GB2616100A - Method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and performance study of primary battery - Google Patents
Method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and performance study of primary battery Download PDFInfo
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- GB2616100A GB2616100A GB2217504.6A GB202217504A GB2616100A GB 2616100 A GB2616100 A GB 2616100A GB 202217504 A GB202217504 A GB 202217504A GB 2616100 A GB2616100 A GB 2616100A
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- 229910021384 soft carbon Inorganic materials 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 26
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000003682 fluorination reaction Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 62
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 34
- 239000003960 organic solvent Substances 0.000 abstract description 10
- 238000000713 high-energy ball milling Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 32
- 239000007789 gas Substances 0.000 description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 18
- 239000011268 mixed slurry Substances 0.000 description 11
- 239000011812 mixed powder Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 7
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum 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
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 235000011201 Ginkgo Nutrition 0.000 description 1
- 241000218628 Ginkgo Species 0.000 description 1
- 235000008100 Ginkgo biloba Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 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
- 239000012495 reaction gas Substances 0.000 description 1
Classifications
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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
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- 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
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- 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
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
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- 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
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- 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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- 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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Abstract
A preparation method of a fluorinated soft carbon material with adjustable crystallinity is disclosed, which can be used for a cathode of a primary lithium battery. A soft carbon material is subjected to high-energy ball milling in an alkane solvent, for example n-pentane or n-heptane,such that the solvent undergoes a certain degree of coating. Further, the soft carbon material whose surface is coated with the organic solvent such as n-pentane and n-heptane is annealed in a furnace to eliminate the organic solvent and form a carbonized structure on the surface of the soft carbon; further, the soft carbon material is fluorinated by use of fluorine in the presence of nitrogen.
Description
METHOD FOR PRECISE PREPARATION OF FLUORINATED SOFT CARBON WITH ADJUSTABLE CRYSTALLINITY, AND PERFORMANCE STUDY OF PRIMARY
BATTERY
TECHNICAL FIELD
100011 The present disclosure belongs to the technical field of new materials for primary batteries, and in particular relates to a method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and a preparation method of a primary battery using an interface-regulated fluorinated carbon material as a cathode material of the primary battery.
BACKGROUND
[0002] In the current energy crisis environment, clean energy and renewable energy, such as wind energy, solar energy, and geothermal energy, have become an urgent need. However, in order to facilitate the use, these energy sources need to be converted into electrical energy, and correspondingly, high-capacity electrochemical power sources are required to store the converted electrical energy. Lithium primary batteries are one of the most common and practical energy supply devices, mainly including lithium/sulfur dioxide batteries, lithium/manganese dioxide batteries, lithium/thionyl chloride batteries, and lithium/carbon fluoride batteries. At present, lithium/sulfur dioxide battery is the most widely used battery, but has low specific capacity and narrow applicable temperature range. The lithium/carbon fluoride battery has a highly wide operating temperature (-40°C to 170°C), and also has stable operating voltage, environmental friendliness, high safety, and low self-discharge, showing a wide range of applications in medical and other fields. However, as the cathode material of lithium/fluoride carbon batteries, carbon fluoride has a relatively high cost. It is an urgent need for the development of lithium/carbon fluoride batteries by preparation of new carbon fluoride materials. The patent 202110866336.6 of a fluorinated carbon material provided a method for preparing a new type of integrated fluorinated carbon-based cathode. A carbon nanotube and graphene are sieved, and transferred using a microporous filter membrane to a vacuum oven for drying. After drying, the microporous filter membrane is peeled off to obtain a p-aphene/carbon nanotube current collector. The graphene/carbon nanotube current collector is placed in a reaction container, and fluorination is conducted with a reaction gas composed of a gas fluorine source and a diluent gas at 600°C to 800°C, to obtain the new type of integrated fluorinated carbon-based cathode.
[0003] The present disclosure provides a simple method for precisely preparing fluorinated soft carbon with adjustable crystallinity at a relatively low fluorination temperature and a preparation method of a primary battery. Organic solvents such as n-pentane and n-heptane regulate the particle size, surface crystallinity, and wettability with an electrolyte of the soft carbon; meanwhile, the soft carbon material whose surface is coated with organic solvents such as n-pentane and n-heptane is annealed to eliminate impurities in the organic solvent and solvent gas molecules, and further form carbonized and graphitized structures on the surface of the soft carbon. The fluorinated soft carbon obtained after the soft carbon material is precisely fluorinated is used as a cathode material, and a prepared lithium/fluorinated soft carbon battery has an excellent performance. Therefore, in the present disclosure, based on the method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and the preparation method of a primary battery, an obtained lithium/fluorinated soft carbon battery has excellent electrical properties. The method lays an important foundation for promoted application of the lithium/fluorinated soft carbon battery.
