CN111244403B - A kind of fluorinated graphene modified niobium pentoxide material and its preparation and application - Google Patents
A kind of fluorinated graphene modified niobium pentoxide material and its preparation and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- -1 fluorinated graphene modified niobium pentoxide Chemical class 0.000 title claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010955 niobium Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- DSYRJFDOOSKABR-UHFFFAOYSA-I niobium(v) bromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Br-].[Nb+5] DSYRJFDOOSKABR-UHFFFAOYSA-I 0.000 claims description 3
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 3
- FWIYBTVHGYLSAZ-UHFFFAOYSA-I pentaiodoniobium Chemical compound I[Nb](I)(I)(I)I FWIYBTVHGYLSAZ-UHFFFAOYSA-I 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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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
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明提供一种氟化石墨烯改性五氧化二铌材料及其制备方法和应用。一种氟化石墨烯改性五氧化二铌材料，由氟化石墨烯与五氧化二铌复合而成；五氧化二铌占整体材料的质量分数为55％‑98％，其中较优的是62％‑97％，最优的是70％‑94％。材料表面含有C‑F‑Nb键和F‑Nb键，五氧化二铌占整体材料的质量分数为55％‑98％，炭元素占整体材料的质量分数为1％‑25％，氟元素占整体材料的质量分数为0.2％‑20％。The invention provides a fluorinated graphene modified niobium pentoxide material and a preparation method and application thereof. A fluorinated graphene modified niobium pentoxide material is composed of fluorinated graphene and niobium pentoxide; 62%-97%, the best is 70%-94%. The surface of the material contains C-F-Nb bonds and F-Nb bonds, niobium pentoxide accounts for 55%-98% of the overall material, carbon element accounts for 1%-25% of the overall material, and fluorine accounts for The mass fraction of the overall material is 0.2%‑20%.
Description
Technical Field
The invention belongs to the field of lithium ion batteries and lithium ion supercapacitors, and particularly relates to a modified niobium dioxide-free negative electrode and a preparation method thereof.
Background
The transition metal oxide niobium pentoxide has a proper working potential (1-2V), and the unique crystal structure of the niobium pentoxide can provide rich storage sites for lithium ions, and meanwhile, the Nb in an orthorhombic crystal form2O5Because the octahedral gaps can provide special ion channels, the charge and discharge speed of the battery is improved.
However, niobium pentoxide is known to have very poor electron conductivity, and it is often desired to compound a conductive base material with it to improve the electron conductivity of the material. However, as the charge and discharge cycle progresses, the niobium pentoxide and the conductive base material tend to fall off, and the battery performance is degraded.
Disclosure of Invention
The invention provides a fluorinated graphene modified niobium pentoxide material and a preparation method and application thereof. A fluorinated graphene modified niobium pentoxide material is formed by compounding fluorinated graphene and niobium pentoxide; the niobium pentoxide accounts for 55-98% of the whole material by mass, preferably 62-97%, most preferably 70-94%.
The surface of the material contains C-F-Nb bonds and F-Nb bonds, the niobium pentoxide accounts for 55-98% of the mass fraction of the whole material, the carbon element accounts for 1-25% of the mass fraction of the whole material, and the fluorine element accounts for 0.2-20% of the mass fraction of the whole material;
the method is better: the niobium pentoxide accounts for 62 to 97 percent of the mass of the whole material, the carbon element accounts for 2 to 20 percent of the mass of the whole material, and the fluorine element accounts for 0.5 to 18 percent of the mass of the whole material;
optimally: the niobium pentoxide accounts for 70-94% of the mass of the whole material, the carbon element accounts for 5-18% of the mass of the whole material, and the fluorine element accounts for 0.8-15% of the mass of the whole material.
