CN114148998A - Accurate fluorinated ginkgo leaf, purification method and functional application of lithium primary battery - Google Patents
Accurate fluorinated ginkgo leaf, purification method and functional application of lithium primary battery Download PDFInfo
- Publication number
- CN114148998A CN114148998A CN202111480392.2A CN202111480392A CN114148998A CN 114148998 A CN114148998 A CN 114148998A CN 202111480392 A CN202111480392 A CN 202111480392A CN 114148998 A CN114148998 A CN 114148998A
- Authority
- CN
- China
- Prior art keywords
- ginkgo
- ginkgo leaves
- fluorinated
- leaves
- carbonized
- 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.)
- Granted
Links
- 235000008100 Ginkgo biloba Nutrition 0.000 title claims abstract description 94
- 235000011201 Ginkgo Nutrition 0.000 title claims abstract description 85
- 241000218628 Ginkgo Species 0.000 title claims abstract description 85
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000746 purification Methods 0.000 title claims abstract description 15
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 244000194101 Ginkgo biloba Species 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000005087 graphitization Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000009656 pre-carbonization Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 12
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- -1 functional group modified carbon Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000011419 induction treatment Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- 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
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a fluorinated ginkgo leaf positive electrode material for a lithium primary battery, which comprises the steps of purifying natural ginkgo leaves and grafting-OH and-COOH in micro-oxidation in air, and impurities are converted into oxides while carbon materials in the ginkgo leaves are reserved. In addition, dilute acid solution is adopted to wash the carbonized ginkgo leaves to remove impurities. Annealing at 900 ℃ and 1100 ℃ to obtain the purified and carbonized ginkgo leaves. Further, the fluorinated ginkgo leaves are prepared by adopting a precise fluorination process. Therefore, the lithium fluorocarbon battery obtained based on the precise fluorinated ginkgo leaf and purification method and the lithium primary battery preparation has certain electrical properties, and lays an important foundation for various preparation methods of carbon fluoride and popularization and application of lithium/carbon fluoride batteries.
Description
Technical Field
The invention belongs to the technical field of new carbon fluoride materials and lithium primary batteries, and particularly relates to a precise fluorinated ginkgo leaf and a purification process method.
Background
The rapid development of new materials brings many opportunities and progresses to new energy lithium batteries. Unlike lithium ion secondary batteries, lithium primary batteries play an irreplaceable role in extreme environments, are not easy to disassemble, have no charging terminals, and the like. Among them, lithium/fluorocarbon primary batteries are receiving attention because of their excellent performance. The lithium/carbon fluoride battery has the advantages of large specific energy, high working voltage, wide working temperature range, excellent storage performance (small self-discharge), convenient use and carrying and the like, can meet the application requirements of power supplies in the fields of military, aviation, medicine and the like, and has great market potential. The theoretical energy density of the lithium/fluorocarbon cell (Li/(CFx) n) system is as high as 2189Wh/kg, the first commercial lithium primary cell to use solid positive electrode materials worldwide. The lithium/carbon fluoride primary battery Li/(CFx) n has a positive electrode made of carbon fluoride material (CFx) n and a negative electrode made of metallic lithium. The performance of a lithium fluorocarbon battery depends mainly on the fluorocarbon cathode material, including the crystallinity, conductivity, particle size distribution, interfacial wettability, etc. of the fluorocarbon. These properties are closely related to carbon sources and precise fluorination techniques. Carbon sources reported at present are carbon nanotubes, graphene, fullerene, hard carbon and the like. For example, chinese patent 202011245792.0 discloses a carbon fluoride material with a core-shell structure, a method for preparing the same, and a lithium battery. The developed fluorination technology comprises fluorination processes of antimony pentafluoride, hydrofluoric acid, fluorine gas and the like. The preparation of carbon fluoride by fluorine gas in combination with a high-temperature environment is relatively low in cost, good in controllability and popularized. Therefore, the search for new carbon sources and the combination of precise fluorination processes are one of the important directions of lithium/fluorocarbon batteries.
