CN108767260A - A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application - Google Patents

A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application Download PDF

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CN108767260A
CN108767260A CN201810575366.XA CN201810575366A CN108767260A CN 108767260 A CN108767260 A CN 108767260A CN 201810575366 A CN201810575366 A CN 201810575366A CN 108767260 A CN108767260 A CN 108767260A
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carbon coating
electrode materials
fep
nano
hollow nano
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CN108767260B (en
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夏冬林
李力
李启东
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Wuhan University of Technology WUT
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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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • H01M4/621—Binders
    • 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 invention discloses a kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application.Assembled by a diameter of 200~300 nanometers of FeP nano particles kernels and carbon shell surface layer；Lamellar spacing in wherein existing between nano particle kernel and carbon shell surface layer, and a diameter of 300~400 nanometers of the nano-electrode material.The present invention reacts five-step approach by simple hydro-thermal-cladding-calcining-etching-high-temp in-situ and prepares the hollow nano-electrode materials of carbon coating FeP, it is simple for process easy to operate, cost is greatly reduced, and preparation process is environmentally protective, there is potential mass market application value；When the material is as anode material of lithium-ion battery under 200mA/g high current densities charge-discharge test, first charge-discharge specific capacity is up to 582mA/g, and charging and discharging capacity is 566.7mA/g, capacity retention ratio 97.4% after 500 long circulatings.

Description

A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application
Technical field
The invention belongs to nanometer material and electrochemical technology fields, and in particular to a kind of hollow nano-electrodes of carbon coating FeP Material and its preparation method and application.
Background technology
In recent years, with the development of industry, a large amount of uses of fossil fuel, cause environmental pollution more serious.It finds new Type green clean energy resource becomes current urgent problem to be solved, and energy storage system is then to develop clean energy resource all the time Bottleneck.Portable electronic device, flexible wearing electronic device, electric vehicle, electric power generate electricity by way of merging two or more grid systems etc. all to energy storage system More stringent requirements are proposed.The energy storage system for preparing high-power high-capacity is to realize the pass of energy transformation and green application Key.Lithium ion battery is one of most potential energy-storage system, the technology with relative maturity.But with lithium ion battery Large-scale application, metal lithium resource just drastically declines.According to statistics, by current wear rate, existing lithium resource is only capable of propping up Support uses 30 years.How to find the novel battery material of alternative metals lithium becomes the research hotspot of current energy field.
As the metallic element sodium of same main group, there is similar chemical property with lithium metal and reserves are extremely abundant, and Have in electrochemical reaction can with compared with lithium capacity contribution and preferable kinetics, be to substitute the most potential gold of lithium Belong to.Sodium-ion battery has excellent high rate performance, higher capacity and good cyclical stability.Nano material has higher Specific surface area and preferable activity, when as sodium ion battery electrode material with electrolyte contacts area is big, sodium ion deintercalation Apart from short, the electro-chemical activity of material can be effectively improved, is had when as high-capacity and long-life sodium ion battery electrode material Significant advantage.Because there is high-specific surface area and contact the diffusion of promotion sodium ion with the good of electrolyte, thus reduce Structural stress present in polarization and charge and discharge process, to improve the electrochemical window and cyclical stability of battery, and wherein The nano material of graded porous structure has more shown great advantage.
As a kind of potential negative material, transition metal phosphide has raw material cheap, rich reserves, synthesis letter The features such as list, theoretical capacity is high, thus widely studied.However there are two causes for this transition metal phosphide electrode material Defect is ordered, first, the conductivity of relative mistake causes the high rate performance of electrode material and power density relatively low；Second is that due to its generation Electrochemical conversion reaction cause material irreversible transition, volume expansion problem is serious, and structure is difficult to maintain, and leads to capacity attenuation Decline with cycle life.In recent years, conductivity and electrochemistry of the transition metal phosphide in electrochemical reaction how is improved to follow Ring stability becomes research hotspot, and main policies are the electrode materials for synthesizing porous hierarchical structure and building nucleocapsid mechanism, but The problems such as that there are synthesis steps is cumbersome for general synthetic method, synthetic product low yield.
