CN111193011A - FeS2/FeNiS2Preparation and application of nanoparticles - Google Patents
FeS2/FeNiS2Preparation and application of nanoparticles Download PDFInfo
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- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052960 marcasite Inorganic materials 0.000 title claims abstract description 50
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 42
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000000034 method Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012621 metal-organic framework Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims 2
- 239000010405 anode material Substances 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 4
- 238000010586 diagram Methods 0.000 abstract description 4
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- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000002073 nanorod Substances 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 10
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000003486 chemical etching Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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 invention belongs to the technical field of lithium ion batteries, and particularly relates to FeS2/FeNiS2A preparation method of nano particles and application thereof in a lithium ion battery cathode material. The preparation method comprises the following steps: firstly, synthesizing Fe-Ni MOF by a hydrothermal method, and taking the Fe-Ni MOF as a precursor in N2Calcining in atmosphere, grinding and mixing with sulfur powder, N2Calcining and vulcanizing under atmosphere to obtain FeS2/FeNiS2And (3) nanoparticles. The material disclosed by the invention is simple in preparation method, has excellent rate capability and cycle performance under high current density when being used as a lithium ion battery cathode material, and the Nyquist diagram shows that the interface mass transfer impedance is small, and Li+The diffusion rate is faster.
Description
The technical field is as follows:
the invention belongs to the field of new energy material technology and lithium ion battery application, and particularly relates to FeS taking Fe-Ni MOF as a precursor2/FeNiS2Preparing nano particles; also relates to the material in the negative electrode material of the lithium ion batteryApplication in materials.
Background art:
lithium Ion Batteries (LIBs) are one of the most important energy storage devices, and have been widely used due to their advantages of high voltage, high specific energy, long working life, etc., whereas currently used graphite negative electrodes have approached their theoretical capacity (372mAh · g)-1) However, this capacity does not meet the requirements of increasingly large-scale power storage devices. Therefore, the development of high-capacity and high-energy-density lithium ion battery cathode materials is particularly critical.
Transition metal oxy/sulfides have attracted considerable attention from researchers over the past decade due to their unique properties and potential applications. Compared with metal oxides, metal sulfides generally have higher electrical conductivity, mechanical strength and better thermal stability, while bimetallic sulfides have higher electrochemical activity and capacity than corresponding monometallic sulfides, and are potential LIBs cathode materials. However, metal sulfides are susceptible to volume expansion during charging and discharging, resulting in pulverization of the electrode material and capacity loss. Therefore, the porous nano material is designed and synthesized, the specific surface area of the electrode in contact with the electrolyte is increased, and Li is shortened+The diffusion distance of the lithium ion battery is reduced, and meanwhile, the pore structure can relieve volume change in the charging and discharging process, so that volume expansion is effectively prevented, and the electrochemical performance of the lithium ion battery is improved.
Metal Organic Frameworks (MOFs) are highly ordered porous materials made up of organic ligands and inorganic metal ions or metal clusters linked by coordination bonds. The material has the advantages of good pore size distribution, large specific surface area, simple synthesis and the like. The preparation of the porous derivative by taking the MOF as the precursor is a method for effectively obtaining the porous nano material, and compared with the traditional chemical replacement or chemical etching method for obtaining the porous structure, the method has simple steps and is easy for large-scale synthesis. The method is adopted to prepare porous FeS at present2/FeNiS2The study of nanoparticles has not been reported.
The present invention has been made in view of the above circumstances.
The invention content is as follows:
aiming at the defects of the prior art and the prior artThe needs of research and application, and one of the purposes of the invention is to provide FeS2/FeNiS2The synthesis method of the nano-particles is that Fe-Ni MOF is synthesized by a hydrothermal method and is used as a precursor in N2Calcining in atmosphere, grinding and mixing with sulfur powder, N2Calcining and vulcanizing under atmosphere to obtain FeS2/FeNiS2And (3) nanoparticles. The method specifically comprises the following steps:
1. preparation of Fe-Ni MOF
(1.1) dissolving terephthalic acid in dimethylformamide to prepare a solution with a certain concentration, adding nickel nitrate hexahydrate and ferric trichloride hexahydrate in a certain molar ratio, and stirring to dissolve the nickel nitrate hexahydrate and the ferric trichloride hexahydrate to form a brownish yellow solution. Adding sodium hydroxide solution with certain concentration, and uniformly stirring to obtain precursor solution.
