CN113401948B - Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application - Google Patents
Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application Download PDFInfo
- Publication number
- CN113401948B CN113401948B CN202110671765.8A CN202110671765A CN113401948B CN 113401948 B CN113401948 B CN 113401948B CN 202110671765 A CN202110671765 A CN 202110671765A CN 113401948 B CN113401948 B CN 113401948B
- Authority
- CN
- China
- Prior art keywords
- composite material
- lithium ion
- ion battery
- negative electrode
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims abstract description 6
- 235000011613 Pinus brutia Nutrition 0.000 claims abstract description 6
- 241000018646 Pinus brutia Species 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract 3
- 150000003839 salts Chemical class 0.000 claims abstract 3
- 238000007599 discharging Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims abstract 2
- 238000005406 washing Methods 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 82
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002505 iron Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention provides a lithium ion battery cathode Fe 7 S 8 /Fe 2 O 3 Dissolving ferric salt, urotropine and sublimed sulfur in water, stirring, carrying out hydrothermal reaction, washing, drying and calcining the obtained product to obtain Fe 7 S 8 /Fe 2 O 3 A composite material. Fe prepared herein 2 O 3 /Fe 7 S 8 The composite material is in a pine needle ball shape, provides a large contact area for the electrolyte and the electrode, and promotes charge and Li + The fast transfer of (2); and the composite material forms a larger space gap, and the volume expansion of the material during lithium intercalation is relieved, so the electrochemical performance of the battery is effectively improved. Thereby Fe 2 O 3 /Fe 7 S 8 The composite electrode exhibits a high reversible capacity. 0.1 C multiplying power is used for charging and discharging for 200 times, and the capacity is as high as 1000 mAh/g.
Description
Technical Field
The invention relates to the technical field of preparation of energy storage materials, in particular to Fe 7 S 8 /Fe 2 O 3 A composite material and a preparation method and application thereof.
Background
Currently, commercial lithium ion batteriesThe cathode material is mainly graphite with good cycling stability, but the specific capacity is lower (the theoretical specific capacity is only 372 mAh 8729g) -1 ) And the requirements of people on the lithium ion battery with high power density and high energy density cannot be met. Therefore, it is necessary to develop a negative electrode material having a high specific capacity, high cycle stability and high rate performance to replace the existing graphite negative electrode.
Fe. O and S widely exist in the nature, are low in price and friendly to the environment, and iron oxides have the advantages of high energy density, safety, no toxicity, stable structure and low price, and are deeply concerned by researchers. Therefore, iron oxides are ideal negative electrode materials for lithium ion batteries. Wherein Fe 2 O 3 The theoretical capacity of the catalyst reaches 1008 mAh g -1 However, the practical discharge capacity is very low, about 300 mAh g-1, and the cycling stability and rate performance can not meet the requirements, which are mainly limited by the volume change and the dynamics of the active material. To improve Fe 2 O 3 Is generally Fe 2 O 3 Nanocrystallization, or preparation of Fe 2 O 3 And C, the reversible capacity and the cycle life of the negative electrode material are improved to a certain extent.
Also, iron has poor sulfide stability, fe 7 S 8 Theoretical capacity of 667 mAh g -1 The actual discharge capacity is slightly higher than that of Fe 3 O 4 Actual discharge capacity of (c). However, fe 7 S 8 The material has the defects of low conductivity, volume expansion in the charge-discharge cycle process, active substance dissolution in electrolyte and the like, so that the cyclicity and the rate capability of the material are poor.
Disclosure of Invention
The invention provides Fe 7 S 8 /Fe 2 O 3 The composite material, the preparation method and the application thereof solve the problem of Fe 2 O 3 And Fe 7 S 8 Low actual discharge specific capacity and bad cycle capacity and cycle life.
