CN111747388A - Preparation method of self-supporting nickel phosphide-iron composite nanosheet - Google Patents
Preparation method of self-supporting nickel phosphide-iron composite nanosheet Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002135 nanosheet Substances 0.000 title claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052742 iron Inorganic materials 0.000 title description 4
- 239000002243 precursor Substances 0.000 claims abstract description 25
- LHLROOPJPUYVKD-UHFFFAOYSA-N iron phosphanylidynenickel Chemical compound [Fe].[Ni]#P LHLROOPJPUYVKD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- 239000002055 nanoplate Substances 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 claims 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract description 8
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 abstract description 8
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 8
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 229940037179 potassium ion Drugs 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 241001460678 Napo <wasp> Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other 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
- H01M10/054—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
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
The invention provides a preparation method of self-supporting nickel-iron-phosphorus (Ni-Fe-P) composite nanosheets, which comprises the specific steps of preparing nickel nitrate, ferric nitrate, ammonium fluoride and urea into a mixed solution in proportion, uniformly stirring, transferring into a reaction kettle, and adding clean foamed nickel (3 × 5 cm)2And the purity is 99 percent), synthesizing a nickel-iron composite precursor by using a hydrothermal reaction, and obtaining the nickel-iron-phosphorus composite nanosheet through a phosphorization reaction. The nickel-iron-phosphorus composite nanosheet is used as a negative electrode material of a sodium ion battery, and compared with a single material of nickel phosphide and iron phosphide, the capacity and stability of the battery during testing are improved, and the surfaceShows better electrochemical performance. The composite material used as a potassium ion battery cathode material also shows good electrochemical performance, and has potential application value in the field of potassium ion batteries.
Description
Technical Field
The invention relates to a nickel-iron-phosphorus composite nano material, in particular to a preparation method of a self-supporting nickel-iron-phosphorus composite nanosheet, which is applied to the negative electrodes of sodium-ion batteries and potassium-ion batteries and belongs to the field of the sodium-ion batteries and the potassium-ion batteries.
Technical Field
Due to the proximity of energy crisis and deterioration of ecological environment, the development of sustainable clean energy and efficient energy storage devices is urgently needed. Lithium ion batteries have been used in various fields of human life as energy storage devices. However, lithium resources are distributed unevenly and have low abundance, which greatly limits the future development of lithium ion batteries. Nowadays, sodium ion batteries are a potential substitute for lithium ion batteries, and are receiving attention due to their abundance and cost. In addition, the potassium ion battery has higher output voltage compared with the lithium ion battery, is beneficial to improving the energy density of the battery and has wide development potential. The invention provides a preparation method of a self-supporting nickel-iron-phosphorus composite nanosheet, and the material can be used as a negative electrode material of sodium ion and potassium ion batteries.
Disclosure of Invention
The invention provides a preparation method of self-supporting nickel-iron-phosphorus composite nanosheets, which comprises the steps of adding deionized water into nickel salt, ferric salt, ammonium salt and urea to prepare a mixed solution, uniformly stirring the mixed solution, transferring the mixed solution into a reaction kettle, obliquely placing foamed nickel in the reaction kettle, and placing the mixed solution at 100 DEG CoC -140oC, carrying out hydrothermal reaction for 2-6 h to prepare a nickel-iron composite precursor; and drying the ferronickel composite precursor at constant temperature, placing the dried ferronickel composite precursor in sintering equipment, placing a phosphorus source at an air inlet of the sintering equipment and at a distance of 8-12 cm from the ferronickel composite precursor in nitrogen atmosphere, and heating the mixture from room temperature at a speed of 2-5 ℃/min to 400 ℃ for a phosphorization reaction for 1-3 h to obtain the self-supporting ferronickel phosphorus composite nanosheet.
The nickel salt is Ni (NO)3)2·6H2O; the iron salt being Fe (NO)3)3·9H2O; the ammonium salt being NH4F。
The molar ratio of nickel nitrate, ferric nitrate, ammonium fluoride and urea is 1: 1.2-3: 3-8: 12-18. Preferably, the molar ratio of the nickel nitrate, the ferric nitrate, the ammonium fluoride and the urea is 1: 2: 6: 15.
the phosphorus source used in the phosphorization process is NaPO2H2·H2O, the addition amount of the phosphorus source is 0.06-0.1 g cm of the surface area of the foamed nickel-2Preferably, the phosphorus source is added in an amount of 0.067g cm of the surface area of the nickel foam-2。
The hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 4 hours; the temperature of the phosphating reaction is 350 ℃, and the time of the phosphating reaction is 2 hours.