(1.2) pouring the solution into a reaction kettle, putting the reaction kettle into an oven, heating for a certain time, naturally cooling to room temperature, centrifugally separating a product, and drying in vacuum to obtain the Fe-Ni MOF.
Further, in the step (1.1), the concentration of terephthalic acid is 0.1mM, the molar ratio of nickel nitrate hexahydrate and ferric chloride hexahydrate is 1:2, and the concentration of sodium hydroxide solution is 0.4 mol.L-1。
In the step (1.2), the volume of the reaction kettle is 50mL, and the temperature of the oven is 100οAnd C, the reaction time is 15 h.
2、FeS2/FeNiS2Preparation of nanoparticles
(2.1) weighing a proper amount of dried Fe-Ni MOF in a quartz boat, and calcining for 2h in a tube furnace to obtain a product 1.
(2.2) weighing the product 1 and a proper amount of sulfur powder, mixing, grinding, putting into a quartz boat, and calcining at high temperature in a tube furnace to obtain FeS2/FeNiS2And (3) nanoparticles.
In the step (2.1), the mass of Fe-Ni MOF is 0.3g, and the temperature of the tube furnace is 500οC, the rate of temperature rise is 2οC·min-1。
In the step (2.2), the mass ratio of the product 1 to the sulfur powder is 1:5, and the temperature of the tubular furnace is 500οC, the rate of temperature rise is 5οC·min-1。
The second purpose of the invention is to provide the FeS2/FeNiS2The nano-particles are applied to the negative electrode material of the lithium ion battery.
Drying a proper amount of active materials, conductive carbon black and polyvinylidene fluoride (PVDF) in vacuum, weighing and grinding according to the ratio of 7:2:1, adding N-methyl pyrrolidone for pulping, coating the pulp on a clean copper foil by a scraper, drying, slicing and weighing. And (3) assembling the battery in the glove box according to the sequence of the positive electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate and the negative electrode shell, and standing for 10 hours.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation of FeS according to the invention2/FeNiS2The method for preparing the nano particles is simple and low in cost.
(2) The precursor Fe-Ni MOF is simple to synthesize and convenient for large-scale production.
(3) The FeS of the invention2/FeNiS2When the nano-particle electrode material is used for a lithium ion battery, the nano-particle electrode material has higher capacity, shows extremely high rate performance and stability, and is an electrode material with extremely high potential.
Description of the drawings:
in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the description of the embodiments or the prior art are briefly introduced below. It is obvious that the drawings described below are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a scanning electron micrograph of Fe-Ni MOF obtained in example 1.
FIG. 2 is the XRD pattern of Fe-Ni MOF obtained in example 1.
FIGS. 3 to 6 show FeS obtained in example 1 and comparative examples 1 to 3, respectively2/FeNiS2Scanning electron micrographs of nanoparticles.
FIG. 7 shows FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2Nanoparticles (individually labeled as FeS)2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3) XRD pattern.
FIG. 8 shows NiFe obtained in comparative example 42O4Scanning electron microscope image of the nanorods.
FIG. 9 shows NiFe obtained in comparative example 42O4XRD pattern of the nano-rod.
FIG. 10 shows FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2Nanoparticles (individually labeled as FeS)2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3) rate performance plot.
FIG. 11 shows FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2Nanoparticles (individually labeled as FeS)2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3) NiFe obtained in comparison with comparative example 42O4Nano-rod (marked as NiFe)2O4) At 1000mA · g-1The current density of (1) is 1000 times of cyclic charge and discharge, and the obtained performance graph is obtained.
FIG. 12 FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2Nanoparticles (individually labeled as FeS)2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3) impedance diagram and equivalent circuit model.
