CN114628668B - FeP@NC taking nitrogen doped carbon as carrier and preparation and application thereof - Google Patents

FeP@NC taking nitrogen doped carbon as carrier and preparation and application thereof Download PDF

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CN114628668B
CN114628668B CN202011455750.XA CN202011455750A CN114628668B CN 114628668 B CN114628668 B CN 114628668B CN 202011455750 A CN202011455750 A CN 202011455750A CN 114628668 B CN114628668 B CN 114628668B
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porcelain boat
ion battery
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CN114628668A (en
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李先锋
王灿沛
郑琼
张华民
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

The FeP@NC particle takes nitrogen doped carbon as a carrier, and a preparation method and application thereof, wherein coralloid FeP composite (FeP@NC) which is formed by anchoring and dispersing FeP nano particles on a nitrogen doped three-dimensional carbon frame is synthesized by in-situ phosphating/carbonizing polymer nano particles; then placing the synthesized precursor and phosphorus source in two porcelain boats respectively, placing the porcelain boat with the phosphorus source at the air flow upstream of a tube furnace, placing the porcelain boat with polymer particles at the air flow downstream of the tube furnace, enabling Ar air flow to flow through the porcelain boat with the polymer particles after passing through the porcelain boat with the phosphorus source, heating the tube furnace from room temperature to 600-1200 ℃ in Ar atmosphere and calcining for a period of time to obtain FeP@NC, which can shorten the ion transmission path, realize rapid electron and ion transmission, improve the reaction rate, show higher electrochemical activity, and have better multiplying power performance and high multiplying power circulation stability.