The technical scheme for realizing the invention is as follows:
lithium ion battery cathode Fe 7 S 8 /Fe 2 O 3 A process for the preparation of a composite material by reacting 0.6g Fe (NO) 3 )·9H 2 O, 1.19g of urotropin and 0.12g of sublimed sulfur are dissolved in 30mL of water, the mixture is continuously stirred for 20min, and then the obtained solution is poured into an autoclave (50 mL) and placed in an oven for reaction at 160-200 ℃ for 8-16h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 450-500 deg.C for 2-3h in the atmosphere, with the heating rate of 5 deg.C/min -1 。
Said Fe 7 S 8 /Fe 2 O 3 The composite material is in a pine needle ball shape, and the particle size is uniform.
The method takes ferric nitrate, urotropine and sublimed sulfur as raw materials, and prepares the composite lithium ion battery cathode material (Fe) through hydrothermal synthesis and high-temperature calcination 2 O 3 /Fe 7 S 8 )。Fe 2 O 3 /Fe 7 S 8 Mixing with Super P, PVDF and N-methyl pyrrolidone in proportion, coating on copper foil, and drying at 80 deg.C for 12 hr; then slicing and drying for 4 hours at 80 ℃ to obtain the lithium ion battery negative pole piece.
The invention has the beneficial effects that: fe prepared herein 2 O 3 /Fe 7 S 8 The composite material is pine needle ball-shaped, provides a large contact area for the electrolyte and the electrode, and promotes charge and Li + Fast transfer of (2); and the composite material forms a larger space gap, and the volume expansion of the material during lithium intercalation is relieved, so the electrochemical performance of the battery is effectively improved. Thereby Fe 2 O 3 /Fe 7 S 8 The composite electrode exhibits a high reversible capacity. 0.1 C multiplying power is charged and discharged for 200 times, and the capacity is up to 1000 mAh/g.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows Fe prepared in example 1 7 S 8 /Fe 2 O 3 Scanning Electron Microscope (SEM) images of (a).
FIG. 2 shows Fe prepared in example 1 7 S 8 /Fe 2 O 3 X-ray diffraction (XRD) pattern of (A) and (B) Fe 2 O 3 And Fe 7 S 8 Standard card drawings.
FIG. 3 is Fe prepared in example 1 7 S 8 /Fe 2 O 3 X-ray photoelectron spectroscopy (XPS).
FIG. 4 shows Fe prepared in example 1 7 S 8 /Fe 2 O 3 A0.1C constant current charge and discharge curve diagram of a battery assembled by the cathode material prepared by the sample is shown.
FIG. 5 shows Fe prepared in example 1 7 S 8 /Fe 2 O 3 Cyclic Voltammetry (CV) curves after the sample prepared negative electrode material was assembled into a battery.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
0.6g of Fe (NO) 3 )·9H 2 O, 1.19g of urotropin and 0.12g of sublimed sulfur were dissolved in 30mL of water, the mixture was stirred for 20min, and the resulting solution was poured into an autoclave (50 mL) and placed in an oven at 180 ℃ for reaction for 10h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 500 deg.C for 2h at a temperature rise rate of 5 deg.C/min -1 。
Example 2
0.6g of Fe (NO) 3 )·9H 2 O, 1.12g of urotropin and 0.12g of sublimed sulfur were dissolved in 30mL of water, and the mixture was stirred for 20min, and then the resulting solution was poured into an autoclave (50 mL) and placed in an oven at 180 ℃ for reaction for 10h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 500 deg.C for 2h at a temperature of 5 deg.C/min -1 。
Example 3
0.6g of Fe (NO) 3 )·9H 2 O, 1.26g of urotropin and 0.12g of sublimed sulfur were dissolved in 30mL of water, the mixture was stirred for 20min, and the resulting solution was poured into an autoclave (50 mL) and placed in an oven at 180 ℃ for reaction for 10h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 500 deg.C for 2h at a temperature of 5 deg.C/min -1 。
Example 4
0.6g of Fe (NO) 3 )·9H 2 O, 1.19g of urotropin and 0.12g of sublimed sulfur were dissolved in 30mL of water, the mixture was stirred for 20min, and then the resulting solution was poured into an autoclave (50 mL) and placed in an oven at 180 ℃ for reaction for 8h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 500 deg.C for 2h at a temperature of 5 deg.C/min -1 。