Invention content
Present invention aims at for current transition metal phosphide electrode material there are the problem of, a kind of carbon coating is provided Hollow nano-electrode materials of FeP and preparation method thereof, simple for process, cost is relatively low, meets the requirement of Green Chemistry, synthesized The hollow nano-electrode materials of carbon coating FeP when as sodium ion battery electrode material have good chemical property.
In order to achieve the above objectives, as follows using technical solution：
A kind of hollow nano-electrode materials of carbon coating FeP, by a diameter of 200~300 nanometers of FeP nano particles kernels and Carbon shell surface layer assembles；Lamellar spacing in wherein existing between nano particle kernel and carbon shell surface layer, and the nano-electrode material Expect a diameter of 300~400 nanometers.
The preparation method of the above-mentioned hollow nano-electrode materials of carbon coating FeP, includes the following steps：
1) Fe(NO3)39H2O is add to deionized water, stirring makes it fully dissolve；Sodium hydroxide solution is added, stirs Mixing makes it be sufficiently mixed；
2) it is fitted into reaction kettle and carries out hydro-thermal reaction, by the product centrifugal filtration of gained, washing, that drying obtains presoma is red Color powder；
3) gained presoma red powder be dispersed in the mixed solution of second alcohol and water, ultrasonic disperse, sequentially add ammonium hydroxide, Resorcinol and formaldehyde, stirring make it be sufficiently mixed, washing, drying to red powder；
4) gained red powder is placed in tube furnace calcines under nitrogen atmosphere, then naturally cools to room temperature, obtains carbon packet Cover Fe3O4Nano particle；
5) by carbon coating Fe3O4Nano particle is mixed with hydrochloric acid solution, utilizes salt acid etch, washing, drying carbon coating Fe3O4Hollow Nanoparticles；
6) by carbon coating Fe3O4It is former that Hollow Nanoparticles and sodium hypophosphite are placed in tube furnace high temperature under nitrogen atmosphere Position reaction, naturally cools to room temperature, obtains the hollow nano-electrode materials of carbon coating FeP.
By said program, the molar ratio of Fe(NO3)39H2O and sodium hydroxide is 1 in step 1:1.
By said program, hydrothermal temperature is 80~140 DEG C in step 2, and the hydro-thermal reaction time is 72~144h.
By said program, presoma red powder, ammonium hydroxide, resorcinol and formaldehyde mass ratio are 2 in step 3：30：1：2.
By said program, calcination temperature is 400~600 DEG C in step 4, and heating rate is 2~5 DEG C/min, calcination time For 4~6h.
By said program, a concentration of 1~4mol/L of hydrochloric acid solution in step 5, etch period is 20~60min.
By said program, carbon coating Fe in step 63O4Hollow Nanoparticles and the mass ratio of sodium hypophosphite are 1：(10- 20)；High-temp in-situ reaction temperature is 300~500 DEG C；Heating rate is 2~5 DEG C/min, and the reaction time is 3~5h.
Application of the above-mentioned hollow nano-electrode materials of carbon coating FeP as anode material of lithium-ion battery.
The present invention solves the problems, such as that transition metal phosphide conductivity in electrochemical reaction is low, shortens sodium ion and exists Diffusion path in electrochemical reaction improves specific surface area and the electro-chemical activity site of active material, in sodium ion deintercalation In the process padded coaming volume change dramatically and ensure its structure and electrochemical stability, by structure, carbon coating FeP is hollow receives Rice electrode material, effectively increases the chemical property of material.In 200mA/g when the material is as anode material of lithium-ion battery Charge-discharge test under high current density, first charge-discharge specific capacity is up to 582mA/g, charge and discharge specific volume after 500 long circulatings Amount is 566.7mA/g, capacity retention ratio 97.4%.Should the result shows that the hollow nano-electrode materials of carbon coating FeP have compared with High capacity and excellent cyclical stability are the potential application materials of high-capacity and long-life sodium-ion battery.