Description

FeP@NC taking nitrogen doped carbon as carrier and preparation and application thereof
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 on earth and resource shortages, the development of new lithium ion battery alternatives is urgent. Sodium ion batteries have attracted considerable attention due to the abundance and low cost advantages of sodium sources. However, since the ionic radius of sodium ions is larger than that of lithium ions, a serious volume change occurs during repeated sodium ion insertion/extraction, exhibiting a continuous decrease in reversible capacity and poor cycle stability. In addition, the radius of sodium ions is larger (0.97 nm) than that of lithium ions by 55%, so that rapid insertion/extraction of sodium ions in the host material is more difficult. The development of new electrode materials with stable microstructure, high reversible capacity and long cycle life is urgent for sodium ion batteries.
Transition Metal Phosphides (TMPs), e.g. FeP, coP, ni 2 P and Sn 4 P 3 And the like, the characteristics of high theoretical capacity, abundant resources, environmental friendliness and the like are paid attention to. FeP has been demonstrated to have good electrochemical performance as a negative electrode material for sodium ion batteries, but has poor rate capability and rapid cycling capacity decay due to large volume changes and poor diffusion kinetics during discharge/charge. Whereas the general method of improving charge transfer kinetics consists essentially of the following steps according to τ=l 2 D (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 constructing ion/electron high-speed paths through appropriate nanostructure engineering can enhance the diffusion of sodium ions and increase the electron conductivity. The preparation of porous composites with unique microstructures has proven to be an effective method to further enhance the electrochemical performance of electrode materials, not only to provide additional free space to buffer volume changes, but also to provide more active sites for sodium intercalation/extraction. However, due to the lack of suitable synthetic methods, controllable preparation methods for transition metal phosphides of coral-like structure (nano-FeP particles anchored dispersed on nano-scale carbon substrates) have 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 invention adopts the technical scheme that:
by in situ phosphating/carbonizing the polymer nanoparticles, coral-shaped FeP composite (FeP@NC) in which FeP nanoparticles are anchored and dispersed on a nitrogen-doped three-dimensional carbon frame is synthesized.
Firstly, taking a surfactant as a template and a carbon source, 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 performing self-polymerization to form a precursor of a coralloid 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 air flow upstream of a tube furnace, placing the porcelain boat with the polymer particles at the air flow downstream of the tube furnace, enabling Ar air flow to flow through the porcelain boat with the phosphorus source and then through the porcelain 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.
Preferably, in the step (1), the alcohol is ethanol, and the volume ratio of ethanol to water is 1: (0.5-2)
Preferably, the surfactant is an addition polymer of polypropylene glycol and ethylene oxide (F127), polyvinylpyrrolidone (PVP), sodium cetyl sulfonate, or other surfactant.
Preferably, the surfactant concentration is 5 to 15 (mg/ml).
Preferably, the concentration of dopamine hydrochloride is 0-15 (mg/ml).
Preferably, the iron source is Fe (NO 3 ) 3 ·9H 2 O，Fe(NO 3 ) 3 ，FeCl 3 ，Fe 2 (SO 4 ) 3 ，FeSO 4 ，Fe(NO 3 ) 2 ，FeCl 2 One 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-trimellitic acid, with Fe (NO) 3 ) 3 ·9H 2 The preferred molar ratio of O is 2: 1-1:2.
Preferably, the phosphorus source is red phosphorus, white phosphorus, naH 2 PO 4 Or Na (or) 2 HPO 4 。
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 ℃ for min -1 。
Preferably, the calcination temperature is 600 to 1200 ℃.
Preferably, the calcination time is 2 to 12 hours.
The invention also aims to provide the application of the nitrogen-doped carbon prepared by the method serving as a carrier in the FeP@NC alkali metal ion battery.
Preferably, the FeP@NC taking the nitrogen-doped carbon as a carrier is used as an alkali metal ion battery anode active material.
Preferably, 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. according to the FeP@NC composite material disclosed by the invention, feP nano particles are anchored and dispersed on a nanoscale carbon substrate, the size of FeP is reduced to about 10nm (average diameter), and the coralline-like structure of the FeP@NC composite material can not only shorten the ion transmission path, realize rapid electron and ion transmission, but also improve the reaction rate, and shows 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 being aggregated during circulation, and has good multiplying power performance and high multiplying power circulation stability.
3. The hard carbon material with the widest application in the sodium ion battery has higher price, the Fe element and the P element have higher content in the crust, the resources are rich, and the FeP@NC composite material with lower price can not only improve the theoretical specific capacity, but also reduce the cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described.
Fig. 1: XRD patterns of fep@nc synthesized in example 1, fep@nc synthesized in example 4 and fep@nc synthesized in example 5.
Fig. 2: a, SEM image of FeP@NC synthesized in example 1; b and c: TEM images of FeP@NC synthesized in example 1 at different magnifications; d: SEM image of FeP@NC synthesized in example 4; e and f: TEM images of FeP@NC synthesized in embodiment 4 at different magnifications; g: SEM images of fep@nc synthesized in example 5; e and f: TEM image of FeP@NC synthesized in example 5 at different magnifications.
Fig. 3: the magnification performance graphs of FeP@NC synthesized in example 1, feP@NC synthesized in example 4 and FeP@NC synthesized in example 5.
Fig. 4: example 1 FeP@NC synthesized at 10 A.g -1 Long cycle diagram at current density.
Detailed Description
The following detailed description of the invention is provided in connection with examples, but the implementation of the invention is not limited thereto, and it is obvious that the examples described below are only some examples of the invention, and that it is within the scope of protection of the invention to those skilled in the art to obtain other similar examples without inventive faculty.
Example 1
1. Synthesis of polymer nanoparticles:
the specific synthesis 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 3 ) 3 ·9H 2 O 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-benzene tricarboxylic acid is added into the mixed solution, after continuous stirring reaction for 30 minutes, the mixture is centrifuged to obtain a separated product, and then the separated product is washed 3 times by a mixed solution of water and ethanol (volume ratio is 1:1) and dried, thus obtaining polymer particles.
2. Synthesis of nitrogen doped coral shaped FeP@NC composite material:
