendliness and the like. FeP has been proved to have good electrochemical performance when being used as a negative electrode material of a sodium ion battery, but poor rate performance and rapid cycle capacity fading are caused due to large volume change and poor diffusion kinetics in the discharging/charging process. To improve charge transferThe general method of kinetics consists essentially in determining τ ═ L2D (τ is the time of the diffusion process) increases the sodium diffusion coefficient (D) and decreases the diffusion length (L). In principle, reducing the feature size of TMPs can effectively reduce the diffusion length, while creating ion/electron high-velocity pathways through appropriate nanostructure engineering can enhance sodium ion diffusion and improve electron conductivity. The preparation of porous composite materials with unique microstructures has proven to be an effective method to further improve the electrochemical performance of electrode materials, not only providing additional free space to buffer volume changes, but also providing more active sites for sodium insertion/extraction. However, due to the lack of suitable synthesis methods, a method for the controlled preparation of transition metal phosphides with coral-like structures (nano-FeP particles anchored and dispersed on a nano-scale carbon substrate) has not been reported.
Disclosure of Invention
The invention aims to provide FeP @ NC taking nitrogen-doped carbon as a carrier and preparation and application thereof.
The technical scheme adopted by the invention is as follows:
through in-situ phosphorization/carbonization of the polymer nanoparticles, coral-like FeP composites (FeP @ NC) with FeP nanoparticles anchored and dispersed on a nitrogen-doped three-dimensional carbon framework are synthesized.
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 a precursor of a coralline FeP @ NC compound; and then placing the synthesized precursor and the phosphorus source in two porcelain boats respectively, placing the porcelain boat with the phosphorus source at the upstream of the airflow of the tube furnace, placing the porcelain boat with the polymer particles at the downstream of the airflow of the tube furnace, enabling the Ar airflow to flow through the porcelain boat with the phosphorus source and then flow through the porcelain boat with the polymer particles, heating the tube furnace from room temperature to 600-1200 ℃ in Ar atmosphere, and calcining for a period of time to obtain FeP @ NC.
Preferably, in the step (1), the alcohol is ethanol, and the volume ratio of the ethanol to the water is 1: (0.5 to 2)
Preferably, the surfactant is other surfactants such as addition polymer (F127) of polypropylene glycol and ethylene oxide, polyvinylpyrrolidone (PVP), sodium hexadecyl sulfonate, and the like.
Preferably, the surfactant concentration is 5-15 (mg/ml).
Preferably, the concentration of the dopamine hydrochloride is 0-15 (mg/ml).
Preferably, the iron source is Fe (NO)3)3·9H2O，Fe(NO3)3，FeCl3，Fe2(SO4)3，FeSO4，Fe(NO3)2，FeCl2One or more of them.
Preferably, the organic ligand is one or more of 1,3, 5-benzene tricarboxylic acid, terephthalic acid, 1,3, 5-trimethylbenzene and dimethyl imidazole.
Preferably, the organic ligand is 1,3, 5-benzenetricarboxylic acid, and Fe (NO)3)3·9H2The preferred molar weight ratio of O is 2: 1-1: 2.
Preferably, the phosphorus source is red phosphorus, white phosphorus, NaH2PO4Or Na2HPO4。
Preferably, the mass ratio of the polymer particles to the phosphorus source red phosphorus is 1 (1-4).
Preferably, the heating rate is 0.1-5 ℃ min-1。
Preferably, the calcination temperature is 600-1200 ℃.
Preferably, the calcination time is 2-12 h.
The invention also aims to provide application of the nitrogen-doped carbon supported FeP @ NC prepared by the method in an alkali metal ion battery.
Preferably, FeP @ NC with nitrogen-doped carbon as a carrier is used as an alkali metal ion battery negative electrode active material.
Preferably, the alkali metal ion battery is a sodium ion battery, a lithium ion battery, or a potassium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the FeP @ NC composite material anchors and disperses FeP nano particles on a nano-scale carbon substrate, the size of FeP is reduced to about 10nm (average diameter), and the coral-like structure of the FeP @ NC composite material can shorten the transmission path of ions, realize rapid electron and ion transmission, improve the reaction rate and show higher electrochemical activity.
2. The FeP @ NC composite material provided by the invention has a three-dimensional carbon skeleton with a highly porous structure, can promote sodium ion diffusion and buffer volume change, can prevent FeP nanoparticles from aggregating during circulation, and has good rate performance and high rate circulation stability.
3. The FeP @ NC composite material has the advantages that the price of the most widely applied hard carbon material in the sodium ion battery is high, the contents of Fe element and P element in the earth crust are high, the resource is rich, the price is low, the theoretical specific capacity can be improved, and the cost can be reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention, reference will now be made briefly to the accompanying drawings, to which embodiments relate.
FIG. 1: XRD patterns for FeP @ NC synthesized in example 1, FeP @ NC synthesized in example 4, and FeP @ NC synthesized in example 5.