Example 5
0.6g of Fe (NO) 3 )·9H 2 O, 1.19g of urotropin and 0.12g of sublimed sulfur were dissolved in 30mL of water, the mixture was stirred for 20min, and then the resulting solution was poured into an autoclave (50 mL) and placed in an oven at 180 ℃ for reaction for 12h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 500 deg.C for 2h at a temperature of 5 deg.C/min -1 。
Example 6
0.6g of Fe (NO) 3 )·9H 2 O, 1.1g of urotropin and 0.12g of sublimed sulfur were dissolved in 30mL of water, the mixture was stirred for 20min, and then the resulting solution was poured into an autoclave (50 mL) and placed in an oven at 160 ℃ for reaction for 8h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 450 deg.C for 2.5h in the atmosphere, and heating rate of 5 deg.C/min -1 。
Example 7
0.6g of Fe (NO) 3 )·9H 2 O, 1.30g of urotropin and 0.12g of sublimed sulfur were dissolved in 30mL of water, the mixture was stirred for 20min, and then the resulting solution was poured into an autoclave (50 mL) and placed in an oven at 200 ℃ for reaction for 16h. After cooling to room temperature, the obtained precipitate was washed with water and ethanol 2-3 times, respectively. Finally, fe 7 S 8 /Fe 2 O 3 The powder was dried in a vacuum oven at 80 ℃ for 8 hours. Then transferred to a tube furnace in N 2 Annealing at 550 ℃ for 3h under the atmosphere, wherein the heating rate is 5 ℃ per minute -1 。
Examples of the effects of the invention
Mixing the black magnetic powder obtained in the above embodiment with Super P, PVDF and N-methylpyrrolidone in proportion, coating the mixture on a copper foil, and drying the copper foil at 80 ℃ for 12 hours; then slicing, and further heating at 80 deg.CAnd drying for 4 hours to obtain the lithium ion battery negative pole piece. And then assembling the pole piece, the sodium metal, the diaphragm and the electrolyte into a battery, and testing, wherein the composite lithium ion battery negative electrode material Fe prepared in the embodiment 1 7 S 8 /Fe 2 O 3 The best results of the charge and discharge performance test after the battery is assembled (as shown in fig. 3).
FIG. 1 shows sample Fe 2 O 3 /Fe 7 S 8 The Scanning Electron Microscope (SEM) image shows that the composite material is like a pine needle ball and has a relatively large surface area to be contacted with the electrolyte.
FIG. 2 shows the Fe prepared by the present invention from the top to the bottom 7 S 8 /Fe 2 O 3 X-ray diffraction (XRD) pattern of (A) and (B) Fe 2 O 3 And Fe 7 S 8 Standard card drawing, which shows that the invention successfully prepares Fe 7 S 8 /Fe 2 O 3 A material.
FIG. 3 shows Fe prepared by the present invention 7 S 8 /Fe 2 O 3 Further illustrating the success of the present invention in the preparation of Fe 7 S 8 /Fe 2 O 3 A material.
FIG. 4 is sample Fe 7 S 8 /Fe 2 O 3 A0.1C constant-current charge-discharge curve diagram after the negative electrode material prepared by the sample is assembled into a battery shows that the discharge capacity reaches 1000 mAh/g after 200 cycles.
FIG. 5 shows Fe in sample 7 S 8 /Fe 2 O 3 Cyclic Voltammetry (CV) curves of the negative electrode materials prepared by the samples after the batteries are assembled.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. Lithium ion battery cathode Fe 7 S 8 /Fe 2 O 3 The preparation method of the composite material is characterized by comprising the following steps:dissolving ferric salt, urotropine and sublimed sulfur in water, stirring, carrying out hydrothermal reaction, washing, drying and calcining the obtained product to obtain Fe 7 S 8 /Fe 2 O 3 A composite material; said Fe 7 S 8 /Fe 2 O 3 The composite material is in a pine needle ball shape; wherein the iron salt is Fe (NO) 3 )·9H 2 The mass ratio of O, ferric salt, urotropine and sublimed sulfur is 0.6: (1.1-1.3): 0.12.