At present, a plurality of problems exist to limit the wide application of the lithium/carbon fluoride battery, the cost of the carbon material and the fluorination process cause the price of the carbon fluoride to be relatively high, and the preparation of the carbon material also causes certain pollution to the environment. Therefore, the method seeks a carbon source in the nature and optimizes the fluorination process, and is expected to open up a new idea for the development of carbon fluoride materials.
Disclosure of Invention
The invention aims to provide a method for preparing a precise fluorinated ginkgo leaf and a purification process method and a lithium primary battery aiming at the defects in the background technology. According to the method, ginkgo leaves are used as a natural carbon source, and a purification process and an accurate fluorination process are combined, so that elements such as impurities Ca and Mg contained in the carbon fluoride material are well removed, and meanwhile, a small amount of-OH and-COOH are grafted on the surface functional group modified carbon source and the activity of a fluorocarbon bond type is regulated and controlled; the lithium/carbon fluoride battery which is derived from natural ginkgo leaves, has high specific capacity and stable voltage platform is obtained by adopting the precise ginkgo leaf fluorination and the purification process method to prepare the carbon fluoride as the anode material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing carbon fluoride material by accurate fluorinated ginkgo leaf and purification process is characterized by comprising the following steps:
And 2, placing 500-2000g of dried ginkgo leaves in a CVD furnace, heating to 120 ℃ at the speed of 10 ℃/min in the air atmosphere, then continuously heating to 900 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping the temperature at 900 ℃ for 30-60min, and naturally cooling to obtain the carbonized ginkgo leaves.
And 3, placing the carbonized ginkgo leaves in a suction filtration device, washing the ginkgo leaves for 2-3 times by using a dilute acid solution, washing the ginkgo leaves for 5-8 times by using deionized water, and then placing the ginkgo leaves in an oven at 50-80 ℃ for 30-60min to obtain the washed carbonized ginkgo leaves.
And 4, placing the washed carbonized ginkgo leaves in the CVD furnace again, heating to 900-1100 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping for 4-6h, regulating and controlling the graphitization degree and the surface defect structure of carbon, and then naturally cooling to obtain the purified carbon source prepared from the ginkgo leaves.
And 5, placing the carbon source prepared from the ginkgo leaves in the mixed gas of fluorine gas and nitrogen, and fluorinating for 30-90 min at the temperature of 200-450 ℃ to obtain the prepared carbon fluoride material with the ginkgo leaves as the raw material.
Further, in the step 3, the dilute acid solution is prepared by acetic acid, nitric acid, hydrochloric acid and deionized water according to a volume ratio of 0.05-0.1: 1.
Further, the mass ratio of the carbonized ginkgo leaves in the step 3 to the dilute acid solution is 1: (2 to 8)
Further, in the step 4, the concentration ratio of the fluorine gas to the mixed gas of the fluorine gas and the nitrogen gas is 5% -10%.
The invention also provides a precise fluorinated ginkgo leaf, a purification method and functional application of the lithium fluorocarbon primary battery.
Further, the carbon fluoride positive electrode material is formed by coating a mixed slurry of a fluorinated ginkgo leaf material, SP and PVDF on an aluminum foil current collector.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a precise fluorinated ginkgo leaf, a purification method and functional application of a lithium primary battery. Washing the carbonized ginkgo leaves by dilute acid solution to remove impurities. And further purifying the carbonized ginkgo leaves at the temperature of 900-1100 ℃. Therefore, the lithium fluorocarbon battery obtained based on the precise fluorinated ginkgo leaf and purification method and the lithium primary battery preparation has certain electrical properties, and lays an important foundation for various preparation methods of carbon fluoride and popularization and application of lithium/carbon fluoride batteries.
