CN115893471A - Method for compounding silver oxide and carbon fluoride through plasma induction and application of lithium primary battery - Google Patents
Method for compounding silver oxide and carbon fluoride through plasma induction and application of lithium primary battery Download PDFInfo
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- CN115893471A CN115893471A CN202211404404.8A CN202211404404A CN115893471A CN 115893471 A CN115893471 A CN 115893471A CN 202211404404 A CN202211404404 A CN 202211404404A CN 115893471 A CN115893471 A CN 115893471A
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 146
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 73
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000006698 induction Effects 0.000 title claims description 13
- 238000013329 compounding Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 85
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005516 engineering process Methods 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 22
- 239000011268 mixed slurry Substances 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 8
- 238000011419 induction treatment Methods 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 abstract description 17
- 238000012986 modification Methods 0.000 abstract description 17
- 238000011282 treatment Methods 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000010287 polarization Effects 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 33
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 description 9
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 9
- 238000009832 plasma treatment Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- 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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Carbon And Carbon Compounds (AREA)
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Abstract
A method for modifying carbon fluoride by combining silver oxide modification and air plasma technology and application of a lithium primary battery belong to the technical field of primary batteries. The invention utilizes the ball milling mixing of the silver oxide and the carbon fluoride material to reduce the particle size, increase the specific surface area of the carbon fluoride material and expose more discharge reaction active sites. In addition, free ions in the air plasma bombard the silver oxide to reduce the silver oxide to realize partial silver doping, and the reduced silver is used as a conductive network in the discharging process to reduce the polarization phenomenon in the discharging process. The oxygen-containing groups of the air plasma and a large number of oxygen-containing groups obtained by reduction of silver oxide realize slight oxidation of the surface of the carbon fluoride material. And the air plasma modification treatment further regulates and controls the F/C value and the C-F bond type of the carbon fluoride material, so that the rate capability and the capacity capability of the carbon fluoride material are improved, the voltage platform is improved, and the voltage hysteresis phenomenon is obviously improved. Therefore, the prepared lithium fluorocarbon primary battery based on the carbon fluoride modified by combining silver oxide doping and air plasma technology has the characteristics of high rate performance, high specific capacity, high energy density and high voltage platform, and lays an important foundation for popularization and application of the lithium fluorocarbon primary battery.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a method for modifying a carbon fluoride material by combining ball milling, silver oxide doping, oxidation and air plasma induction treatment, and a lithium-carbon fluoride primary battery is prepared by taking the modified carbon fluoride material as an anode material of the lithium primary battery.
Background
The carbon fluoride material as the positive electrode material of the lithium primary battery has the advantages of large specific energy, high working voltage, wide working temperature range, small self-discharge and the like, so that the carbon fluoride material is widely applied to the fields of energy, military, medical treatment and the like. However, the fluorocarbon material has poor conductivity, so that the discharge performance of the fluorocarbon material under a high rate is poor, and the problems of voltage delay, low discharge platform and the like exist, so that the fluorocarbon lithium battery cannot meet the discharge requirement of the high rate. Therefore, the difficulty of research on the carbon fluoride material is to improve the electrochemical performance of the lithium carbon fluoride primary battery system and to realize high energy density and good discharge performance of the carbon fluoride material under the condition of large current output. At present, aiming at the research difficulty of carbon fluoride materials, methods such as mixing other anode materials, modifying anode materials by metal oxides and compounds thereof, coating carbon or coating other conductive materials and the like are mostly adopted to improve the disadvantages of the carbon fluoride materials in electrochemical performance. For example, chinese patent 202110553040.9 discloses a method for preparing a carbon fluoride composite positive active material, which improves the voltage hysteresis of a lithium-carbon fluoride battery at the initial discharge stage by using a carbon fluoride composite positive active material prepared by ball-milling and mixing carbon fluoride and ketjen black. However, in the method, if the proportion of the cathode material mixed with the Ketjen black is too high, the specific capacity of the carbon fluoride is reduced, so that the high specific capacity of the lithium carbon fluoride battery is difficult to realizeTo maintain. For another example, chinese patent 202110722710.5 discloses a method for modifying a carbon fluoride anode material by using chromium oxide or a compound thereof, and the invention adopts a high-energy ball milling method to mill Cr 2 O 5 @ C or Cr 8 O 21 Uniformly mixing with carbon fluoride material, and calcining at high temperature to obtain small amount of uniformly coated Cr on the surface 2 O 5 @ C or Cr 8 O 21 The carbon fluoride material of (1). Although the rate performance of the lithium-carbon fluoride battery is improved and the temperature rise of the lithium-carbon fluoride battery in the discharging process is reduced, the capacity of a small amount of carbon fluoride material is sacrificed, the problem of voltage hysteresis is still serious after the problem is improved, and the voltage platform is still lower after the voltage platform is improved. Therefore, it is important to develop a carbon fluoride anode material which can ensure that the specific capacity of the carbon fluoride material is not damaged, can meet the requirement of high-rate discharge, can improve the voltage delay phenomenon and can improve the voltage platform.