2. the method of claim 1, wherein: the hydrothermal reaction temperature is 160-200 ℃ and the time is 8-16h.
3. The production method according to claim 1, characterized in that: the calcination temperature of the dried product is 450-500 ℃ and the time is 2-3h.
4. A composite material produced by the production method according to any one of claims 1 to 3, characterized in that: said Fe 7 S 8 /Fe 2 O 3 The composite material is in a pine needle ball shape, and the particle size is uniform.
5. Use of the composite material of claim 4 in a negative electrode material for a lithium ion battery.
6. Use according to claim 5, characterized in that: the battery capacity is up to 1000 mAh/g after charging and discharging circulation for 200 times at 0.1C multiplying power.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110671765.8A CN113401948B (en) | 2021-06-17 | 2021-06-17 | Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110671765.8A CN113401948B (en) | 2021-06-17 | 2021-06-17 | Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113401948A CN113401948A (en) | 2021-09-17 |
CN113401948B true CN113401948B (en) | 2022-11-11 |
Family
ID=77684687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110671765.8A Active CN113401948B (en) | 2021-06-17 | 2021-06-17 | Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113401948B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114023937A (en) * | 2021-11-02 | 2022-02-08 | 欣旺达电动汽车电池有限公司 | Fe3O4/Fe7S8@ C composite material, preparation method thereof, lithium ion battery cathode and lithium ion battery |
CN115154482B (en) * | 2022-01-14 | 2023-05-02 | 河北金益合生物技术有限公司 | Application of ferric sulfide nano enzyme in resisting human papilloma virus |
CN115676900B (en) * | 2022-10-24 | 2024-04-09 | 江西师范大学 | Lithium ion battery cathode Fe 7 S 8 Composite material/C, preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4143213A (en) * | 1978-04-26 | 1979-03-06 | Exxon Research & Engineering Co. | Cells having cathodes containing chalcogenide compounds of the formula Ma FeXb and species thereof exhibiting alkali metal incorporation |
CN103259012A (en) * | 2013-05-15 | 2013-08-21 | 江西师范大学 | Three-dimensional conductive ferroelectric battery K2FeO4Preparation method of/C composite positive electrode material |
CN108598403A (en) * | 2018-04-16 | 2018-09-28 | 江西师范大学 | The forming method of lithium ion battery transiton metal binary oxides negative material |
CN111217350A (en) * | 2018-11-24 | 2020-06-02 | 启东茂材实业有限公司 | Preparation method of pine needle-shaped carbon nanotube/carbon fiber composite carbon material |
CN111517374A (en) * | 2020-04-20 | 2020-08-11 | 鸡西市唯大新材料科技有限公司 | Fe7S8Preparation method of/C composite material |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104672357B (en) * | 2013-11-29 | 2018-04-10 | 合肥杰事杰新材料股份有限公司 | A kind of composite material and preparation method thereof of graphene/carbon nanotube hybrid thing enhancing polymer |
CN107394174B (en) * | 2017-07-28 | 2020-10-09 | 鲁东大学 | Preparation method of iron oxide-mesoporous carbon lithium ion battery cathode material |
CN109449407B (en) * | 2018-10-30 | 2022-02-18 | 西南科技大学 | Preparation method of Fe7S8@ C nanorod material applicable to lithium ion battery |
CN110357168B (en) * | 2019-05-14 | 2020-04-21 | 江西师范大学 | Preparation method of lithium ion battery negative electrode material |
CN111477847B (en) * | 2020-04-08 | 2022-07-19 | 扬州大学 | Box-shaped necklace multilevel structure Fe7S8/WS2@ C-CNFs lithium ion battery negative electrode material and preparation method thereof |
CN111883758B (en) * | 2020-07-29 | 2022-01-14 | 江西师范大学 | Three-dimensionally crosslinked composite Fe3O4/FeS/rGO and preparation method and application thereof |
-
2021
- 2021-06-17 CN CN202110671765.8A patent/CN113401948B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4143213A (en) * | 1978-04-26 | 1979-03-06 | Exxon Research & Engineering Co. | Cells having cathodes containing chalcogenide compounds of the formula Ma FeXb and species thereof exhibiting alkali metal incorporation |