SUMMARY
[0004] In view of defects in the background, an objective of the present disclosure is to provide a method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and a preparation method of a primary battery. In the present disclosure, the soft carbon material is subjected to high-energy ball milling in a solvent such as n-pentane and n-heptane, and coated and carbonized to a certain extent to form a soft carbon structure with amorphous carbon, so as to control a particle size, surface crystallinity, an interface, and wettability with an electrolyte of the soft carbon. The soft carbon material is further precisely fluorinated to obtain an adjustable fluorinated soft carbon material The fluorinated soft carbon material after precise fluorination is used as a cathode material, to obtain a lithium/fluoride carbon battery with excellent el ectrochemi cal performances.
[0005] To achieve the above objective, the present disclosure adopts the following technical solutions.
[0006] The present disclosure provides a method for precise preparation of fluorinated soft carbon with adjustable crystallinity, including the following steps: [0007] step 1, dissolving a soft carbon powder in a n-alkane solvent such as a n-pentane solvent to form a mixed solution; [0008] step 2, placing the mixed solution in a high-energy ball mill tank, adding 5 mm zirconia balls, 8 mm zirconia balls, and 10 mm zirconia balls at a mass ratio of 5:3:2, and conducting ball milling at 500 r/min to 900 r/min for 0.5 h to 2 h to obtain a mixed slurry; [0009] step 3, annealing the mixed slurry at 1,000°C to 1,750°C for 1 h to 4 h to obtain a mixed powder, grinding the mixed powder, and drying in a vacuum oven at 60°C to 80°C for 6 h to 12 h to obtain a fluorinated soft carbon material with adjustable crystallinity; and 100101 step 4, conducting fluorination on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 300°C to 500°C for 0.5 h to 2 h to obtain a fluorinated soft carbon material.
[0011] Further, in step 1, the soft carbon and the n-alkane solvent such as n-pentane and nheptane that form the mixed solution have a mass ratio of (3-5):1.
100121 Further, in step 2, in the mixed solution placed in the high-energy ball mill tank, the soft carbon powder and the zirconia balls have a mass ratio of 1:(1-2).
100131 Further, in step 2, the high-energy ball milling is conducted for 5 min and then stopped for 10 min, alternating 3 to 5 times.
[0014] Further, in step 4, in the mixed gas, the fluorine and the nitrogen have a concentration ratio of 8% to 11%.
[0015] The present disclosure further provides use of the fluorinated soft carbon obtained by precise fluoridation as a cathode material of a primary lithium/carbon fluoride battery, where the primary lithium/carbon fluoride battery includes a fluorinated soft carbon-based cathode material, a lithium metal anode, an electrolyte, and a diaphragm.
[0016] Further, the fluorinated carbon fluoride-based cathode material is formed by coating a mixed slurry of the fluorinated soft carbon obtained by precise fluoridation, SP, and polyvinylidene fluoride (PVDF) at 8:8:1 on an aluminum foil current collector.
[0017] Compared with the prior art, the present disclosure has the following beneficial effects. 100181 The present disclosure provides a method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and a preparation method of a primary battery. Organic solvents such as n-pentane and n-heptane regulate a particle size, surface crystallinity, an interplanar spacing, an interface, a density, and wettability with an electrolyte of the soft carbon; meanwhile, the soft carbon material whose surface is coated with organic solvents such as n-pentane and n-heptane is annealed to eliminate organic solvent gas molecules, and further form carbonized and graphitized structures on the surface of the soft carbon. The fluorinated soft carbon obtained after the soft carbon material is precisely fluorinated is used as a cathode material, and a prepared lithium/fluorinated soft carbon battery has an excellent performance. Therefore, in the present disclosure, based on the precise preparation of fluorinated soft carbon with adjustable crystallinity, and the preparation method of a primary lithium battery, an obtained lithium/fluorinated soft carbon battery has certain electrical properties. The method lays an important foundation for promoted application of the lithium/fluorinated soft carbon battery.
BRIEF DESCRIPTION OF THE DRAWINGS
100191 FIG. 1 shows an high-resolution transmission electron microscopy (HRTEM) image of fluorinated soft carbon prepared by Example 3 and an appearance of a button battery assembled; 100201 FIG. 2 shows a field-emission scanning electron microscopy (FESEM) image of soft carbon prepared by mixing soft carbon obtained in Example 1 with n-pentane; [0021] FIG. 3 shows a FESEM image of soft carbon prepared by mixing soft carbon obtained in Example 2 with n-heptane; 100221 FIG. 4 shows a FESEM image of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3; 100231 FIG. 5 shows a FESEM image of fluorinated soft carbon annealed at 1,550°C and fluorinated at 300°C obtained in Example 8; [0024] FIG. 6 shows an HRTEM image of soft carbon prepared by mixing soft carbon obtained in Example 1 with n-pentane; [0025] FIG. 7 shows an HRTEM image of soft carbon prepared by mixing soft carbon obtained in Example 2 with n-heptane; [0026] FIG. 8 shows an HR;1EM image of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3; [0027] FIG. 9 shows an X-ray diffraction (XRD) pattern of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3; [0028] FIG. 10 shows a Raman spectrum of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3; 100291 FIG. 11 shows a particle size distribution of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3; 100301 FIG. 12 shows discharge curves of batteries assembled with the fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C to 500°C obtained in Examples 3 to 7 at a rate of 0.01 C; 100311 FIG. 13 shows discharge curves of batteries assembled with the fluorinated soft carbon annealed at 1,550°C and fluorinated at 300°C to 500°C obtained in Examples 8 to 12 at a rate of 0.01 C; and 100321 FIG. 14 shows discharge curves of batteries assembled with the fluorinated soft carbon annealed at 1,750°C and fluorinated at 300°C to 500°C obtained in Examples 13 to 17 at a rate of 0.01 C.
DETAILED DESCRIPTION OF THE EMBODIMENTS
100331 The technical solutions of the present disclosure will be further described below through specific examples.
100341 Example 1
100351 A method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and a performance study of a primary battery were provided, where the method included the following steps: [0036] step 1, a soft carbon powder was dissolved in a n-pentane solvent to form a mixed solution; 100371 step 2, the mixed solution was placed in a high-energy ball mill tank, 5 mm zirconia balls, 8 mm zirconia balls, and 10 mm zirconia balls were added at a mass ratio of 5:3:2, and ball milling was conducted at 900 r/min for 0.5 h to obtain a mixed slurry; and 100381 step 3, the mixed slurry was annealed at 1,350°C for 4 h to obtain a mixed powder, the mixed powder was ground, and dried in a vacuum oven at 80°C for 12 h to obtain a fluorinated soft carbon material with adjustable crystallinity.
[0039] Example 2
100401 Compared with Example 1, this example differed in that: step 1, a soft carbon powder was dissolved in a n-heptane solvent to form a mixed solution.
[0041] Example 3
[0042] A method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and a performance study of a primary battery were provided, where the method included the following steps: [0043] step 1, a soft carbon powder was dissolved in a n-pentane solvent to form a mixed solution; [0044] step 2, the mixed solution was placed in a high-energy ball mill tank, 5 mm zirconia balls, 8 mm zirconia balls, and 10 mm zirconia balls were added at a mass ratio of 5:3:2, and ball milling was conducted at 900 r/min for 0.5 h to obtain a mixed slurry; and 100451 step 3, the mixed slurry was annealed at 1,350°C for 4 h to obtain a mixed powder, the mixed powder was ground, and dried in a vacuum oven at 80°C for 12 h to obtain a fluorinated soft carbon material with adjustable crystallinity.
[0046] step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 300°C for 1 h to obtain a fluorinated soft carbon material.
[0047] Example 4
100481 This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 350°C for 1 h to obtain a fluorinated soft carbon material.
[0049] Example 5
100501 This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 400°C for 1 h to obtain a fluorinated soft carbon material.
[0051] Example 6
[0052] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 450°C for 1 h to obtain a fluorinated soft carbon material.
[0053] Example 7
[0054] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 500°C for 1 h to obtain a fluorinated soft carbon material.
[0055] Example 8
[0056] A method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and a performance study of a primary battery were provided, where the method included the following steps: [0057] step 1, a soft carbon powder was dissolved in a n-pentane solvent to form a mixed solution; [0058] step 2, the mixed solution was placed in a high-energy ball mill tank, 5 mm zirconia balls, 8 mm zirconia balls, and 10 mm zirconia balls were added at a mass ratio of 5:3:2, and ball milling was conducted at 900 r/min for 0.5 h to obtain a mixed slurry; and [0059] step 3, the mixed slurry was annealed at 1550t for 4 h to obtain a mixed powder, the mixed powder was ground, and dried in a vacuum oven at 80°C for 12 h to obtain a fluorinated soft carbon material with adjustable crystallinity.
[0060] step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 300°C for 1 h to obtain a fluorinated soft carbon material.
[0061] Example 9
[0062] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 350°C for 1 h to obtain a fluorinated soft carbon material.