The preparation method of the self-supporting nickel-iron-phosphorus composite nanosheet disclosed by the invention has the following characteristics:
(1) the raw material cost is low, and the nickel source and the iron source are rich.
(2) The experimental period is short, and the experimental repeatability is good.
(3) The prepared composite nano sheet material has uniform growth and is not easy to fall off, and the thickness is about 200 nm.
(4) Compared with single materials of nickel phosphide and iron phosphide, the composite material has certain advantages in electrochemical performance.
Drawings
Figure 1 comparative XRD of samples prepared from examples 1, 2, 3, 4 with standard cards.
FIG. 2 SEM images of samples prepared in example 1 at different magnifications before charge-discharge cycling, (a) is 5000 times and (b) is 20000 times.
FIG. 3 is a graph showing the charge and discharge characteristics of the samples prepared in example 1.
FIG. 4 comparative graph of performance of the samples prepared in examples 1, 2, 3 cycling through 100 cycles.
FIG. 5 SEM images of samples prepared in example 1 at different magnifications after charge and discharge cycles, wherein (a) is 5000 times and (b) is 20000 times.
FIG. 6 TEM images of the samples prepared in example 1, (a) is a high resolution transmission image, (b) is a selected area electron diffraction image, (c) is a low power transmission, and (d) is a high power transmission.
FIG. 7 mapping plots of samples prepared in example 1.
FIG. 8 SEM images of samples prepared in example 2 at different magnifications before charge-discharge cycling, wherein (a) is 5000 times and (b) is 20000 times.
Fig. 9 is a graph showing charge and discharge characteristics of the sample prepared in example 2.
FIG. 10 SEM images of samples prepared in example 2 at different magnifications after charge-discharge cycles, wherein (a) is 5000 times and (b) is 20000 times.
FIG. 11 SEM images of samples prepared in example 3 at different magnifications before charge-discharge cycles, wherein (a) is 5000 times and (b) is 20000 times.
Fig. 12 is a graph showing charge and discharge performance of the sample prepared in example 3.
FIG. 13 SEM images of samples prepared in example 3 at different magnifications after charge and discharge cycles, wherein (a) is 5000 times and (b) is 20000 times.
Fig. 14 charge and discharge performance profiles of samples prepared in example 4.
Figure 15 performance graph of 50 cycles of the sample prepared in example 4.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
1 mmol of Ni (NO)3)2·6H2O、2 mmol Fe(NO3)3·9H2O、6 mmol NH4F and 15 mmol CO (NH)2)2Placed in a beaker and 70 mL of deionized water was added and the solution was stirred well using a magnetic stirrer. The solution was transferred to a 100 mL reaction vessel and nickel foam (3 cm) was added at an incline2) And carrying out hydrothermal reaction at 120 ℃ for 4 h to prepare the nickel-iron composite precursor. Drying the nickel-iron composite precursor at constant temperature, placing the dried precursor in sintering equipment, and under the atmosphere of nitrogen, adding 0.2g of NaPO2H2·H2And placing the O in an air inlet of sintering equipment, keeping the distance of the O and the nickel-iron composite precursor to be 10cm, and heating the O from room temperature to 350 ℃ at the speed of 2 ℃/min for carrying out a phosphorization reaction for 2 h to obtain the self-supporting nickel-iron-phosphorus composite nanosheet.
FIG. 1 is a comparison of XRD and standard cards of a composite material with a single material of nickel phosphide and iron phosphide, the composite material showing characteristic peaks of nickel phosphide and iron phosphide and Ni2P（JCPDS No.03-0953）、Fe2The P (JCPDS No. 74-2533) standard card is identical. FIG. 2 is an SEM image of a nickel-iron-phosphorus composite material, showing that the composite material is of a nanosheet structure and the nanosheet thicknessAnd (4) uniformity. FIG. 3 shows the Ni-Fe-P composite material at 0.1A g-1The charge-discharge performance diagram under current density is used as a negative electrode material of a sodium ion battery to assemble a sodium ion half battery, and the initial discharge capacity is up to 650 mAh g-1Then the capacity is stabilized at 350 mAh g-1And about, the electrochemical performance is better. FIG. 4 is a comparison graph of the cycle performance of the composite material and the single material of nickel phosphide and iron phosphide, and after 100 cycles, the capacity and stability of the composite material are better. Fig. 5 is an SEM image after charge and discharge cycles, showing that the composite material still maintains the nanosheet structure after cycles, and the structural stability is good. Fig. 6 is a TEM correlation of the composite material with the selected area electron diffraction pattern being a plurality of rings and with the presence of lattice fringes in the high resolution TEM, illustrating that the composite material is grown in crystalline form on a nickel mesh and is polycrystalline. The polycrystalline material improves the stability of the battery due to the synergistic effect of the bimetal. Fig. 7 is a mapping diagram of the composite material, wherein the nickel, iron and phosphorus elements are uniformly distributed, which shows that the nickel phosphide and the iron phosphide uniformly grow on the nickel mesh substrate, thereby enhancing the synergistic effect of the bimetal, relieving the volume expansion of the material in the charging and discharging processes and improving the cycle performance of the battery.
Example 2
1 mmol of Ni (NO)3)2·6H2O、6 mmol NH4F and 15 mmol CO (NH)2)2Placed in a beaker and 70 mL of deionized water was added and the solution was stirred well using a magnetic stirrer. The solution was transferred to a 100 mL reaction vessel and nickel foam (3 cm) was added at an incline2) And carrying out hydrothermal reaction at 120 ℃ for 4 h to prepare a precursor. Drying the prepared precursor at constant temperature, placing the dried precursor in sintering equipment, and adding 0.2g of NaPO in nitrogen atmosphere2H2·H2And placing the O in an air inlet of sintering equipment, keeping the distance between the O and the precursor by 10cm, and heating the O from room temperature to 350 ℃ at the speed of 2 ℃/min for carrying out a phosphating reaction for 2 h to obtain the nickel phosphide nanosheet.
Nickel (Ni) phosphide2P) XRD of the nanosheets is shown in figure 1. Fig. 8 is an SEM image of nickel phosphide single material before cycling, showing that the sample was of nanosheet structure and the nanosheets were composed of small particles. FIG. 9 shows that the sample is at 0.1A g-1The charge-discharge performance diagram under the current density is used as a negative electrode material of the sodium-ion battery to assemble a sodium-ion half battery, and the first discharge capacity reaches 630 mAh g-1After that, the capacity is from 350 mAh g-1The electrochemical performance is general. Fig. 10 is an SEM image of the sample after 100 cycles of charge and discharge cycles, and shows that the sample still maintains the nanosheet structure after cycles, and the structural stability is good.
Example 3
2 mmol of Fe (NO)3)3·9H2O、6 mmol NH4F and 15 mmol CO (NH)2)2Placed in a beaker and 70 mL of deionized water was added and the solution was stirred well using a magnetic stirrer. The solution was transferred to a 100 mL reaction vessel and nickel foam (3 cm) was added at an incline2) And carrying out hydrothermal reaction at 120 ℃ for 4 h to prepare a precursor. Drying the prepared precursor at constant temperature, placing the dried precursor in sintering equipment, and adding 0.2g of NaPO in nitrogen atmosphere2H2·H2And placing the O in an air inlet of sintering equipment, keeping the distance between the O and the precursor by 10cm, and heating the O from room temperature to 350 ℃ at the speed of 2 ℃/min for carrying out a phosphating reaction for 2 h to obtain the ferric phosphide nanosheet.
Iron phosphide nanosheet (Fe)2P) is shown in figure 1. Fig. 11 is an SEM image of iron phosphide single material before circulation, showing that the sample is of a nanosheet structure, and the nanosheets self-assemble into spheres. FIG. 12 shows that the sample is at 0.1A g-1The charge-discharge performance diagram under the current density is used as a negative electrode material of the sodium-ion battery to assemble a sodium-ion half battery, and the first discharge capacity reaches 530 mAhg-1After that the capacity is from 280 mAh g-1The electrochemical performance is poor because the attenuation begins to occur. Fig. 13 is an SEM image of the sample after charge and discharge cycles, showing that the sample cannot maintain the nanosheet structure after cycling, and the structural stability is poor.