Drawings
FIG. 1 is an SEM photograph of a sample of ginkgo biloba leaves obtained in example 1 after carbonization at 700 deg.C, wherein (a) and (b) are SEM photographs at different magnifications;
FIG. 2 is an SEM photograph of a sample of ginkgo biloba leaves obtained in example 2 after carbonization at 800 ℃, wherein (a) and (b) are SEM photographs at different magnifications;
FIG. 3 is an SEM photograph of a sample of ginkgo biloba leaves obtained in example 3 after carbonization at 900 deg.C, wherein (a) and (b) are SEM photographs at different magnifications;
FIG. 4 is a Raman plot of the sample obtained in example 6 after fluorination at 400 ℃;
FIG. 5 is the XRD pattern of the sample obtained in example 6 after fluorination at 400 ℃;
FIG. 6 is an SEM image of a sample obtained in example 5 after fluorination at 350 ℃;
FIG. 7 is an SEM image of a sample obtained in example 5 after fluorination at 375 ℃;
FIG. 8 is an SEM image of a sample obtained in example 4 after fluorination at 375 ℃;
FIG. 9 is an SEM image of a sample obtained in example 4 after fluorination at 400 ℃;
FIG. 10 is an SEM image of a sample obtained in example 6 after fluorination at 400 ℃;
FIG. 11 is a Mapping chart of a sample obtained in example 5 after fluorination at 375 ℃; wherein, (a) is SEM picture, (b) element general spectrogram, (c), (d), (e) and (f) are element spectrograms of carbon, fluorine, calcium and magnesium respectively;
FIG. 12 is an XPS plot of samples obtained in example 5 after fluorination at 375 deg.C;
FIG. 13 is a TEM image of a sample obtained in example 5 after fluorination at 375 ℃, wherein (a), (b), (c) (d), (e) and (f) are TEM images of the sample after precision fluorination at different magnifications;
FIG. 14 is a graph of the discharge curves at different discharge rates for a sample assembled cell after fluorination at 350 ℃ as obtained in example 4;
FIG. 15 is a graph of the discharge of a sample assembled cell after fluorination at 375 deg.C obtained in example 5 at different discharge rates;
fig. 16 is a graph of the discharge curves at different discharge rates for sample assembled batteries after fluorination at 400 c obtained in example 6.
Detailed Description
The technical scheme of the invention is further detailed in the following by combining the drawings and the specific examples.
Example 1
An accurate fluorinated ginkgo leaf and a purification method and functional application of a lithium primary battery are characterized by comprising the following steps:
And 2, placing 500g of air-dried ginkgo leaves in a CVD (chemical vapor deposition) furnace, heating to 120 ℃ at the speed of 10 ℃/min in the air atmosphere, then continuously heating to 700 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping the temperature at 700 ℃ for 60min, and naturally cooling to obtain the carbonized ginkgo leaves.
And 3, placing the carbonized ginkgo leaves in a suction filtration device, washing the ginkgo leaves for 3 times by using a dilute acid solution, washing the ginkgo leaves for 8 times by using deionized water, and then placing the ginkgo leaves in an oven at 50 ℃ for 60min to obtain the washed carbonized ginkgo leaves.
Example 2
This example is different from example 1 in that: the process of step 2 is adjusted as follows: placing 500g of air-dried ginkgo leaves in a CVD furnace, heating to 120 ℃ at the speed of 10 ℃/min in the air atmosphere, then continuously heating to 800 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping the temperature at 800 ℃ for 60min, and naturally cooling to obtain the carbonized ginkgo leaves.
Example 3
This example is different from example 1 in that: the process of step 2 is adjusted as follows: placing 500g of air-dried ginkgo leaves in a CVD furnace, heating to 120 ℃ at the speed of 10 ℃/min in the air atmosphere, then continuously heating to 900 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping the temperature at 900 ℃ for 60min, and naturally cooling to obtain the carbonized ginkgo leaves.
Example 4
An accurate fluorinated ginkgo leaf and a purification method and functional application of a lithium primary battery are characterized by comprising the following steps:
And 2, placing 500g of air-dried ginkgo leaves in a CVD (chemical vapor deposition) furnace, heating to 120 ℃ at the speed of 10 ℃/min in the air atmosphere, then continuously heating to 900 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping the temperature at 900 ℃ for 60min, and naturally cooling to obtain the carbonized ginkgo leaves.
And 3, placing the carbonized ginkgo leaves in a suction filtration device, washing the ginkgo leaves for 3 times by using a dilute acid solution, washing the ginkgo leaves for 8 times by using deionized water, and then placing the ginkgo leaves in an oven at 50 ℃ for 60min to obtain the washed carbonized ginkgo leaves.
And 4, placing the washed carbonized ginkgo leaves in the CVD furnace again, heating to 1000 ℃ at the speed of 10 ℃/min for 4 hours in the nitrogen atmosphere, regulating and controlling the graphitization degree and the surface defect structure of the carbon, and then naturally cooling to obtain the purified carbon source prepared from the ginkgo leaves.
And 5, placing the carbon source prepared from the ginkgo leaves in the mixed gas of fluorine gas and nitrogen, and fluorinating for 60min at 350 ℃ to obtain the carbon fluoride material prepared from the ginkgo leaves.
Example 5
This example is different from example 4 in that: the process of step 5 is adjusted as follows: placing a carbon source prepared from folium ginkgo in a mixed gas of fluorine gas and nitrogen, and fluorinating for 60min at 375 ℃ to obtain the carbon fluoride material prepared from folium ginkgo.
Example 6
This example is different from example 4 in that: the process of step 5 is adjusted as follows: placing a carbon source prepared from folium ginkgo in a mixed gas of fluorine gas and nitrogen gas, and fluorinating for 60min at 400 ℃ to obtain the carbon fluoride material prepared from folium ginkgo.
FIGS. 1-3 SEM pictures of ginkgo leaves obtained in example 1-3 after carbonization at 700 deg.C, 800 deg.C and 900 deg.C. SEM images of the carbon fluoride raw material before induction treatment under different magnifications show that the carbonized ginkgo leaf has porous microstructure and flaky characteristics capable of providing active sites for lithium ion reaction.
FIG. 4 is a Raman diagram of a carbon material treated in example 6 and fluorinated at 400 ℃. In FIG. 4, 1341cm-1And 1587cm-1The peak appears as a characteristic peak of carbon, corresponding to the D peak and the G peak, respectively, and ID/IGThe value of (A) is 0.97, indicating that the structure of the carbon material after fluorination is still ordered.
FIG. 5 is an XRD pattern of a carbon material fluorinated at 400 ℃ obtained by treatment in example 6. FIG. 5 is a tableThe carbon material after fluorination has more diffraction peaks, wherein the diffraction peaks at 2 theta of 13.28 degrees and 40.4 degrees respectively correspond to a (001) plane and a (100) plane of C-C of the fluorinated carbon; diffraction peaks at 28.2 °, 46.96 °, 55.72 °, 68.52 ° and 75.76 ° of 2 θ each represent CaF2。
FIG. 6 is an SEM photograph of a carbon material treated in example 4 and fluorinated at 350 ℃. As shown in the figure, when the fluorination is carried out at 350 ℃, the fluorination effect is not ideal because the temperature is too low.
FIGS. 7 and 8 are SEM images of a carbon material obtained by the treatment of example 6 after fluorination at 375 ℃. It is shown that after the treatment of example 6, due to the increase of temperature, the morphology of the material collapses, which leads to the increase of the compactness of the material and the decrease of the specific surface area, and finally influences the specific energy and the specific power of the battery.
FIGS. 9 and 10 are SEM images of the carbon material after fluorination at 400 ℃ obtained by the treatment of example 5. It is shown that after the treatment of example 5, the material is able to substantially maintain the morphology of the flakes, while the conductivity of the material after fluorination decreases, leading to the accumulation of secondary electrons and the picture becomes brighter.
FIG. 11 is a Mapping chart of the carbon material after fluorination at 400 ℃ obtained by the treatment of example 6. The Mapping analysis of the sample fluorinated by ginkgo leaves at 400 ℃ shows that: the material contains elements such as carbon, fluorine, magnesium, calcium and the like because the raw materials are remained due to incomplete purification process.