The specific implementation mode is as follows:
for a further understanding of the invention, reference will now be made to the following examples and drawings, which are not intended to limit the invention in any way.
Example 1:
1. preparation of Fe-Ni MOF
(1.1) dissolving a proper amount of terephthalic acid in a dimethylformamide solution, adding nickel nitrate hexahydrate and ferric trichloride hexahydrate in a certain molar ratio, and stirring to dissolve the mixture to form a brown yellow solution. Adding sodium hydroxide solution with certain concentration into the mixture, and uniformly stirring to obtain precursor solution.
(1.2) pouring the solution into a reaction kettle, putting the reaction kettle into an oven, heating for a certain time, naturally cooling to room temperature, centrifugally separating a product, and drying in vacuum to obtain the Fe-Ni MOF.
Further, the terephthalic acid in the step (1) was 2.7mmol, the dimethylformamide solution was 27mL, the molar ratio of nickel nitrate hexahydrate and ferric chloride hexahydrate was 1:2, and the concentration of the sodium hydroxide solution was 0.4 mol. L-1，
The volume of the reaction kettle in the step (2) is 50mL, and the temperature of the oven is 100 DEGοAnd C, the reaction time is 15 h.
2、FeS2/FeNiS2Preparation of nanoparticles
(2.1) weighing a proper amount of dried Fe-Ni MOF in a quartz boat and N in a tube furnace2Calcining for 2h under the atmosphere to obtain the product 1.
(2.2) weighing the product 1 and a proper amount of sulfur powder, mixing, grinding, placing in a quartz boat, and placing in a tube furnace N2Calcining at high temperature under atmosphere to obtain FeS2/FeNiS2And (3) nanoparticles.
In the step (2.1), the mass of Fe-Ni MOF is 0.3g, and the temperature of the tube furnace is 500οC, the rate of temperature rise is 2οC·min-1。
In the step (2.2), the mass of the product 1 is 0.0831g, the mass of the sulfur powder is 0.4155g, and the temperature of the tube furnace is 500οC, the rate of temperature rise is 5οC·min-1。
3. Assembly of lithium ion batteries
Drying a proper amount of active materials, conductive carbon black and polyvinylidene fluoride (PVDF) in vacuum, weighing and grinding according to the ratio of 7:2:1, adding N-methyl pyrrolidone for pulping, coating the pulp on a clean copper foil by a scraper, drying, slicing and weighing. And (3) assembling the battery in the glove box according to the sequence of the positive electrode shell, the electrode plate, the electrolyte, the diaphragm, the electrolyte, the lithium plate and the negative electrode shell, and standing for 10 hours.
Comparative example 1:
1. preparation of Fe-Ni MOF
Same as in example 1
2、FeS2/FeNiS2Preparation of nanoparticles
(2.1) weighing a proper amount of dried Fe-Ni MOF and a proper amount of sulfur powder, mixing, grinding, placing in a quartz boat, and placing in a tube furnace N2Calcining at high temperature under atmosphere to obtain FeS2/FeNiS2And (3) nanoparticles.
In the step (2.1), the mass of Fe-Ni MOF is 0.2g, the mass of sulfur powder is 1g, and the temperature of the tube furnace is 500οC, the rate of temperature rise is 2οC·min-1。
3. Assembly of lithium ion batteries
Same as in example 1.
Comparative example 2:
this example is substantially the same as the preparation of the nanomaterial of comparative example 1, except that FeS is used in step 22/FeNiS2In the preparation of the nanoparticles, the rate of temperature rise of the tube furnace was 5οC·min-1。
Comparative example 3:
1. preparation of Fe-Ni MOF
Same as in example 1
2、FeS2/FeNiS2Preparation of nanoparticles
(2.1)NiFe2O4Preparation of nanorods
Weighing proper amount of Fe-Ni MOF in a quartz boat, placing the quartz boat in a tube furnace in an air atmosphere of 450 DEGοCalcining C for 2h to obtain NiFe2O4And (4) nanorods.