Beneficial effects of the present invention are as follows：
The present invention reacts five-step approach by simple hydro-thermal-cladding-calcining-etching-high-temp in-situ and prepares carbon coating FeP Hollow nano-electrode material, preparation process is simple to operation, greatly reduces the manufacturing cost of electrode material, and prepares Journey is environmentally protective, has potential mass market application value；
The hollow nano-electrode materials of carbon coating FeP that the present invention synthesizes have that high degree of dispersion, size are uniform, object phase purity is high The characteristics of, convenient for preparing the electrode material of high quality；
When as anode material of lithium-ion battery, the hollow nano-electrode materials of carbon coating FeP show excellent electricity Chemical electrical conductance, higher capacity and excellent cyclical stability are the potential application materials of high-capacity and long-life sodium-ion battery Material.
Description of the drawings
Fig. 1：Flow chart prepared by the hollow nano-electrode materials of carbon coating FeP of the present invention；
Fig. 2：The XRD diagram of the hollow nano-electrode material presomas of 1 carbon coating FeP of embodiment；
Fig. 3：The SEM of the hollow nano-electrode material presomas of 1 carbon coating FeP of embodiment schemes；
Fig. 4：The XRD diagram of the hollow nano-electrode materials of carbon coating FeP of embodiment 1；
Fig. 5：The SEM of the hollow nano-electrode materials of carbon coating FeP of embodiment 1 schemes；
Fig. 6：The hollow nano-electrode material cycle performance of battery curve graphs of carbon coating FeP of embodiment 1.
Specific implementation mode
Following embodiment further illustrates technical scheme of the present invention, but not as limiting the scope of the invention.
Embodiment 1
The preparation method of the hollow nano-electrode materials of carbon coating FeP, synthesis step as shown in Figure 1,
1) by 0.1mol Fe(NO3)39H2Os (Fe (NO3)3·9H2O it) is put into beaker, 100mL deionized waters is added, stir Mixing 30min makes it fully dissolve；The sodium hydroxide solution (NaOH) of the 1mol/L of 100mL is added, stirring 30min keeps it fully mixed It closes；
2) solution obtained by step 1) is fitted into 100 DEG C of hydro-thermal reaction 96h in reaction kettle, takes out reaction kettle, natural cooling To room temperature；By the product centrifugal filtration of gained, it is used in combination water and absolute ethyl alcohol to wash 6 times, 80 DEG C of drying 12h are to obtain in an oven Presoma red powder；As shown in Fig. 2, X-ray diffracting spectrum (XRD) shows that presoma is cubic phase, free from admixture.Such as figure Shown in 3, field emission scanning electron microscope (FESEM) test result shows presoma dispersibility preferably, shows a monodisperse distribution substantially, grain Cube block structure of the diameter at 200~300 nanometers.
3) product obtained by step 2) is dispersed in 70mL ethyl alcohol and the mixed solution of 10mL deionized waters, ultrasonic disperse 30min sequentially adds 3mL ammonium hydroxide, 0.1g resorcinols and 0.14mL formaldehyde, and stirring 2h makes it be sufficiently mixed, by product water It is washed 6 times with absolute ethyl alcohol, 80 DEG C of drying 12h are to obtain red powder in an oven；
4) by the nano particle of the Coated with Organic Matter obtained by step 3) in tube furnace in nitrogen atmosphere 2 DEG C/min liters Temperature, holding temperature are 550 DEG C；Calcination time makes annealing treatment for 4h, naturally cools to room temperature and can be obtained carbon coating Fe3O4Nanometer Particle；
5) product obtained by step 4) is put into beaker, 2mol/L salt acid etch 30min, product water and anhydrous is added Ethyl alcohol washs 6 times, and 80 DEG C of drying 12h are up to carbon coating Fe in an oven3O4Hollow Nanoparticles；
6) by the carbon coating Fe obtained by step 5)3O4Hollow Nanoparticles and sodium hypophosphite (NaH2PO2·H2O) with quality Than 1：The 20 2 DEG C/min heatings in nitrogen atmosphere in tube furnace, holding temperature is 400 DEG C；Calcination time makes annealing treatment for 4h, It naturally cools to room temperature and can be obtained the hollow nano-electrode materials of carbon coating FeP.
As shown in figure 4, X-ray diffracting spectrum (XRD) shows that the hollow nano-electrode materials of carbon coating FeP are cubic crystal Phase, without other dephasigns.As shown in figure 5, the bright the present embodiment of SEM charts is prepared for the hollow nano-electrode materials of carbon coating FeP, the carbon Coat and form the structure in middle level gap.The electrical conductance for improving electrode material, when as anode material of lithium-ion battery The volume expansion of the effective buffer electrode material impulse electricity process of energy is shunk, and improves the structural stability of material, while effectively The contact area for increasing material and electrolyte, to obtain the chemical property of long-life, high power capacity.
For the hollow nano-electrode materials of carbon coating FeP prepared by the present invention be used as anode material of lithium-ion battery, sodium from Remaining step of the preparation method of sub- battery is identical as usual way.The preparation method of negative plate is as follows：Using in carbon coating FeP Empty nano-electrode material is as active material, and for acetylene black as conductive agent, sodium carboxymethylcellulose (CMC) is used as binder, living Property material, acetylene black, sodium carboxymethylcellulose mass ratio be 80：15：5；They are sufficiently mixed in proportion, it is ultrasonic to equal It is even, in coating to copper foil, punching about 1cm is carried out after vacuum drying on sheet-punching machine2Size；With sodium perchlorate (NaClO4) conduct Electrolyte, sodium piece are used as to electrode, and for Celgard2325 as diaphragm, CR2025 type stainless steels are that battery case is assembled into button Sodium-ion battery.
By taking the hollow nano-electrode materials of this example carbon coating FeP as an example, when the material is as anode material of lithium-ion battery, Cycle performance of battery curve graph under 200mA/g current densities as shown in Figure 6.The charge and discharge under 500mA/g high current densities Test, first charge-discharge specific capacity are 566.7mA/g up to 582mA/g, after 500 long circulatings, and capacity retention ratio is 97.4%.This result shows that the hollow nano-electrode materials of carbon coating FeP have higher capacity and excellent cyclical stability, It is the potential application material of high-capacity and long-life sodium-ion battery.
Embodiment 2
The preparation method of the hollow nano-electrode materials of carbon coating FeP, it includes the following steps：
1) by 0.2mol Fe(NO3)39H2Os (Fe (NO3)3·9H2O it) is put into beaker, 200mL deionized waters is added, stir Mixing 30min makes it fully dissolve；The sodium hydroxide solution (NaOH) of the 1mol/L of 200mL is added, stirring 30min keeps it fully mixed It closes；
2) solution obtained by step 1) is fitted into 80 DEG C of hydro-thermal reaction 120h in reaction kettle, takes out reaction kettle, natural cooling To room temperature；By the product centrifugal filtration of gained, it is used in combination water and absolute ethyl alcohol to wash 6 times, 80 DEG C of drying in an oven obtain for 24 hours Presoma red powder；
3) product obtained by step 2) is dispersed in 70mL ethyl alcohol and the mixed solution of 10mL deionized waters, ultrasonic disperse 40min sequentially adds 3mL ammonium hydroxide, 0.15g resorcinols and 0.21mL formaldehyde, and stirring 2h makes it be sufficiently mixed, by product water It is washed 4 times with absolute ethyl alcohol, 80 DEG C of drying 12h are to obtain red powder in an oven；
4) by the nano particle of the Coated with Organic Matter obtained by step 3) in tube furnace in nitrogen atmosphere 3 DEG C/min liters Temperature, holding temperature are 550 DEG C；Calcination time makes annealing treatment for 4h, naturally cools to room temperature and can be obtained carbon coating Fe3O4Nanometer Particle；
5) product obtained by step 4) is put into beaker, 1mol/L salt acid etch 30min, product water and anhydrous is added Ethyl alcohol washs 6 times, and 60 DEG C of drying 12h are up to carbon coating Fe in an oven3O4Hollow Nanoparticles；
6) by the carbon coating Fe obtained by step 5)3O4Hollow Nanoparticles and sodium hypophosphite (NaH2PO2·H2O) with quality Than 1：The 10 2 DEG C/min heatings in nitrogen atmosphere in tube furnace, holding temperature is 350 DEG C；Calcination time makes annealing treatment for 4h, It naturally cools to room temperature and can be obtained the hollow nano-electrode materials of carbon coating FeP.