Example 4
1 mmol of Ni (NO)3)2·6H2O、2 mmol Fe(NO3)3·9H2O、6 mmol NH4F and 15 mmol CO (NH)2)2Placed in a beaker and 70 mL of deionized water was added and the solution was stirred well using a magnetic stirrer.The solution was transferred to a 100 mL reaction vessel and nickel foam (3 cm) was added at an incline2) And carrying out hydrothermal reaction at 120 ℃ for 4 h to prepare the nickel-iron composite precursor. After drying the precursor at constant temperature, transferring the dried precursor into sintering equipment and keeping the sintering equipment under the nitrogen atmosphere, and adding 0.2g of NaPO2H2·H2And placing the O in an air inlet of sintering equipment, keeping the distance of the O and the nickel-iron composite precursor to be 10cm, and heating the O from room temperature to 350 ℃ at the speed of 2 ℃/min for carrying out a phosphorization reaction for 2 h to obtain the nickel-iron-phosphorus composite nanosheet.
The XRD pattern is the same as that of Ni-Fe-P of example 1. FIG. 14 shows that the sample is at 0.2A g-1The charge and discharge performance diagram under current density is used as a potassium ion battery cathode material to assemble a potassium ion half battery, and the first discharge capacity is up to 1100 mAh g-1After that the capacity is from 600mAh g-1The attenuation begins to occur, and the electrochemical performance is good. FIG. 15 is a graph of the cycle performance of the composite material, after 50 cycles, the capacity dropped to 200 mAh g-1The stability of the composite material in the application of potassium electricity needs to be improved.
Claims (7)
1. A preparation method of self-supporting nickel-iron-phosphorus composite nanosheets is characterized by comprising the following steps: adding deionized water into nickel salt, ferric salt, ammonium salt and urea to prepare a mixed solution, uniformly stirring, transferring the mixed solution into a reaction kettle, obliquely placing foamed nickel at 100 DEG CoC-140oC, carrying out hydrothermal reaction for 2-6 h to prepare a nickel-iron composite precursor; drying the ferronickel composite precursor at constant temperature, placing the dried ferronickel composite precursor in sintering equipment, placing a phosphorus source in an air inlet of the sintering equipment under the nitrogen atmosphere, and enabling the phosphorus source to be spaced from the ferronickel composite precursor by 8-12 cm, and performing heat treatment at room temperature by 2-5 cmoThe temperature rises to 300-400 ℃ at the rate of C/minoAnd C, carrying out a phosphating reaction for 1-3 h to obtain the self-supporting nickel-iron-phosphorus composite nanosheet.
2. A method of making self-supporting nickel iron phosphorus composite nanoplates as in claim 1, wherein: the nickel salt being Ni (NO)3)2·6H2O; the iron salt being Fe (NO)3)3·9H2O; the ammonium salt being NH4F。
3. A method of preparing self-supporting nickel iron phosphide composite nanoplates as claimed in claim 2, characterised in that: the mol ratio of nickel nitrate, ferric nitrate, ammonium fluoride and urea is 1: 1.2-3: 3-8: 12-18.
4. A method of preparing self-supporting nickel iron phosphide composite nanoplates as claimed in claim 3, characterised in that: the mol ratio of nickel nitrate, ferric nitrate, ammonium fluoride and urea is 1: 2: 6: 15.
5. a method of making self-supporting nickel iron phosphorus composite nanoplates as in claim 1, wherein: the phosphorus source used in the phosphorization process is NaH2PO2·H2O, the addition amount of the phosphorus source is 0.06-0.1 g cm of the surface area of the foamed nickel-2。
6. A method of making self-supporting nickel iron phosphorus composite nanoplates as in claim 5, wherein: the addition amount of the phosphorus source is 0.067g cm of the surface area of the foamed nickel-2。
7. A method of making self-supporting nickel iron phosphorus composite nanoplates as in claim 1, wherein: the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 4 hours; the temperature of the phosphating reaction is 350 ℃, and the time of the phosphating reaction is 2 hours.
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