FIG. 2: a SEM picture of FeP @ NC synthesized in example 1; b and c: TEM images of FeP @ NC synthesized in example 1 at different magnifications; d: SEM picture of FeP @ NC synthesized in example 4; e and f: TEM images of FeP @ NC synthesized in example 4 at different magnifications; g: SEM image of synthetic FeP @ NC of example 5; e and f: TEM images of FeP @ NC synthesized in example 5 at different magnifications.
FIG. 3: magnification representation of FeP @ NC synthesized in example 1, FeP @ NC synthesized in example 4, and FeP @ NC synthesized in example 5.
FIG. 4: FeP @ NC synthesized in example 1 at 10A. g-1Long cycle 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 nanoparticles:
the specific synthetic process comprises the following steps: 1.0g of an addition polymer of polypropylene glycol and ethylene oxide (F127) and 1.0g of dopamine hydrochloride (DA) were dissolved in 100mL of a mixed solution of water and ethanol (volume ratio 1: 1), and vigorously stirred at room temperature to obtain a clear solution; 5.8083g of Fe (NO) are then added3)3·9H2O was added to the above solution at a stirring rate of 500rpm to form a clear solution; after stirring for 30 minutes, 3.0212g of 1,3, 5-benzenetricarboxylic acid was added to the above mixed solution, and after continuously stirring and reacting for 30 minutes, the mixture was centrifuged to obtain a separated product, and then the separated product was washed 3 times with a mixed solution of water and ethanol (volume ratio: 1) and dried to obtain polymer particles.
2. Synthesis of nitrogen-doped coralliform FeP @ NC composite material:
respectively placing the polymer particles synthesized in the step (1) and red phosphorus (the mass ratio is 1: 2) in two porcelain boats, placing the porcelain boat containing the red phosphorus at the upstream of the airflow of the tube furnace, placing the porcelain boat containing the polymer particles at the downstream of the airflow of the tube furnace, introducing Ar airflow to pass through the porcelain boat containing the red phosphorus and then pass through the porcelain boat containing the polymer particles, and then carrying out treatment at 1 ℃ for min in Ar atmosphere-1The FeP @ NC is obtained by heating the tube furnace from room temperature to 600 ℃ and calcining for 6 hours.
Through detection, the mass content of N in the porous carrier NC is 0.97%, and the carrier NC is a cluster with the particle size of 1-3 μm, which is formed by aggregating particles with the particle size of 100-500nm and is called a coral-shaped cluster;
the active ingredient FeP is distributed on the inner and outer surfaces of the porous carrier NC, and is particles with the particle size of 4-20 nm.
3. Performance testing of nitrogen-doped coralliform FeP @ NC composites:
preparing slurry by using the FeP @ NC prepared by the method as an electrode active substance, super P as a conductive agent and polyvinylidene fluoride (PVDF) as a binder, wherein the composition ratio of the slurry to the PVDF 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 is about 1mg cm-2. In a diameter of 1.6mmSodium sheet as counter electrode, glass fiber membrane as diaphragm, 1M NaPF6And DGME is used as an electrolyte, and the sodium | FeP @ NC half cell is assembled. At 0.1A g-1(vs FeP @ 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 10A g-1A long cycle test of a large current is performed at a current density of (1).
Examples 2 to 18:
the same nitrogen-doped coralliform FeP @ NC composite material as that of example 1 was prepared and assembled into a battery, except that the concentration of F127, the concentration of dopamine hydrochloride, the kind of metal salt, the molar ratio of metal salt to 1,3, 5-benzenetricarboxylic acid, the phosphorus source, the temperature increase rate, the calcination temperature, the calcination time and the mass content of N were used, the data are shown in Table 1, and the data of the prepared sodium ion battery are shown in Table 3.
Comparative examples 1 to 7:
the same nitrogen-doped coralliform FeP @ NC composite material as that of example 1 was prepared, assembled into a battery, and tested for performance, except for the type of organic ligand, the rate of temperature rise, and the order of materials, and the data for the performance test of the sodium ion battery prepared are shown in Table 2 and Table 3, respectively.
TABLE 1 preparation Process parameters for examples 1-18
TABLE 2 Process parameters for comparative examples 1-7
TABLE 3 results of Performance test of examples 1 to 18 and comparative examples 1 to 6
FeP @ NC synthesized in example 1 exhibited the best electrochemical activity when electrochemically tested against various amounts of dopamine hydrochloride (DA) synthesized FeP @ NC. The prepared composite material also shows higher rate performance under the condition of containing 48.8 percent of carbon, and the rate performance is 20 A.g-1Has a current density of 176.5mAh g-1Specific capacity of 10 A.g-1The current density of the current is 10000 cycles and then 89mAh g-1The specific capacity of the composite material has better rate performance and large-current long-cycle performance.