Embodiment 3
The preparation method of the hollow nano-electrode materials of carbon coating FeP, it includes the following steps：
1) by 0.2mol Fe(NO3)39H2Os (Fe (NO3)3·9H2O it) is put into beaker, 100mL deionized waters is added, stir Mixing 30min makes it fully dissolve；The sodium hydroxide solution (NaOH) of the 2mol/L of 100mL is added, stirring 60min keeps it fully mixed It closes；
2) solution obtained by step 1) is fitted into 100 DEG C of hydro-thermal reaction 96h in reaction kettle, takes out reaction kettle, natural cooling To room temperature；By the product centrifugal filtration of gained, it is used in combination water and absolute ethyl alcohol to wash 6 times, 80 DEG C of drying in an oven obtain for 24 hours Presoma red powder；
3) product obtained by step 2) is dispersed in 60mL ethyl alcohol and the mixed solution of 8mL deionized waters, ultrasonic disperse 30min, sequentially adds 2.4mL ammonium hydroxide, 0.1g resorcinols and 0.14mL formaldehyde, and stirring 2h makes it be sufficiently mixed, product is used Water and absolute ethyl alcohol wash 6 times, and 80 DEG C of drying 12h are to obtain red powder in an oven；
4) by the nano particle of the Coated with Organic Matter obtained by step 3) in tube furnace in nitrogen atmosphere 2 DEG C/min liters Temperature, holding temperature are 500 DEG C；Calcination time makes annealing treatment for 4h, naturally cools to room temperature and can be obtained carbon coating Fe3O4Nanometer Particle；
5) product obtained by step 4) is put into beaker, 1mol/L salt acid etch 30min, product water and anhydrous is added Ethyl alcohol washs 6 times, and 80 DEG C of drying 12h are up to carbon coating Fe in an oven3O4Hollow Nanoparticles；
6) by the carbon coating Fe obtained by step 5)3O4Hollow Nanoparticles and sodium hypophosphite (NaH2PO2·H2O) with quality Than 1：The 20 2 DEG C/min heatings in nitrogen atmosphere in tube furnace, holding temperature is 400 DEG C；Calcination time makes annealing treatment for 6h, It naturally cools to room temperature and can be obtained the hollow nano-electrode materials of carbon coating FeP；
Embodiment 4
The preparation method of the hollow nano-electrode materials of carbon coating FeP, it includes the following steps：
1) by 0.15mol Fe(NO3)39H2Os (Fe (NO3)3·9H2O it) is put into beaker, 100mL deionized waters is added, stir Mixing 30min makes it fully dissolve；The sodium hydroxide solution (NaOH) of the 1.5mol/L of 100mL is added, stirring 60min makes it fully Mixing；
2) solution obtained by step 1) is fitted into 100 DEG C of hydro-thermal reaction 120h in reaction kettle, takes out reaction kettle, natural cooling To room temperature；By the product centrifugal filtration of gained, it is used in combination water and absolute ethyl alcohol to wash 6 times, 80 DEG C of drying 12h are to obtain in an oven Presoma red powder；
3) product obtained by step 2) is dispersed in 70mL ethyl alcohol and the mixed solution of 10mL deionized waters, ultrasonic disperse 30min sequentially adds 3mL ammonium hydroxide, 0.2g resorcinols and 0.28mL formaldehyde, and stirring 2h makes it be sufficiently mixed, by product water It is washed 6 times with absolute ethyl alcohol, 60 DEG C of drying 12h are to obtain red powder in an oven；
4) by the nano particle of the Coated with Organic Matter obtained by step 3) in tube furnace in nitrogen atmosphere 2 DEG C/min liters Temperature, holding temperature are 600 DEG C；Calcination time is 4h, naturally cools to room temperature and can be obtained carbon coating Fe3O4Nano particle；
5) product obtained by step 4) is put into beaker, 2mol/L salt acid etch 30min, product water and anhydrous is added Ethyl alcohol washs 6 times, and 80 DEG C of drying 12h are up to carbon coating Fe in an oven3O4Hollow Nanoparticles；
6) by the carbon coating Fe obtained by step 5)3O4Hollow Nanoparticles and sodium hypophosphite (NaH2PO2·H2O) with quality Than 1：The 10 2 DEG C/min heatings in nitrogen atmosphere in tube furnace, holding temperature is 400 DEG C；Calcination time makes annealing treatment for 4h, It naturally cools to room temperature and can be obtained the hollow nano-electrode materials of carbon coating FeP；