FIG. 12 is an XPS plot of a carbon material treated in example 6 and fluorinated at 400 ℃. XPS analysis of samples of ginkgo leaves fluorinated at 400 degrees celsius found: the high resolution scan of C1s indicated the presence of 6 peaks with binding energies of 284.7eV,285.6eV,287.1eV,288.7eV,290.3eV,293.3eV, where the tables represent C-C bonds, C ═ C bonds, semi-ionic C-F bonds, covalent C-F bonds, C-F3 bonds. In particular, the binding energy is 290.3eV, which corresponds to the C element in calcium carbonate and acetic acid adsorbed on MgO. It can be seen that certain elements of Mg and Ca are present in this sample.
FIG. 13 is a TEM image at different magnifications of a carbon fluoride material at 400 ℃ obtained by the treatment of example 6. The overall appearance presents a sheet shape, the material can be seen to have good crystallinity locally, large-area carbon in a crystalline form can appear, and a good foundation can be provided for the subsequent precise fluorination process and the improvement of the battery performance.
Assembling the battery:
the fluorinated ginkgo leaf samples obtained in example 4, example 5 and example 6 were mixed with conductive agent ketjen black and binder PVDF at a mass ratio of 8:1:1 to prepare slurry, the slurry was uniformly coated on a current collector aluminum foil, and vacuum-dried at 80 ℃ for 12 hours to obtain a positive plate. And then, assembling the button cell in a glove box by taking metal lithium as a negative electrode and taking an electrode plate prepared from fluorinated ginkgo leaves as a positive electrode, and standing for 24 hours to wait for testing.
FIG. 14 is a graph of the discharge curves at different discharge rates for a sample assembled cell after fluorination at 350 ℃ as obtained in example 4; it can be seen that the discharge curve of the fluorinated ginkgo biloba sample fluorinated at 350 ℃ is complete at the discharge rate of 0.01, 0.05, 0.1, 0.5 and 1C, and the voltage plateau decreases with the increase of the rate. The fluorinated ginkgo leaf sample fluorinated at 350 ℃ shows the best discharge performance under the discharge rate of 0.5C, and the specific capacity is about 300mAh/g when the discharge rate is cut to 1.5V.
FIG. 15 is a graph of the discharge of a sample assembled cell after fluorination at 375 deg.C obtained in example 5 at different discharge rates; it can be seen that the 375 ℃ fluorinated ginkgo biloba samples had complete discharge curves at discharge rates of 0.01, 0.05, 0.1, 0.5, 1C and are compared to fig. 14. The fluorinated ginkgo leaf sample fluorinated at 375 ℃ has more excellent specific capacity under different multiplying rates. And the best discharge performance is shown under the discharge rate of 0.5C, and the specific capacity is about 400mAh/g when the discharge rate is cut off to 1.5V.
FIG. 16 is a graph of the discharge at different discharge rates of a sample assembled cell after fluorination at 400 ℃ as obtained in example 6; it can be seen that the discharge curve of the fluorinated ginkgo biloba leaf sample fluorinated at 400 ℃ is complete under the discharge rate of 0.01, 0.05, 0.1, 0.5 and 1C. However, in comparison with fig. 14 and 15, the fluorinated ginkgo biloba leaf sample fluorinated at 400 ℃ has a larger fluorination depth, and the discharge curve has no obvious voltage plateau at the larger discharge rate of 0.5 and 1C. The fluorinated ginkgo leaf sample fluorinated at 400 ℃ has more excellent specific capacity under lower rate. The best discharge performance is shown under the discharge rate of 0.05C, and the specific capacity is more than 400mAh/g when the discharge rate is cut off to 1.5V.
Claims (7)
1. An accurate fluorinated ginkgo leaf and a purification method and functional application of a lithium primary battery are characterized by comprising the following steps:
step 1, collecting natural ginkgo leaves, washing dust and sandy soil by deionized water, and then airing.
And 2, placing the dried ginkgo leaves in a CVD furnace, heating to 120 ℃ in an air atmosphere for pre-carbonization, then continuously heating to 900 ℃ in a nitrogen atmosphere, keeping the temperature at 900 ℃ for 30-60min for carbonization, and naturally cooling to obtain the carbonized ginkgo leaves.