1) Fully dispersing and mixing organic alcohol, fluorinated graphene and ammonia water to form uniform liquid;
2) adding niobium halide with the mass of 1.0-20 times (preferably 2.0-15 times, most preferably 4.0-10 times) of the mass of the liquid into the liquid, stirring for 0.5-10 hours (preferably stirring time is 1-8 hours, most preferably stirring time is 1.5-6 hours), stopping stirring, filtering, centrifuging or evaporating the liquid to obtain a mesophase, calcining the mesophase at 300-;
the above-mentioned homogeneous liquid comprises the following components in parts by mass: 40-90 parts by mass of organic alcohol, 0.1-5 parts by mass of fluorinated graphene and 0.5-10 parts by mass of ammonia water (calculated by 40% of ammonia water in mass fraction).
The organic alcohol comprises one or more than two of methanol, ethanol, propanol, isopropanol and butanol;
the inert atmosphere gas is one or more than two of nitrogen, argon and helium;
the F/C ratio in the fluorinated graphene is 0.1-1.5, preferably 0.3-1.3, and most preferably 0.5-1.2; the number of layers of the fluorinated graphene is 1-15, preferably 1-10, and most preferably 1-5.
The niobium halide is one or more than two of niobium fluoride, niobium chloride, niobium bromide and niobium iodide.
The fluorinated graphene modified niobium pentoxide material is applied to a lithium battery cathode as an electrode active material.
According to the method, a C-F-Nb bond can be formed on the surface of the niobium pentoxide, the niobium pentoxide and graphene atoms are compounded in a scale through the C-F-Nb bond, the electronic conduction resistance is greatly reduced, the rate capability of the niobium pentoxide material is improved, the niobium pentoxide structure after the F atoms are doped in situ is more stable, and the cycle performance is greatly improved.
Detailed Description
Dissolving 9.3g of the prepared modified niobium pentoxide material, 0.3g of polyvinylidene fluoride and 0.4g of conductive agent into 18g N-methyl pyrrolidone, uniformly dispersing, and blade-coating on an aluminum foil with an electrode loading of 2mg/cm2. The prepared electrode is subjected to a flexible package battery test, the working electrode is modified niobium pentoxide, the counter electrode is a lithium plate, and the electrolyte is 1mol/L lithium hexafluorophosphate (the solvent is ethylene carbonate: dimethyl carbonate: diethyl carbonate: 1: 1 (volume ratio)). The charge and discharge multiplying power of the battery is 1C/20C/100C, the charge and discharge cutoff voltage is 1V-2.5V, and the unit gram capacity of the electrode is considered. And when the charge-discharge multiplying power is 1C, the percentage of the capacity after 1000 cycles to the initial capacity is considered, namely the capacity retention rate.
Example 1
After 45g of ethanol, 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 2g of ammonia water are mixed uniformly, 50g of niobium chloride is slowly added, the mixture is stirred for 5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The material is subjected to element analysis, wherein the mass fraction of carbon elements accounts for 10%, the mass fraction of fluorine elements accounts for 5%, and the balance is niobium pentoxide.
The XPS test and peak separation are carried out on the material, wherein 670.5e V belongs to a Nb-F bond 686.6e V belongs to a C-F bond, and 675.3e V belongs to a C-F-Nb bond, so that the fluorinated graphene modified niobium pentoxide material is proved to contain the C-F-Nb bond, the Nb-F bond and the C-F bond, and the bonds are beneficial to greatly reducing the electronic conduction resistance by compounding niobium pentoxide and fluorinated graphene on an atomic scale.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Comparative examples 1,
After 45g of ethanol and 2g of ammonia water are mixed uniformly, 50g of niobium chloride is slowly added, the mixture is stirred for 5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The above material was subjected to elemental analysis to obtain niobium pentoxide.
The above materials were XPS tested and peak fractionated with no 670.5e V, 686.6e V, 675.3e V present.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Comparative example 2
After mixing 45g of ethanol, 2g of graphene (5 layers) and 2g of ammonia water uniformly, slowly adding 50g of niobium chloride, stirring for 5 hours, and evaporating the liquid to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
And performing element analysis on the material, wherein the mass fraction of carbon elements accounts for 10.5%, and the balance is niobium pentoxide.
The above materials were XPS tested and peak fractionated with no 670.5e V, 686.6e V, 675.3e V present.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 2
After 45g of methanol, 3g of fluorinated graphene (with an F/C ratio of 1.2 and 4 layers) and 2g of ammonia water are mixed uniformly, 50g of niobium fluoride is slowly added, the mixture is stirred for 4.5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining the mixture for 6 hours at 800 ℃ in the nitrogen atmosphere, and cooling the mixture to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 3
After 80g of isopropanol, 2.7g of ammonia water and 3g of fluorinated graphene (F/C ratio is 1.1, 5 layers) are mixed uniformly, 100g of niobium bromide is slowly added, the mixture is stirred for 3 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining the mixture for 10 hours at 500 ℃ in an argon atmosphere, and cooling the mixture to prepare a powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 4
After 50g of ethanol, 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 4g of ammonia water are mixed uniformly, 60g of niobium chloride is slowly added, the mixture is stirred for 7 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 700 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 5
After 50g of butanol, 1.6g of fluorinated graphene (with an F/C ratio of 1.2 and 3 layers) and 6g of ammonia water are uniformly mixed, 70g of niobium chloride is slowly added, the mixture is stirred for 5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 6
Mixing 50g of ethanol, 2g of fluorinated graphene (with an F/C ratio of 0.28 and 12 layers) and 7g of ammonia uniformly, slowly adding 60g of niobium chloride, stirring for 5 hours, and evaporating the liquid to dryness to obtain an intermediate phase. Then calcining the mixture for 8 hours at 550 ℃ in an argon atmosphere, and cooling the mixture to prepare a powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 7
After 50g of methanol, 3g of fluorinated graphene (with an F/C ratio of 1.4 and 12 layers) and 5g of ammonia water are uniformly mixed, 80g of niobium iodide is slowly added, the mixture is stirred for 6 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 7.5 hours at 700 ℃ in the argon atmosphere, and cooling to prepare a powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 8
40g of propanol, 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 6g of ammonia water are mixed uniformly, 60g of niobium chloride is slowly added, the mixture is stirred for 5 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 9
Mixing 37g of ethanol, 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 5g of ammonia water uniformly, slowly adding 50g of niobium chloride, stirring for 5 hours, and evaporating the liquid to obtain an intermediate phase. Then calcining for 8 hours at 600 ℃ in the argon atmosphere, and cooling to prepare the powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
Example 10
After 50g of ethanol, 2g of fluorinated graphene (F/C ratio of 1.1, 5 layers) and 8g of ammonia water are mixed uniformly, 65g of niobium chloride is slowly added, the mixture is stirred for 7 hours, and then the liquid is evaporated to dryness to obtain an intermediate phase. Then calcining the mixture for 12 hours at 800 ℃ in an argon atmosphere, and cooling the mixture to prepare a powder material.
The materials are subjected to electrode preparation and battery test, and the conditions of the electrode preparation and the battery test are shown in a table.
The data in the table show that when the electrode material is applied to a lithium ion battery as a negative electrode, the discharge capacity of the battery is obviously increased under a high-rate condition, the battery structure is more stable, and the capacity retention rate is improved by nearly one time.
Claims (10)
1. The application of the fluorinated graphene modified niobium pentoxide material as an electrode active material in a lithium battery cathode is characterized in that the fluorinated graphene modified niobium pentoxide material is formed by compounding fluorinated graphene and niobium pentoxide, and the surface of the material contains C-F-Nb bonds and F-Nb bonds; the niobium pentoxide accounts for 55-98% of the mass fraction of the fluorinated graphene modified niobium pentoxide material;
the preparation method of the fluorinated graphene modified niobium pentoxide material comprises the following specific steps:
1) fully dispersing and mixing organic alcohol, fluorinated graphene and ammonia water to form uniform liquid;
2) adding niobium halide with the mass of 1.0-20 times of that of the liquid into the liquid, stirring for 0.5-10 hours, stopping stirring, filtering, centrifuging or evaporating the liquid to obtain an intermediate phase, calcining the intermediate phase at the high temperature of 1000 ℃ under the inert atmosphere for 1-24 hours, and cooling to prepare a powder material;
the homogeneous liquid comprises the following components in parts by mass: 40-90 parts of organic alcohol, 0.1-5 parts of fluorinated graphene and 0.5-10 parts of ammonia water by mass percent, wherein the mass percent of the ammonia water is 40%.
2. Use according to claim 1, characterized in that:
the niobium pentoxide accounts for 55-98% of the mass fraction of the fluorinated graphene modified niobium pentoxide material, the carbon element accounts for 1-25% of the mass fraction of the fluorinated graphene modified niobium pentoxide material, and the fluorine element accounts for 0.2-20% of the mass fraction of the fluorinated graphene modified niobium pentoxide material.
3. Use according to claim 1, characterized in that: the mass fraction of niobium pentoxide in the fluorinated graphene modified niobium pentoxide material is 62-97%, the mass fraction of carbon in the fluorinated graphene modified niobium pentoxide material is 2-20%, and the mass fraction of fluorine in the fluorinated graphene modified niobium pentoxide material is 0.5-18%.
4. Use according to claim 1, characterized in that: the mass fraction of niobium pentoxide in the fluorinated graphene modified niobium pentoxide material is 70-94%, the mass fraction of carbon in the fluorinated graphene modified niobium pentoxide material is 5-18%, and the mass fraction of fluorine in the fluorinated graphene modified niobium pentoxide material is 0.8-15%.
5. Use according to claim 1, characterized in that:
and 2) adding niobium halide with the mass being 2.0-15 times of that of the liquid into the liquid, stirring for 1-8 hours, stopping stirring, filtering, centrifuging or evaporating the liquid to obtain an intermediate phase, calcining the intermediate phase at the temperature of 900 ℃ under an inert atmosphere for 2-20 hours at the temperature of 350-.
6. Use according to claim 1, characterized in that:
and 2) adding niobium halide with the mass being 4.0-10 times of that of the liquid into the liquid, stirring for 1.5-6 hours, stopping stirring, filtering, centrifuging or evaporating the liquid to obtain an intermediate phase, calcining the intermediate phase at the high temperature of 850 ℃ under an inert atmosphere, calcining for 3-12 hours, and cooling to prepare the powder material.
7. Use according to claim 1, characterized in that: the organic alcohol comprises one or more than two of methanol, ethanol, propanol, isopropanol and butanol;
the inert atmosphere is one or more than two of nitrogen, argon and helium;
the F/C ratio in the fluorinated graphene is 0.1-1.5; the number of layers of the fluorinated graphene is 1-15.
8. Use according to claim 1, characterized in that: the F/C ratio in the fluorinated graphene is 0.3-1.3; the number of layers of the fluorinated graphene is 1-10.
9. Use according to claim 1, characterized in that: the F/C ratio in the fluorinated graphene is 0.5-1.2; the number of layers of the fluorinated graphene is 1-5.
10. Use according to claim 1, characterized in that: the niobium halide is one or more than two of niobium fluoride, niobium chloride, niobium bromide and niobium iodide.
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| CN107413355A (en) * | 2017-06-13 | 2017-12-01 | 中国矿业大学 | A kind of Nb3O7The preparation method of F nano-arrays/graphene heterojunction composite |
| CN108448104A (en) * | 2018-05-10 | 2018-08-24 | 中南大学 | A kind of niobium pentoxide/carbon double quantum dot nanocomposite material and its preparation method and application |
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| CN107413355A (en) * | 2017-06-13 | 2017-12-01 | 中国矿业大学 | A kind of Nb3O7The preparation method of F nano-arrays/graphene heterojunction composite |
| CN108448104A (en) * | 2018-05-10 | 2018-08-24 | 中南大学 | A kind of niobium pentoxide/carbon double quantum dot nanocomposite material and its preparation method and application |
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| Title |
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| Chongfu Shi，et al.."Nb2O5 nanospheres/surface-modified graphene composites as superior anode materials in lithium ion batteries".《Ceramics International》.2017,第43卷(第8期),第6232-6238页. * |
| Liaona She，et al..（"Nb2O5 Nanoparticles Anchored on an N-Doped Graphene Hybrid Anode for a Sodium-Ion Capacitor with High Energy Density".《ACS Omega》.2018,第3卷(第11期),第15943-15951页. * |
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