Embodiment 5
The preparation method of the hollow nano-electrode materials of carbon coating FeP, it includes the following steps：
1) by 0.2mol Fe(NO3)39H2Os (Fe (NO3)3·9H2O it) is put into beaker, 100mL deionized waters is added, stir Mixing 30min makes it fully dissolve；The sodium hydroxide solution (NaOH) of the 2mol/L of 100mL is added, stirring 60min keeps it fully mixed It closes；
2) solution obtained by step 1) is fitted into 100 DEG C of hydro-thermal reaction 96h in reaction kettle, takes out reaction kettle, natural cooling To room temperature；By the product centrifugal filtration of gained, water and absolute ethyl alcohol is used in combination to wash 6 times, in an oven 80 DEG C of drying for 24 hours to get To presoma red powder；
3) product obtained by step 2) is dispersed in 70mL ethyl alcohol and the mixed solution of 10mL deionized waters, ultrasonic disperse 30min sequentially adds 3mL ammonium hydroxide, 0.1g resorcinols and 0.14mL formaldehyde, and stirring 2h makes it be sufficiently mixed, by product water It is washed 6 times with absolute ethyl alcohol, 60 DEG C of drying are for 24 hours to get to red powder in an oven；
4) by the nano particle of the Coated with Organic Matter obtained by step 3) in tube furnace in nitrogen atmosphere 2 DEG C/min liters Temperature, holding temperature are 500 DEG C；Calcination time makes annealing treatment for 6h, naturally cools to room temperature and can be obtained carbon coating Fe3O4Nanometer Particle；
5) product obtained by step 4) is put into beaker, 3mol/L salt acid etch 30min, product water and anhydrous is added Ethyl alcohol washs 6 times, and 80 DEG C of drying 12h are up to carbon coating Fe in an oven3O4Hollow Nanoparticles；
6) by the carbon coating Fe obtained by step 5)3O4Hollow Nanoparticles and sodium hypophosphite (NaH2PO2·H2O) with quality Than 1：The 20 2 DEG C/min heatings in nitrogen atmosphere in tube furnace, holding temperature is 400 DEG C；Calcination time is 4h, natural cooling The hollow nano-electrode materials of carbon coating FeP are can be obtained to room temperature.
Embodiment 6
The preparation method of the hollow nano-electrode materials of carbon coating FeP, it includes the following steps：
1) by 0.2mol Fe(NO3)39H2Os (Fe (NO3)3·9H2O it) is put into beaker, 100mL deionized waters is added, stir Mixing 60min makes it fully dissolve；The sodium hydroxide solution (NaOH) of the 2mol/L of 100mL is added, stirring 30min keeps it fully mixed It closes；
2) solution obtained by step 1) is fitted into 100 DEG C of hydro-thermal reaction 120h in reaction kettle, takes out reaction kettle, natural cooling To room temperature；By the product centrifugal filtration of gained, it is used in combination water and absolute ethyl alcohol to wash 6 times, 80 DEG C of drying in an oven obtain for 24 hours Presoma red powder；
3) product obtained by step 2) is dispersed in 70mL ethyl alcohol and the mixed solution of 10mL deionized waters, ultrasonic disperse 60min sequentially adds 3mL ammonium hydroxide, 0.1g resorcinols and 0.14mL formaldehyde, and stirring 2h makes it be sufficiently mixed, by product water It is washed 6 times with absolute ethyl alcohol, 60 DEG C of drying are for 24 hours to get to red powder in an oven；
4) by the nano particle of the Coated with Organic Matter obtained by step 3) in tube furnace in nitrogen atmosphere 2 DEG C/min liters Temperature, holding temperature are 550 DEG C；Calcination time is 6h, naturally cools to room temperature and can be obtained carbon coating Fe3O4Nano particle；
5) product obtained by step 4) is put into beaker, 2mol/L salt acid etch 30min, product water and anhydrous is added Ethyl alcohol washs 6 times, and 80 DEG C of drying 12h are up to carbon coating Fe in an oven3O4Hollow Nanoparticles；
6) by the carbon coating Fe obtained by step 5)3O4Hollow Nanoparticles and sodium hypophosphite (NaH2PO2·H2O) with quality Than 1：The 20 3 DEG C/min heatings in nitrogen atmosphere in tube furnace, holding temperature is 400 DEG C；Calcination time is 4h, natural cooling The hollow nano-electrode materials of carbon coating FeP are can be obtained to room temperature.