And 3, alternately washing the carbonized ginkgo leaves with a dilute acid solution and deionized water, filtering with a suction filtration device, and then placing in a drying oven at 50-80 ℃ for drying to obtain the washed and impurity-removed carbonized ginkgo leaves.
And 4, placing the washed carbonized ginkgo leaves in the CVD furnace again, heating to 900-1100 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping for 4-6h, regulating and controlling the graphitization degree and the surface defect structure of carbon, and then naturally cooling to obtain the purified carbon source prepared from the ginkgo leaves.
And 5, placing the carbon source prepared from the ginkgo leaves in the mixed gas of fluorine gas and nitrogen gas for fluorination to obtain the prepared carbon fluoride material with the ginkgo leaves as the raw material.
And 6, assembling the battery by using the fluorinated ginkgo leaves obtained in the step 3 as a positive electrode material of the lithium primary battery.
2. The diluted acid solution in the step 3 of claim 1 is a solution prepared by mixing acetic acid, nitric acid, hydrochloric acid and deionized water in a volume ratio of 0.05-0.1: 1.
3. The mass ratio of the ginkgo biloba leaves carbonized in the step 3 to the dilute acid solution in the claim 1 is 1: (2-8).
4. The process according to claim 1, wherein the mixed gas in step 5 is a mixed gas of fluorine gas and nitrogen gas having a concentration ratio of fluorine gas to fluorine gas of 5% to 10%.
5. The process of claim 1, wherein the fluorination temperature in step 5 is 200-450 ℃ and the fluorination time is 30-90 min.
6. The method for assembling a battery according to claim 1, wherein the positive electrode material of the lithium primary battery in step 6 is prepared by mixing fluorinated ginkgo leaves: conductive agent: the binder was mixed at a ratio of 8:1: 1.
7. Use of fluorinated ginkgo biloba leaves obtainable by the method according to any of the claims 1 to 6 as a positive electrode material for lithium primary batteries.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111480392.2A CN114148998B (en) | 2021-12-06 | 2021-12-06 | Precise fluorinated ginkgo leaf, purification method and functional application of lithium primary battery |
| GB2217450.2A GB2616099A (en) | 2021-12-06 | 2022-11-22 | Precise fluorination and purification method for ginkgo leaf, and functional use of primary lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111480392.2A CN114148998B (en) | 2021-12-06 | 2021-12-06 | Precise fluorinated ginkgo leaf, purification method and functional application of lithium primary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114148998A true CN114148998A (en) | 2022-03-08 |
| CN114148998B CN114148998B (en) | 2023-08-04 |
Family
ID=80453227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111480392.2A Active CN114148998B (en) | 2021-12-06 | 2021-12-06 | Precise fluorinated ginkgo leaf, purification method and functional application of lithium primary battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114148998B (en) |
| GB (1) | GB2616099A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2616099A (en) * | 2021-12-06 | 2023-08-30 | Yangtze Delta Region Institute Of Univ Of Electronic Science And Technology Of China Huzhou | Precise fluorination and purification method for ginkgo leaf, and functional use of primary lithium battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875475A (en) * | 2018-09-04 | 2020-03-10 | 天津大学 | Method for preparing high-specific-energy carbon fluoride anode material by gas-phase fluoridation of fruit shell carbon |
| CN110880599A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of high-performance fluorinated peanut shell hard carbon electrode material |
| CN111943168A (en) * | 2020-08-21 | 2020-11-17 | 华南农业大学 | Doping method and application of bio-based carbon material based on green bristlegrass |
| US20200381731A1 (en) * | 2019-05-30 | 2020-12-03 | Panasonic Intellectual Property Management Co., Ltd. | Active material for fluoride-ion secondary battery and fluoride-ion secondary battery using same |
| CN112441573A (en) * | 2019-09-03 | 2021-03-05 | 天津大学 | Preparation method and application of fluorine-doped hard carbon material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832109A (en) * | 2018-06-25 | 2018-11-16 | 扬州工业职业技术学院 | A method of anode material of lithium battery is prepared using ultrasonic wave |
| CN114335455B (en) * | 2021-12-06 | 2023-11-10 | 电子科技大学长三角研究院(湖州) | Method for precisely fluorinating soft carbon with adjustable crystallinity and primary battery performance research |
| CN114148998B (en) * | 2021-12-06 | 2023-08-04 | 电子科技大学长三角研究院(湖州) | Precise fluorinated ginkgo leaf, purification method and functional application of lithium primary battery |
-
2021
- 2021-12-06 CN CN202111480392.2A patent/CN114148998B/en active Active
-
2022
- 2022-11-22 GB GB2217450.2A patent/GB2616099A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875475A (en) * | 2018-09-04 | 2020-03-10 | 天津大学 | Method for preparing high-specific-energy carbon fluoride anode material by gas-phase fluoridation of fruit shell carbon |
| CN110880599A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of high-performance fluorinated peanut shell hard carbon electrode material |
| US20200381731A1 (en) * | 2019-05-30 | 2020-12-03 | Panasonic Intellectual Property Management Co., Ltd. | Active material for fluoride-ion secondary battery and fluoride-ion secondary battery using same |
| CN112441573A (en) * | 2019-09-03 | 2021-03-05 | 天津大学 | Preparation method and application of fluorine-doped hard carbon material |
| CN111943168A (en) * | 2020-08-21 | 2020-11-17 | 华南农业大学 | Doping method and application of bio-based carbon material based on green bristlegrass |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2616099A (en) * | 2021-12-06 | 2023-08-30 | Yangtze Delta Region Institute Of Univ Of Electronic Science And Technology Of China Huzhou | Precise fluorination and purification method for ginkgo leaf, and functional use of primary lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114148998B (en) | 2023-08-04 |
| GB2616099A (en) | 2023-08-30 |
| GB202217450D0 (en) | 2023-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107681142B (en) | Molybdenum disulfide coated carbon nanofiber used as lithium ion battery negative electrode material and preparation method thereof | |
| CN113346054B (en) | Preparation method and application of MXene-carbon nanocage-sulfur composite material | |
| CN110429282B (en) | Novel nano carbon sphere negative electrode material for lithium ion battery | |
| CN111244414A (en) | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction | |
| CN109148850B (en) | Preparation method of fluorinated graphene capsule and application of fluorinated graphene capsule in lithium primary battery | |
| CN113036121B (en) | Carbon-coated transition metal sulfide nanoflower structure, preparation method and application thereof | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| CN114520323A (en) | Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof | |
| GB2616100A (en) | Method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and performance study of primary battery | |
| CN108281627B (en) | Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN114597532A (en) | Method for directly regenerating failed lithium cobaltate positive electrode into high-voltage lithium cobaltate positive electrode and product | |
| CN111370656B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN111564610A (en) | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof | |
| CN114148998B (en) | Precise fluorinated ginkgo leaf, purification method and functional application of lithium primary battery | |
| CN112803018B (en) | Silicon-doped graphene composite material and preparation method and application thereof | |
| CN110265646B (en) | Nitrogen-doped graphene-like activated carbon material and preparation method and application thereof | |
| CN108878823B (en) | Preparation method of metal olivine coated nano silicon | |
| CN112234194B (en) | Iodine modified MXene material and preparation method and application thereof | |
| CN109671923A (en) | A kind of preparation method and lithium-sulfur cell of ordered nano array nitrogen sulphur codope carbon sulphur composite carbon bar material | |
| CN116207244A (en) | High-density high-purity silicon-carbon negative electrode material and preparation method thereof | |
| CN113506873A (en) | MXene composite modified VO2Zinc ion battery anode material and preparation method thereof | |
| CN110504450B (en) | Preparation method of heteroatom-doped hierarchical pore carbon material and application of heteroatom-doped hierarchical pore carbon material in lithium battery negative electrode slurry | |
| CN113540460A (en) | Composite material and preparation method and application thereof | |
| CN111244452A (en) | Novel lithium ion battery based on biomass porous carbon material as negative electrode material | |
| CN112794360A (en) | Preparation of nano SnO2Method for preparing/GC composite anode material |
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 |