(2.2) weighing a proper amount of NiFe2O4Mixing with sulfur powder, grinding for 10min, placing in quartz boat, and tube furnace N2Calcining for 2h at 500 ℃ under the atmosphere to obtain FeS2/FeNiS2And (3) nanoparticles.
Further, the mass of Fe-Ni MOF in step 2.1 is 0.3g, and the heating rate is 2οC·min-1。
NiFe in step 2.22O4Has a mass of 0.11g, a mass of 0.55g of sulfur powder, and a rate of temperature rise of 5 in the tube furnaceοC·min-1。
3. Assembly of lithium ion batteries
Same as in example 1.
Comparative example 4:
1. preparation of Fe-Ni MOF
Same as in example 1
2、NiFe2O4Preparation of nanorods
Same as in step 2.1 of comparative example 3
3. Assembly of lithium ion batteries
Same as in example 1.
FIG. 1 is a scanning electron micrograph of Fe-Ni MOF obtained in example 1. The obtained precursor is the octadecyl-hedron nanorod with the two hexagonal pyramids, the appearance is uniform, the surface is smooth, the length is about 800nm, and the width is about 180 nm.
FIG. 2 is the XRD pattern of Fe-Ni MOF obtained in example 1, consistent with previous literature reports, with all peaks strong and narrow, indicating high product crystallinity. No impurity peak appears in the spectrogram, which indicates that the MOF obtained by the method is relatively pure and has few impurities.
FIG. 3 shows FeS obtained in example 12/FeNiS2Scanning electron micrographs of nanoparticles. It can be seen that the appearance of the vulcanized nanorods is completely absent, the vulcanized nanorods are changed into an interconnected porous structure, have a higher specific surface area and are more fully contacted with the electrolyte, so that the vulcanized nanorods have better electrochemical performance. FIGS. 4-6 are FeS of comparative examples 1-3, respectively2/FeNiS2Scanning electron micrographs of nanoparticles. As in example 1, the product was essentially free of bipyramid nanorod structures of Fe-Ni MOF, resulting in some nanoparticles below 500nm in size.
FIG. 7 shows FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2XRD patterns of the nanoparticles, respectively labeled as FeS2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3. It can be seen that the products are all FeS2/FeNiS2。
FIG. 8 shows comparative example 4The obtained NiFe2O4Scanning electron microscope image of the nanorods. It can be seen that the path 450οAnd after calcining for 2h in the air atmosphere, the product basically keeps the appearance of the precursor nanorod, and the whole body shrinks a little. The surface thereof becomes rough, many grains are grown, some bipyramids of the nanorods are destroyed during the sintering process, and the nanorods have some sticking phenomenon
FIG. 9 NiFe obtained in comparative example 42O4XRD pattern of the nano-rod. The results show that the Fe-Ni MOF has become NiFe after air atmosphere calcination2O4With a broad peak shape and low crystallinity, except for NiFe2O4No other miscellaneous peak is present outside the characteristic peak, which indicates that the product has high purity.
FIG. 10 shows FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2Nanoparticles (individually labeled as FeS)2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3) rate performance plot. FeS2/FeNiS2The best rate capability of (2), 100mA · g-1，200mA·g-1，500mA·g-1，1000mA·g-1After 10 times of circulation, the discharge specific capacities are respectively 258, 202, 126 and 92mAh g-1When the current density returns to 100mA g-1In this case, the charge/discharge capacity was increased to 347mAh g-1And 353mAh · g-1. After 20 cycles, the charge-discharge capacity was 439 mA-g-1And 432mA · g-1Showing good rate performance.