Utilizing the characteristic that both ends of F127 are respectively provided with a hydrophilic group and a hydrophobic group, the middle part is a long chain, the hydrophilic group has electronegativity, and is combined with ferric iron, so that ferric iron ions 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 can be self-polymerized to form polydopamine and has certain viscosity, so that a certain nitrogen element can be doped; meanwhile, we also find that when the dosage of dopamine hydrochloride is changed, the proportion of FeP is changed little, so that FeP does not participate in the polymerization process of the whole reaction and mainly serves as a nitrogen source. Fe (NO)3)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 ion may be coordinated with the micelle by entering the micelleThe particles are compounded, so that the size of the particles is effectively controlled.
According to the experimental results, the change of the dopamine hydrochloride amount does not greatly cause the proportion of FeP in the whole compound, mainly serves as a nitrogen source, and the preferable concentration of the dopamine hydrochloride is 0-15 (mg/ml).
From the experimental results, it can be seen that the proportion of FeP in the final complex is mainly determined by the amount of ferric ion, and the addition of excessive ferric salt or ligand does not greatly affect the experimental results. Preferred ligands in the present invention are 1,3, 5-benzenetricarboxylic acid, and Fe (NO)3)3·9H2The preferred molar weight ratio of O is 2: 1-1: 2.
When 1,3, 5-benzene tricarboxylic acid is replaced by 1,3, 5-trimethylbenzene, micelle-shaped particles can be formed firstly, 1,3, 5-trimethylbenzene can also act with hydrophobic ends of a surfactant through van der waals force to promote the assembly of micelles, but because iron ions in the micelle particles lack organic ligands, the size of the polymer particles cannot be well controlled, so that the polymer particles are large and the performance is slightly poor.
When 1,3, 5-trimethylbenzene is added to the solution first or Fe (NO) is added first3)3·9H2When O is dissolved together with F127 and dopamine hydrochloride, uniform micelle-shaped particles cannot be formed first, the average particle size of the particles is larger, and the overall performance is poorer. 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 FeP particles formed are enlarged, so that the performance is poor.
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, particles are enlarged finally, and the performance is deteriorated, wherein the preferable heating rate is 0.1-5 ℃ for min-1。
Because the carbonization temperature of the dopamine hydrochloride is influenced by the surfactant, the organic ligand and the carbonization temperature of the dopamine hydrochloride in the colloidal particles and needs to be higher than 600 ℃, when the calcination temperature is increased, the graphitization degree of the calcined carbon and the content of oxygen-containing groups on the surface of the calcined carbon are only influenced, and the content of FeP is not obviously influenced, so that the overall performance is basically unchanged. The preferable calcination temperature in the invention is 600-1200 ℃.
When the time for calcination is too long, the FeP particles may be agglomerated and the overall properties may be deteriorated. The preferable calcination time in the invention is 2-12 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. A preparation method of FeP @ NC with nitrogen-doped carbon as a carrier is characterized by comprising the following steps:
(1) sequentially adding an iron source and an organic ligand into a surfactant serving as a template and a carbon source, an alcohol and water serving as solvents and dopamine hydrochloride serving as a nitrogen source and a carbon source of a precursor, and carrying out self-polymerization to form a precursor of the FeP @ NC compound;
(2) and (2) respectively placing the precursor and the phosphorus source synthesized in the step (1) into two porcelain boats, then placing the porcelain boat with the phosphorus source at the upstream of the airflow of the tube furnace, placing the porcelain boat with the precursor at the downstream of the airflow of the tube furnace, enabling the inert gas to flow through the porcelain boat with the phosphorus source and then flow through the porcelain boat with the precursor, heating the tube furnace to 600-1200 ℃ from room temperature, and calcining for a period of time to obtain FeP @ NC.
2. The method according to claim 1, wherein the alcohol in the step (1) is ethanol, and the volume ratio of ethanol to 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)2And FeCl2One or more than two of them.
5. The process according to claim 4, wherein the organic ligand in the step (1) is one or more selected from the group consisting of 1,3, 5-benzenetricarboxylic acid, terephthalic acid, 1,3, 5-trimethylbenzene 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 claim 5, wherein the phosphorus source in the step (2) is red phosphorus, white phosphorus, NaH2PO4And Na2HPO4One or more than two of them; the mass ratio of the precursor to the phosphorus source is 1 (1-4).
7. The method according to claim 6, wherein the heating rate in the step (2) is 0.1 to 5 ℃ for min-1(ii) a The calcination time is 2-12 h; the inert gas is Ar.
8. FeP @ NC particles with nitrogen-doped carbon as a carrier are characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. Use of the nitrogen-doped carbon supported FeP @ NC particle of claim 8 in an alkali metal ion battery.
10. The use of claim 9, characterized in that the nitrogen-doped carbon supported FeP @ NC particles are used as an alkali metal ion battery anode 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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