CN103259012A (en) * | 2013-05-15 | 2013-08-21 | 江西师范大学 | Three-dimensional conductive ferroelectric battery K2FeO4Preparation method of/C composite positive electrode material |
CN108598403A (en) * | 2018-04-16 | 2018-09-28 | 江西师范大学 | The forming method of lithium ion battery transiton metal binary oxides negative material |
CN111217350A (en) * | 2018-11-24 | 2020-06-02 | 启东茂材实业有限公司 | Preparation method of pine needle-shaped carbon nanotube/carbon fiber composite carbon material |
CN111517374A (en) * | 2020-04-20 | 2020-08-11 | 鸡西市唯大新材料科技有限公司 | Fe7S8Preparation method of/C composite material |
Non-Patent Citations (4)
Title |
---|
Fe/FeO/FeS混合物的Hugoniot线研究;黄海军等;《高压物理学报》;20060625(第02期);第29-34页 * |
多孔金属氧(硫)化物负极材料的制备及锂电性能研究;周琪;《中国优秀硕士学位论文全文数据库 》;工程科技Ⅰ辑;20170501;B020-464 * |
用作锂离子电池负极的FeS_2微球的制备及性能;荣华等;《高等学校化学学报》;20200310(第03期);第81-89页 * |
铁基电极材料在锂/钠离子电池中的应用研究进展;许希军等;《中国材料进展》;20191231(第11期);第5-16页 * |
Also Published As
Publication number | Publication date |
---|---|
CN113401948A (en) | 2021-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113401948B (en) | Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application | |
CN103441259B (en) | A kind of high magnification aquo-base metal electrochemical cells positive electrode and preparation method thereof | |
CN111180709B (en) | Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof | |
CN112018344B (en) | Carbon-coated nickel sulfide electrode material and preparation method and application thereof | |
CN113140722A (en) | Positive electrode lithium supplement material and preparation method and application thereof | |
CN108899531A (en) | A kind of preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material | |
CN110416530B (en) | Flower-like manganese dioxide/carbon composite material and preparation method and application thereof | |
CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
CN112635706A (en) | Preparation method of graphene-manganese dioxide nanorod-shaped negative electrode material | |
CN111933904A (en) | Bimetal sulfide and preparation method thereof, compound and preparation method thereof, lithium-sulfur positive electrode material and lithium-sulfur battery | |
CN108400296A (en) | Heterogeneous element doped ferroferric oxide/graphene negative material | |
CN111477872A (en) | Water-based lithium/sodium ion battery with iron-doped sodium titanium phosphate as negative electrode active material and preparation method thereof | |
CN108767231A (en) | L iNixCoyMnl-x-yO2/Li2O·B2O3Preparation method of composite positive electrode material | |
CN113346055A (en) | Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof | |
CN110980698B (en) | H1.07Ti1.73O4Preparation method of/rGO compound sodium ion battery anode material | |
CN112408487A (en) | Ramsdellite type manganese dioxide @ C composite material and preparation method and application thereof | |
CN107591530B (en) | Modification method of lithium titanate negative electrode material | |
CN107732206B (en) | Preparation method of bimetallic oxide composite negative electrode material with multilevel structure | |
CN107256962B (en) | A kind of the tertiary cathode material nickel cobalt aluminium and preparation method and application of aluminium foil growth in situ | |
CN106972171B (en) | Three-dimensional network structure material, preparation method and application thereof | |
CN108199034A (en) | Lithium ion battery zinc sulphide/ferrous sulfide anode material and preparation method | |
CN112201782B (en) | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof | |
CN110518194B (en) | Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof | |
CN108400319B (en) | Preparation method of nano-structure cobalt molybdate electrode material | |
CN112694132A (en) | ZnMn2O4Negative electrode material, preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |