CN111204735B - A kind of preparation method of fluorocarbon material and application thereof - Google Patents
A kind of preparation method of fluorocarbon material and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims description 7
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 claims description 3
- -1 Super P Chemical compound 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- BLIQUJLAJXRXSG-UHFFFAOYSA-N 1-benzyl-3-(trifluoromethyl)pyrrolidin-1-ium-3-carboxylate Chemical compound C1C(C(=O)O)(C(F)(F)F)CCN1CC1=CC=CC=C1 BLIQUJLAJXRXSG-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 229920002261 Corn starch Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 244000151018 Maranta arundinacea Species 0.000 claims description 2
- 235000010804 Maranta arundinacea Nutrition 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000012419 Thalia geniculata Nutrition 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000008103 glucose Substances 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
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000000227 grinding Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 5
- 239000007770 graphite material Substances 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 abstract 2
- 238000002203 pretreatment Methods 0.000 abstract 2
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/10—Carbon fluorides, e.g. [CF]nor [C2F]n
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种氟化碳材料的制备方法，包括如下步骤：S1、称取质量百分比为70～98%的硬碳原材料和2～30%的石墨类碳材料并在溶剂中混合，搅拌均匀后于保护气氛300～2800℃中烧结1～24 h，得到预处理材料；S2、将步骤S1中得到的预处理材料研磨并制成粉末状产物；S3、将步骤S2中得到的粉末状产物放入氟化设备，通入氟化气体，保持压强90～120 kPa，在350～450℃条件下反应8～16 h，得到氟化碳材料。本发明制作出的氟化碳材料具有高比功率和高比能量，可实现在30 A/g电流下放电，比能量大于500 Wh/kg，比功率大于41000 W/kg，可以应用于锂氟化碳电池正极材料使用。
The invention discloses a preparation method of carbon fluoride material, which comprises the following steps: S1. Weighing 70-98% by mass of hard carbon raw material and 2-30% of graphite carbon material, mixing them in a solvent, stirring After uniform, sintering in a protective atmosphere of 300-2800 ° C for 1-24 h to obtain a pre-treatment material; S2, grinding the pre-treatment material obtained in step S1 to make a powdery product; S3, grinding the powdery product obtained in step S2 The product is put into the fluorination equipment, fluorinated gas is introduced, the pressure is maintained at 90-120 kPa, and the reaction is carried out at 350-450 °C for 8-16 h to obtain the carbon fluoride material. The carbon fluoride material produced by the invention has high specific power and high specific energy, can be discharged at a current of 30 A/g, the specific energy is greater than 500 Wh/kg, and the specific power is greater than 41000 W/kg, and can be applied to lithium fluoride Used as cathode material for carbonized batteries.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage of power supply technology, and particularly relates to a preparation method and application of a carbon fluoride material.
Background
When the carbon fluoride is used as the positive electrode material of the lithium primary battery, the theoretical specific energy of mass is as high as 2180 Wh kg-1, and the carbon fluoride is the commercial lithium primary battery material with the highest theoretical specific energy at present. The lithium fluorocarbon battery is widely applied to various civil and military fields such as electronic radio frequency identification systems, cardiac pacemakers, missile ignition systems, small satellites or space weapons and the like for maneuvering orbital transfer launching, kinetic energy interception missiles, space stations and the like. The specific energy of the carbon fluoride material is determined by the fluorination degree of the material, the higher the fluorination degree is, the higher the theoretical specific energy is, but the higher the fluorination degree is, the poorer the electronic conductance of the material is, when the fluorine-carbon ratio is close to 1, the carbon fluoride is equivalent to an electronic insulator, the large-rate discharge performance of the material is limited, the specific capacity and the rate performance are mutually restricted, and the two are difficult to simultaneously achieve the optimization.
In order to improve the rate capability of carbon fluoride materials, researchers have developed various material modification approaches. For example, the measure of coating the surface with the high-conductivity material plays a certain role in improving the rate capability of the material. The direct addition of highly conductive carbon nanotubes, graphene, and the like in the positive electrode formulation is also a traditional modification measure. In addition, it is also a way to improve the discharge performance of the material by compounding a second phase positive electrode active material having a good rate capability or a higher discharge voltage with carbon fluoride. However, the methods are difficult to achieve the optimization of the specific capacity and the rate capability of the carbon fluoride material at the same time, and how to achieve the property of high specific energy while obtaining the performance of high specific power puts requirements on the structural design of the carbon fluoride material.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for producing a carbon fluoride material having both high specific power and high specific energy, and use thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a carbon fluoride material, comprising the steps of:
s1, weighing 70-98% of hard carbon raw material and 2-30% of graphite carbon material by mass, mixing in a solvent, uniformly stirring, and sintering at 300-2800 ℃ in a protective atmosphere for 1-24 hours to obtain the pretreatment material.
S2, grinding the pretreatment material obtained in the step S1 and preparing a powdery product.
S3, putting the powdery product obtained in the step S2 into fluorination equipment, introducing fluorination gas, keeping the pressure at 90-120 kPa, and reacting at 350-450 ℃ for 8-16 h to obtain the carbon fluoride material.
Further, in the step S2, the pretreatment material is ground until the particle size reaches below 60 um, and then the powder is sequentially sieved through a 200-mesh sieve, a 400-mesh sieve and a 800-mesh sieve to obtain a powdery product.
Further, the fluorocarbon material prepared in step S3 has a fluorocarbon ratio of 0.7 to 1.0.
Further, the hard carbon raw material is one or a combination of acetylene black, Super P, glucose, sucrose, cellulose, a metal organic framework material, ionic liquid, starch, a high molecular polymer and resin.
Wherein the starch is one or more of potato starch, corn starch, wheat starch, sweet potato starch and arrowroot starch. The high molecular polymer is one or a combination of polyacrylonitrile, polyaniline, polyvinylpyrrolidone, polypyrrole and polyvinyl chloride. The resin is one or the combination of more of phenolic resin, epoxy resin, polyfurfuryl alcohol resin and polyvinyl alcohol resin.
Further, the graphite-like carbon material is one or a combination of natural graphite, artificial graphite, graphene and carbon nanotubes.
Further, the solvent is one or more of water, ethanol, acetone, methyl methacrylate, butyl acrylate, acrylic acid, isopropanol, butyl glycol ether, tetrahydrofuran, benzene, toluene, xylene and dimethylformamide.
Further, the protective atmosphere is one or a combination of nitrogen, argon, neon and helium.
Further, the fluoridizing gas is one or a combination of more of xenon difluoride, nitrogen trifluoride, fluorine gas, boron trifluoride and mixed gas of fluorine gas and argon gas.
The invention also discloses an application of the carbon fluoride material prepared by the preparation method in preparation of a lithium carbon fluoride battery.
The invention has the following beneficial effects: the carbon fluoride material prepared by the preparation method has high specific power and high specific energy, can realize discharge under the current of 30A/g, has the specific energy of more than 500 Wh/kg and the specific power of more than 41000W/kg, and can be applied to the anode material of the lithium carbon fluoride battery.
Drawings
FIG. 1 is a diagram illustrating the electrochemical performance test results of the carbon fluoride material prepared in the first embodiment.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example one
A method for preparing a carbon fluoride material, comprising the steps of:
the method comprises the following steps: according to the mass ratio of the hard carbon raw material sucrose to the graphene material of 98%: 2 percent, mixing the sucrose material and the graphene material in a deionized water solvent, adding a little ethanol solvent, uniformly stirring, and sintering for 8 hours at 800 ℃ in a protective atmosphere to obtain the pretreatment material.
And step two, grinding the pretreated product obtained in the step one until the particle size reaches below 60 microns, and sequentially sieving the ground product with 200-mesh, 400-mesh and 800-mesh sieves to obtain a powdery product.
Step three: and (3) putting the powder material obtained in the step two into fluorination equipment, introducing a fluorination gas NF3, keeping the pressure at 100 kPa, and reacting for 12 h at 430 ℃ to obtain the carbon fluoride material with the bulk phase containing grapheme carbon and the fluorine-carbon ratio of 0.85.
The carbon fluoride material prepared by the method is used as a lithium battery anode material to be assembled into a button cell to be tested for electrochemical performance: (1) the working electrode is a bulk phase containing graphene carbon, the mass ratio of the carbon fluoride to the acetylene black to the polyvinylidene fluoride is 0.85, and the mass ratio of the carbon fluoride to the acetylene black to the polyvinylidene fluoride is 8: 1: 1, mixing materials; (2) the counter electrode is a lithium metal sheet; (3) the electrolyte is 1M lithium tetrafluoroborate solution dissolved in ethylene carbonate and dimethyl carbonate (volume ratio is 1: 1); (4) the discharge cut-off voltage is 1.5V; 5) the discharge current was 30A/g.
The performance results obtained from the above tests are shown in FIG. 1, and the material shows excellent rate performance, discharge to 1.5V at 30A/g, discharge time of 48 s, specific energy of 709 Wh/kg, and specific power of 53175W/kg.
Example two
A method for preparing a carbon fluoride material, comprising the steps of:
the method comprises the following steps: according to the mass ratio of the hard carbon raw material sucrose to the graphene material of 70%: 30 percent, mixing the sucrose material and the graphene material in a deionized water solvent, adding a little ethanol solvent, uniformly stirring, and sintering for 24 hours at the temperature of 300 ℃ in a protective atmosphere to obtain the pretreatment material.
And step two, grinding the pretreated product obtained in the step one until the particle size reaches below 60 microns, and sequentially sieving the ground product with 200-mesh, 400-mesh and 800-mesh sieves to obtain a powdery product.
Step three: and (3) putting the powder material obtained in the step two into fluorination equipment, introducing a fluorination gas NF3, keeping the pressure at 90 KPa, and reacting for 8 hours at 350 ℃ to obtain the carbon fluoride material with the bulk phase containing grapheme carbon and the fluorine-carbon ratio of 0.75.
The carbon fluoride material prepared in the embodiment is tested, and the material shows excellent rate performance, and is discharged to 1.5V at 30A/g, the discharge time is 45 s, the specific energy is 520 Wh/kg, and the specific power is 41600W/kg.
EXAMPLE III
A method for preparing a carbon fluoride material, comprising the steps of:
the method comprises the following steps: according to the mass ratio of the hard carbon raw material sucrose to the graphene material of 85%: 15 percent, mixing the sucrose material and the graphene material in a deionized water solvent, adding a little ethanol solvent, uniformly stirring, and sintering for 1 hour at 2800 ℃ in a protective atmosphere to obtain the pretreatment material.
And step two, grinding the pretreated product obtained in the step one until the particle size reaches below 60 microns, and sequentially sieving the ground product with 200-mesh, 400-mesh and 800-mesh sieves to obtain a powdery product.
Step three: and (3) putting the powder material obtained in the step two into fluorination equipment, introducing a fluorination gas NF3, keeping the pressure at 120kPa, and reacting for 10 hours at 450 ℃ to obtain the carbon fluoride material with the bulk phase containing grapheme carbon and the fluorine-carbon ratio of 0.8.
The carbon fluoride material prepared in the embodiment is tested, and the material shows excellent rate performance, and is discharged to 1.5V at 30A/g, the discharge time is 47 s, the specific energy is 601 Wh/kg, and the specific power is 46034W/kg.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010047718.1A CN111204735B (en) | 2020-01-16 | 2020-01-16 | A kind of preparation method of fluorocarbon material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010047718.1A CN111204735B (en) | 2020-01-16 | 2020-01-16 | A kind of preparation method of fluorocarbon material and application thereof |
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| CN113422059B (en) * | 2021-06-17 | 2022-06-28 | 贵州梅岭电源有限公司 | High-voltage carbon fluoride composite cathode material and preparation method thereof |
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