FIG. 11 shows FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2Nanoparticles (individually labeled as FeS)2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3) NiFe obtained in comparison with comparative example 42O4Nano-rod (marked as NiFe)2O4) At 1000mA · g-1The current density of (1) is 1000 times of cyclic charge and discharge, and the obtained performance graph is obtained. In which FeS obtained in example 12/FeNiS2The performance is best, and the first discharge capacity is 1189mAh g-1，1000The charge-discharge capacity after the secondary cycle is 626mAh g-1，617mAh·g-1Same FeS2/FeNiS2-1，FeS2/FeNiS2The discharge capacity after-21000 cycles is 443mAh g-1，181mAh·g-1。FeS2/FeNiS2-3 with NiFe2O4The cycling stability was good, but the capacity was lower. This is mainly due to FeS2/FeNiS2The porous nano structure enlarges the contact area between the porous nano structure and the electrolyte and reduces Li+The migration path, while the sulfide has higher conductivity than the oxide, has better cycle capacity at high current density.
FIG. 12 FeS obtained in example 1 and comparative examples 1 to 32/FeNiS2Nanoparticles (individually labeled as FeS)2/FeNiS2，FeS2/FeNiS2-1，FeS2/FeNiS2-2，FeS2/FeNiS2-3) impedance diagram and equivalent circuit model. A typical nyquist plot consists of a semicircle of high frequency regions and a diagonal line of low frequency regions. R in equivalent circuit diagramΩResistance between battery cover, separator, gasket and electrolyte, R, for assembly into a battery devicectThe charge transfer resistance between the electrolyte and the surface of the material influences the diameter of the high-frequency region semi-circle, ZwIs Vainer impedance (solid state diffusion resistance), and Li in bulk phase+The diffusion speed of (2) is related to the slope of the oblique line. As can be seen from the figure, FeS2/FeNiS2The diameter of the semicircle of the Nyquist plot of (1) is minimum, the slope of the oblique line is maximum, which shows that the charge transfer resistance between the electrolyte and the material surface is small, and the Li of the material itself+The diffusion rate is faster, and thus the rate capability and the cycle performance under a large current density are better. The slopes of the other three materials are substantially the same, Li+The diffusion rates in bulk materials are uniform.
Claims (6)
1. FeS2/FeNiS2The preparation method of the nano-particles is characterized by comprising the following specific steps of:
(1) preparation of Fe-Ni MOF:
dissolving terephthalic acid in dimethylformamide to prepare a solution with a certain concentration, adding nickel nitrate hexahydrate and ferric trichloride hexahydrate in a certain molar ratio, stirring to dissolve the nickel nitrate hexahydrate and the ferric trichloride hexahydrate to form a brown yellow solution, adding a proper amount of sodium hydroxide solution into the brown yellow solution, and uniformly stirring to obtain a precursor solution; pouring the solution into a reaction kettle, putting the reaction kettle into an oven, heating for a certain time, naturally cooling to room temperature, centrifugally separating a product, and drying in vacuum to obtain Fe-Ni MOF;
(2)FeS2/FeNiS2preparing nano particles:
weighing a proper amount of dried Fe-Ni MOF in a quartz boat, and calcining for 2h in a tube furnace to obtain a product 1; weighing the product 1 and a proper amount of sulfur powder, mixing, grinding, placing in a quartz boat, and calcining at high temperature in a tube furnace to obtain FeS2/FeNiS2And (3) nanoparticles.
2. An FeS according to claim 12/FeNiS2The nano-particles are characterized in that the precursor of the nano-particles is an octadecyl nanometer rod with uniform appearance and hexagonal pyramid at two ends.
3. The FeS of claim 12/FeNiS2The preparation method of the nano particles is characterized in that a step-by-step vulcanization method is adopted, and Fe-Ni MOFs is calcined firstly and then reacts with sulfur powder for vulcanization.
4. The FeS of claim 12/FeNiS2The preparation method of the nano-particles is characterized in that the atmosphere of the tubular furnace in the step 2.1 is N2The atmosphere is 450-500 ℃, and the heating rate is 2 ℃ min-1。
5. The FeS of claim 12/FeNiS2The preparation method of the nano-particles is characterized in that the mass ratio of the product to the sulfur powder in the step 2.2 is 1:5, the temperature of the tubular furnace is 450 ℃ and 500 ℃, and the heating rate is 5 ℃ and min-1。
6. An FeS according to claim 12/FeNiS2Nanoparticles, characterized in that the material is used as a lithium ion battery anode material.
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