placing the polymer particles synthesized in the step (1) and red phosphorus (the mass ratio is 1:2) in two porcelain boats respectively, placing the porcelain boat with the red phosphorus in the air flow upstream of a tube furnace, placing the porcelain boat with the polymer particles in the air flow downstream of the tube furnace, introducing Ar air flow through the porcelain boat with the red phosphorus, then flowing through the porcelain boat with the polymer particles, and then in Ar atmosphere at 1 ℃ for min -1 Heating the tube furnace from room temperature to 600 ℃ and calcining for 6 hours to obtain FeP@NC.
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 diameter of 1-3 mu m, which is formed by gathering particles with the particle diameter of 100-500nm, and is called 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 test of nitrogen doped coral FeP@NC composite material:
the FeP@NC prepared by the method is taken as an electrode active substance, super P is taken as a conductive agent, polyvinylidene fluoride (PVDF) is taken as a binder to prepare slurry, and the composition ratio is 8:1:1; copper foil is used as a current collector, the thickness of the copper foil is 80 microns, an electrode is coated by scraping, and the copper foil is dried at 60 ℃. At this time, the electrode loading was about 1mg cm -2 . Sodium sheet with diameter of 1.6mm is used as counter electrode, glass fiber membrane is used as diaphragm, 1M NaPF is used 6 As an electrolyte, DGME was used as an electrolyte to assemble sodium |fep@nc half cells. At 0.1A g -1 (relative to FeP@NC), 0.2A g -1 ，0.5A g -1 ，1A g -1 ，2A g -1 ，5A g -1 ，10A g -1 20A g -1 The charge and discharge test of the multiplying power performance is carried out under the condition of 10A g -1 Long-cycle testing of large currents was performed at current densities of (c).
Examples 2 to 18:
the same nitrogen-doped coral-shaped FeP@NC composite material as in example 1 was prepared and assembled into a battery and performance was tested, 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-benzene tricarboxylic acid, the phosphorus source, the temperature rise rate, the calcination temperature, the calcination time and the mass content of N were all as shown in Table 1, and the performance test data of the prepared sodium ion battery were as shown in Table 3.
Comparative examples 1 to 7:
the preparation process of the nitrogen-doped coral-shaped FeP@NC composite material and the assembly thereof into a battery and the performance test process were the same as in example 1 except that the kind of the organic ligand, the temperature rise rate and the order of materials, the related data are shown in Table 2, and the performance test data of the prepared sodium ion battery are shown in Table 3.
Table 1 preparation process parameters of examples 1-18
Table 2 process parameters of comparative examples 1-7
TABLE 3 results of Performance test of examples 1-18 and comparative examples 1-6
The FeP@NC synthesized in example 1 showed the best electrochemical activity when electrochemically tested on different amounts of FeP@NC synthesized from dopamine hydrochloride (DA). The composite material prepared also shows a higher multiplying power table at the carbon content of 48.8 percentAt 20 A.g -1 Has a current density of 176.5 mAh.g -1 Specific capacity of 10 A.g -1 After 10000 circles of current density, 89 mAh.g -1 Has better multiplying power performance and large current long cycle performance.
The characteristic that both ends of F127 are respectively provided with a hydrophilic group and a hydrophobic group, and the middle is long-chain is utilized, the hydrophilic group shows electronegativity, and is combined with ferric iron, so that ferric iron ions form micelle-like particles under the stirring condition; the micelle-like structure of the hydrophobic groups at the long chain and the other end can prevent the combination with other micelles, so that the agglomeration is avoided, and the dispersity is higher. The dopamine hydrochloride is mainly used as a nitrogen source, and can be self-polymerized to form polydopamine and have certain viscosity, so that certain nitrogen element can be doped; meanwhile, we also found that when the amount of dopamine hydrochloride is changed, the proportion of FeP changes little, so that it does not participate in the polymerization process of the whole reaction, and is mainly used as a nitrogen source. Fe (NO) 3 ) 3 ·9H 2 O is used as an iron source, and is firstly subjected to electrostatic interaction with F127 to form micelle-like particles, and then is subjected to coordination polymerization with 1,3, 5-benzene tricarboxylic acid. On the one hand, 1,3, 5-benzene tricarboxylic acid can promote the assembly of micelle through the action of Van der Waals force and the hydrophobic end of the surfactant; on the other hand, the particles can enter the inside of the micelle to carry out coordination and recombination with 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 amount of dopamine hydrochloride does not greatly cause the proportion of FeP in the whole complex, and the concentration of dopamine hydrochloride is preferably 0-15 (mg/ml) as a nitrogen source.
From the experimental results, it can be seen that the proportion of FeP in the final complex is mainly dependent on the amount of ferric ion species, and that the addition of too much ferric salt or ligand does not significantly affect the experimental results. Preferred ligands in the present invention are 1,3, 5-trimellitic acid, and Fe (NO) 3 ) 3 ·9H 2 The preferred molar ratio of O is 2: 1-1:2.
When 1,3, 5-benzene tricarboxylic acid is replaced by 1,3, 5-trimethylbenzene, the micelle-shaped particles can be formed first, and the 1,3, 5-trimethylbenzene can also promote the assembly of the micelle through the action of Van der Waals force and the hydrophobic end of the surfactant, but the size of the polymer particles cannot be controlled well due to the fact that iron ions in the micelle particles lack organic ligands, so that the polymer particles are larger and have poorer performance.
When 1,3, 5-trimethylbenzene is added to the solution first or Fe (NO) 3 ) 3 ·9H 2 When O, F127 and dopamine hydrochloride are dissolved together, uniform colloid-shaped particles cannot be formed first, the average particle size of the particles is larger, and the overall performance is poor. When 1,3, 5-benzene tricarboxylic acid is changed into terephthalic acid, the symmetrical structure of terephthalic acid enlarges the organic framework formed by the terephthalic acid and iron ions, and further enlarges the formed FeP particles, so the performance is poor.
As the formed colloidal particles are obtained by weak bond force combination, the structure of the colloidal particles is destroyed when the temperature rising rate is too high, and finally the particles become larger and the performance is deteriorated, the preferable heating rate in the invention is 0.1-5 ℃ for min -1 。
The carbonization temperature of the surfactant, the organic ligand and the dopamine hydrochloride in the colloidal particles is influenced by the carbonization temperature, the carbonization temperature is required to be higher than 600 ℃, and 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 influenced, and the content of FeP is not obviously influenced, so that the overall performance is basically unchanged. The preferred calcination temperature in the present invention is 600 to 1200 ℃.
When the calcination time is too long, agglomeration of FeP particles may occur, and the overall performance may be deteriorated. The preferred calcination time in the present invention is 2 to 12 hours.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (9)

1. The preparation method of the FeP@NC taking nitrogen doped carbon as a carrier is characterized by comprising the following steps of:
(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 performing self-polymerization to form the precursor of the FeP@NC compound;
(2) Placing the precursor synthesized in the step (1) and a phosphorus source in two porcelain boats respectively, then placing the porcelain boat with the phosphorus source at the air flow upstream of a tube furnace, placing the porcelain boat with the precursor at the air flow downstream of the tube furnace, enabling inert gas to flow through the porcelain boat with the phosphorus source and then 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;
the surfactant in the step (1) is 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.
2. The method according to claim 1, wherein in the step (1), the alcohol is ethanol, and the volume ratio of ethanol to water is 1: (0.5-2).
3. The method of claim 1, wherein the iron source in step (1) is Fe (NO 3 ) 3 ·9H 2 O、Fe(NO 3 ) 3 、FeCl 3 、Fe 2 (SO 4 ) 3 、FeSO 4 、Fe(NO 3 ) 2 And FeCl 2 One or more than two of them.
4. The method according to claim 3, wherein the organic ligand in the step (1) is one or more of 1,3, 5-benzene tricarboxylic acid, terephthalic acid, 1,3, 5-trimethylbenzene and dimethylimidazole; the molar ratio of organic ligand to Fe in the iron source is 2: 1-1:2.
5. The process of claim 4, wherein the phosphorus source in step (2) is red phosphorus, white phosphorus, naH 2 PO 4 And Na (Na) 2 HPO 4 One or more than two of them; the mass ratio of the precursor to the phosphorus source is 1 (1-4).
6. The process according to claim 5, wherein the heating rate in step (2) is 0.1 to 5℃for a minute -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcination time is 2-12 h; the inert gas is Ar.
7. A fep@nc particle with nitrogen-doped carbon as a carrier, characterized by being produced by the production method according to any one of claims 1 to 6.
8. Use of the fep@nc particles of claim 7 with nitrogen-doped carbon as a carrier in an alkali metal ion battery.
9. The use according to claim 8, characterized in that the fep@nc particles with nitrogen-doped carbon as carrier 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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CN110142058A (en) * 2019-05-21 2019-08-20 大连理工大学 A kind of three-dimensional porous FeNi-NC bifunctional electrocatalyst and preparation method thereof of F127 induction
CN110265638A (en) * 2019-05-29 2019-09-20 北京科技大学 Coated porous hollow bowl-type ferric oxide powder material of nitrogen-doped carbon and preparation method thereof
CN110459768A (en) * 2019-08-14 2019-11-15 中南大学 A kind of octahedral structure iron phosphide/carbon composite and the preparation method and application thereof
CN111188126A (en) * 2020-01-08 2020-05-22 嘉兴学院 Flexible iron phosphide/carbon nanofiber membrane and preparation method and application thereof

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