Claims (9)

1. a kind of hollow nano-electrode materials of carbon coating FeP, it is characterised in that by a diameter of 200~300 nanometers of FeP nanometers Intragranular core and carbon shell surface layer assemble；Lamellar spacing in wherein existing between nano particle kernel and carbon shell surface layer, and described receive A diameter of 300~400 nanometers of electrode material of rice.
2. the hollow nano-electrode materials of carbon coating FeP as described in claim 1, it is characterised in that include the following steps：
1) Fe(NO3)39H2O is add to deionized water, stirring makes it fully dissolve；Sodium hydroxide solution is added, stirring makes It is sufficiently mixed；
2) it is fitted into reaction kettle and carries out hydro-thermal reaction, by the product centrifugal filtration of gained, washing, drying obtain presoma red powder End；
3) gained presoma red powder is dispersed in the mixed solution of second alcohol and water, and ultrasonic disperse sequentially adds ammonium hydroxide, isophthalic Diphenol and formaldehyde, stirring make it be sufficiently mixed, washing, drying to red powder；
4) gained red powder is placed in tube furnace calcines under nitrogen atmosphere, then naturally cools to room temperature, obtains carbon coating Fe3O4Nano particle；
5) by carbon coating Fe3O4Nano particle is mixed with hydrochloric acid solution, utilizes salt acid etch, washing, drying carbon coating Fe3O4 Hollow Nanoparticles；
6) by carbon coating Fe3O4Hollow Nanoparticles and sodium hypophosphite are placed in tube furnace that high-temp in-situ is anti-under nitrogen atmosphere It answers, naturally cools to room temperature, obtain the hollow nano-electrode materials of carbon coating FeP.
3. the hollow nano-electrode materials of carbon coating FeP as described in claim 1, it is characterised in that Fe(NO3)39H2O in step 1 Molar ratio with sodium hydroxide is 1:1.
4. the hollow nano-electrode materials of carbon coating FeP as described in claim 1, it is characterised in that hydrothermal temperature in step 2 It it is 80~140 DEG C, the hydro-thermal reaction time is 72~144h.
5. the hollow nano-electrode materials of carbon coating FeP as described in claim 1, it is characterised in that presoma red powder in step 3 End, ammonium hydroxide, resorcinol and formaldehyde mass ratio are 2：30：1：2.
6. the hollow nano-electrode materials of carbon coating FeP as described in claim 1, it is characterised in that calcination temperature is 400 in step 4 ~600 DEG C, heating rate is 2~5 DEG C/min, and calcination time is 4~6h.
7. the hollow nano-electrode materials of carbon coating FeP as described in claim 1, it is characterised in that hydrochloric acid solution is dense in step 5 Degree is 1~4mol/L, and etch period is 20~60min.
8. the hollow nano-electrode materials of carbon coating FeP as described in claim 1, it is characterised in that carbon coating Fe in step 63O4In Empty nano particle and the mass ratio of sodium hypophosphite are 1：(10-20)；High-temp in-situ reaction temperature is 300~500 DEG C；Heating speed Rate is 2~5 DEG C/min, and the reaction time is 3~5h.
9. application of the hollow nano-electrode materials of carbon coating FeP as anode material of lithium-ion battery described in claim 1.
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