[0063] Example 10
[0064] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 400°C for 1 h to obtain a fluorinated soft carbon material.
[0065] Example 11
[0066] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 450°C for 1 h to obtain a fluorinated soft carbon material.
[0067] Example 12
[0068] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 500°C for 1 h to obtain a fluorinated soft carbon material.
[0069] Example 13
[0070] A method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and a performance study of a primary battery were provided, where the method included the following steps: [0071] step 1, a soft carbon powder was dissolved in a n-pentane solvent to form a mixed solution; [0072] step 2, the mixed solution was placed in a high-energy ball mill tank, 5 mm zirconia balls, 8 mm zirconia balls, and 10 mm zirconia balls were added at a mass ratio of 5:3:2, and ball milling was conducted at 900 r/min for 0.5 h to obtain a mixed slurry; and [0073] step 3, the mixed slurry was annealed at 1750t for 4 h to obtain a mixed powder, the mixed powder was ground, and dried in a vacuum oven at 80°C for 12 h to obtain a fluorinated soft carbon material with adjustable crystallinity.
[0074] step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 300°C for 1 h to obtain a fluorinated soft carbon material.
[0075] Example 14
[0076] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 350°C for 1 h to obtain a fluorinated soft carbon material.
[0077] Example 15
[0078] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 400°C for 1 h to obtain a fluorinated soft carbon material.
[0079] Example 16
[0080] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 450°C for 1 h to obtain a fluorinated soft carbon material.
[0081] Example 17
[0082] This example differed from Example 3 in that: step 4, fluorination was conducted on the fluorinated soft carbon material with adjustable crystallinity in a mixed gas of fluorine and nitrogen at 500°C for 1 h to obtain a fluorinated soft carbon material.
[0083] FIG. 2 and FIG. 3 were a FESEM image of the soft carbon prepared by mixing the soft carbon obtained in Example 1 with the n-pentane solvent, and a FESEM image of the soft carbon prepared by mixing the soft carbon obtained in Example 2 with the n-heptane solvent, respectively. It was seen that the prepared soft carbon samples were in a block shape.
[0084] FIG. 4 and FIG. 5 were a FESEM image of the fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3, and a FESEM image of the fluorinated soft carbon annealed at 1,850°C and fluorinated at 300°C obtained in Example 8, respectively. It was seen that the fluorinated soft carbon samples prepared after fluorination were layered.
[0085] FIG. 6 and FIG. 7 were an HRTEM image of the soft carbon prepared by mixing the soft carbon obtained in Example 1 with the n-pentane solvent, and an HRTEM image of the soft carbon prepared by mixing the soft carbon obtained in Example 2 with the n-heptane solvent. It was seen that the edges of the samples had thin walls, indicating that the surface crystallinity of the soft carbon was regulated by the organic solvent.
[0086] FIG. 8 showed an HRTEM image of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3. It was seen that after the organic solvent regulated the particle size, surface crystallinity, interplanar spacing, density, and wettability of the soft carbon, the fluorinated soft carbon material after fluorination had a denser edge.
[0087] FIG. 9 showed an XRD pattern of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3. The diffraction peak at 20=26° corresponded to a (002) plane of the graphite structure, indicating that the fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C still had a graphite structure.
[0088] FIG. 10 showed a Raman spectrum of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3. As shown in the figure, the peaks at 1,341 cm-1 and 1,587 cm' were characteristic peaks of carbon, corresponding to peak D and peak G, respectively, and an kik value was 1.05, indicating that the fluorinated soft carbon material structure was still orderly after fluorination.
[0089] FIG. 11 showed a particle size distribution of fluorinated soft carbon annealed at 1,350°C and fluorinated at 300°C obtained in Example 3. it was seen that the fluorinated soft carbon samples had a particle size mainly concentrated in 0 pm to 20 pm, and most of them were the fluorinated soft carbon samples with a particle size of 0 p.m to 10 Rm.
[0090] Assembly of a battery: 10091] The fluorinated soft carbon samples obtained in Examples 3 to 17, a conductive agent Ketjen black, and a binder PVDF were prepared in a mass ratio of 8: 1:1 to obtain a slurry separately; the slurry was evenly coated on an aluminum foil current collector, and vacuum-dried at 80°C for 12 h to obtain a cathode sheet. In a glove box, metal lithium was used as an anode, and the electrode sheet prepared from fluorinated ginkgo leaf was used as a cathode. A button battery was assembled in the glove box, and then allowed to stand for 24 h for the test.
100921 FIG. 12 showed discharge curves of batteries assembled with the fluorinated soft carbon annealed at 1,350°C and fluorinated at 300-500°C obtained in Examples 3 to 7 at a rate of 0.01 C. It was seen that the fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 500°C and annealing at 1,350°C had a specific capacity of not less than 800 mAh/g at a discharge rate of 0.01C, but had a low voltage plateau and an unstable discharge curve. The fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 400°C and annealing at 1,350°C had a better discharge performance at a discharge rate of 0.01 C, showing a specific capacity of about 700 mAh/g at E5 V. 100931 FIG. 13 showed discharge curves of batteries assembled with the fluorinated soft carbon annealed at 1,550°C and fluorinated at 300°C to 500°C obtained in Examples 8 to 12 at a rate of 0.01 C. It was seen that the fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 400°C and annealing at 1,550°C had a higher voltage plateau in the discharge curve at a discharge rate of 0.01 C, but had a lower specific capacity of about 500 mAh/g. It was seen that the fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 500°C and annealing at 1,550°C had a better specific capacity at a discharge rate of 0.01C, but had a low voltage plateau and an unstable discharge curve. The fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 450°C and annealing at 1,550°C had a better discharge performance at a discharge rate of 0.01 C, showing a voltage plateau exceeding 2.5 V, and a specific capacity of about 700 mAh/g at 1.5 V. 100941 FIG. 14 showed discharge curves of batteries assembled with the fluorinated soft carbon annealed at 1,750°C and fluorinated at 300°C to 500°C obtained in Examples 13 to 17 at a rate of 0.01 C. It was seen that the fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 400°C and annealing at 1,750°C had a higher voltage plateau in the discharge curve at a discharge rate of 0.01 C, but had a lower specific capacity below 200 mAh/g. It was seen that the fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 500°C and annealing at 1,750°C had a better specific capacity at a discharge rate of 0.01 C, but had a low voltage plateau and an unstable discharge curve. The fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 450°C and annealing at 1,750°C had a better discharge performance at a discharge rate of 0.01 C, showing a voltage plateau exceeding 2.6 V. and a specific capacity of about 700 mAh/g at 1.5 V. Compared with FIG. 12 and FIG. 13, it was seen that the fluorinated soft carbon sample obtained by fluorinating the soft carbon material at 450°C and annealing at 1,750°C generally showed a more excellent discharge performance.
Claims (7)
- WHAT IS CLAIMED IS: I. A method for precise preparation of fluorinated soft carbon with adjustable crystallinity, comprising the following steps: step 1, dissolving a soft carbon powder in a n-alkane solvent such as a n-heptane solvent to form a mixed solution; step 2, placing the mixed solution in a high-energy ball mill, and conducting ball milling at a rotational speed, such that molecules of the n-alkane solvent are coated and carbonized to a certain extent, to regulate a particle size, surface crystallinity, an interplanar spacing of 0.35-0.42 nm, a density of 0.9-1.2 g/cm3, and wettability with an electrolyte of the soft carbon; step 3, annealing soft carbon obtained in step 1 in a high-temperature carbon tube furnace for 1 h to 4 h to remove residual solvent molecules and further carbonize the soft carbon; step 4, placing soft carbon obtained in step 2 into a tubular furnace, introducing fluorine to conduct fluorination to obtain fluorinated soft carbon, and re-optimizing the crystallinity and the particle size of the soft carbon; and step 5, conducting battery assembling using the fluorinated soft carbon obtained in step 3 as a cathode material of a primary lithium battery.
- 2. The method for precise preparation of fluorinated soft carbon with adjustable crystallinity according to claim 1, wherein in step 1, the soft carbon and the n-alkane have a mass ratio of (35): 1.
- 3. The method for precise preparation of fluorinated soft carbon with adjustable crystallinity according to claim 1, wherein in step 2, the ball milling is conducted in the high-energy ball mill at 500 r/min to 900 r/min for 0.5 h to 1 h.
- 4. The method for precise preparation of fluorinated soft carbon with adjustable crystallinity according to claim 1, wherein in step 3, the annealing is conducted at 1,000°C to 1,750°C
- 5. The method for precise preparation of fluorinated soft carbon with adjustable crystallinity according to claim 1, wherein in step 4, the fluorination is conducted at 350°C to 450°C for 0.5 h to 2 h under a concentration ratio of the fluorine to the nitrogen at 8% to 11%.
- 6 The method for precise preparation of fluorinated soft carbon with adjustable crystallinity according to claim 1, wherein in step 5, the cathode material of the primary lithium battery is prepared by mixing the fluorinated soft carbon, a conductive agent, and a binder at a ratio of 8:1:1.
- 7. Use of the fluorinated soft carbon prepared by the method according to any one of claims 1 to 6 as a cathode material of a primary lithium battery.
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