Disclosure of Invention
The invention aims to provide a method for treating carbon fluoride material by combining silver oxide doping and air plasma induction treatment technologies, aiming at the defects in the prior art. The modification thought of the invention is mainly divided into four aspects: ball-milling and mixing the silver oxide and the carbon fluoride material to reduce the particle size; free ions in the air plasma bombard the silver oxide to reduce the silver oxide to realize partial silver doping; besides the oxygen-containing groups in the air plasma, the silver oxide is reduced to enable a large number of oxygen-containing groups in free ions to achieve slight oxidation of the surface of the carbon fluoride material; the air plasma induction further regulates and controls the F/C value and the C-F bond type of the carbon fluoride material. The carbon fluoride modified by the combined technology is used as a positive electrode material, so that the lithium carbon fluoride battery with high rate performance, high specific capacity, high energy density, high voltage platform and obviously improved voltage hysteresis effect is obtained.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a method for modifying and treating carbon fluoride by combining silver oxide doping and air plasma induction technology is characterized by comprising the following steps:
and 4, weighing 0.1-100 g of silver oxide doped carbon fluoride material, placing the carbon fluoride material into a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, starting a vacuum pump, vacuumizing the cavity in air atmosphere to maintain the vacuum degree in the cavity within the range of 10-30 Pa for 10-30 min, starting a plasma excitation source, and performing plasma induction treatment at the power of 50-150W for 1-120 min to obtain the carbon fluoride anode material modified by the combined silver oxide doping and air plasma induction technology.
The mass ratio of the total mass of the carbon fluoride powder and the silver oxide to the absolute ethyl alcohol forming the mixture in the step 1 is (3-5): 1.
in the step 2, the mass ratio of the total mass of the carbon fluoride powder and the silver oxide in the mixture arranged in the ball milling tank to the mass of the added zirconia balls is 1: (1. About.2)
In the step 2, the ball milling is carried out for 30min and then stopped for 10min
The invention also provides application of the fluorinated carbon subjected to modification treatment by combining silver oxide doping and air plasma induction technology as a positive electrode material of a lithium fluorinated carbon primary battery, wherein the lithium fluorinated carbon primary battery comprises the fluorinated carbon positive electrode material, a lithium metal negative electrode, electrolyte and a diaphragm.
Further, the carbon fluoride cathode material is formed by coating a mixed slurry of carbon fluoride, SP and PVDF subjected to combined ball milling, silver oxide doping and air plasma induction technology modification treatment on an aluminum foil current collector.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for modifying and treating carbon fluoride by combining silver oxide doping and air plasma induction technology and preparation of a lithium primary battery. In addition, free ions in the air plasma bombard the silver oxide to reduce the silver oxide to realize partial silver doping, so that the silver can be used as a conductive network in the discharge process of the lithium fluorocarbon primary battery, the problem of poor discharge performance under high multiplying power and the voltage hysteresis phenomenon can be improved, and a high discharge voltage platform of the lithium fluorocarbon primary battery is maintained. In addition to the oxygen-containing groups themselves in the air plasma, silver oxide reduction results in a large number of oxygen-containing groups in the free ions to achieve a slight oxidation of the carbon fluoride material surface. The air plasma induction further regulates the F/C value and the C-F bond type of the carbon fluoride material, so that the lithium carbon fluoride primary battery provides more capacity. Therefore, the carbon fluoride modified by the combined silver oxide doping and air plasma induction technology has the characteristics of high rate performance, high specific capacity, high energy density and high voltage platform, and lays an important foundation for popularization and application of the lithium carbon fluoride battery.
Drawings
FIG. 1 shows a modified fluorocarbon composite material CF obtained in example 2 and subjected to a combination of silver oxide doping and air plasma technology x -SEM images of 3 (silver oxide: CFx = 0.9) at different magnifications;
FIG. 2 is a graph of the discharge curves at different discharge rates for a lithium fluorocarbon primary cell assembled with virgin fluorocarbon materials, CF x -1 is a raw carbon fluoride material;
FIG. 3 shows a composite CF of ball-milled silver oxide and air plasma treated fluorocarbon obtained in example 1 x -2 (silver oxide: CFx = 0.1) discharge curves at different discharge rates for assembled lithium fluorocarbon primary cells, CF x -2 is the carbon fluoride material obtained in example 1 after ball milling and air plasma treatment;
FIG. 4 shows the combined silver oxide obtained in example 2Carbon fluoride composite material CF after doping and air plasma technology modification treatment x -3 (silver oxide: CFx = 0.9); CF (compact flash) x -3 is the carbon fluoride material obtained in example 2 after modification treatment by combining silver oxide doping and air plasma technology;
FIG. 5 shows the original carbon fluoride material CF x -1 carbon fluoride material CF obtained in example 1 x -2 and fluorinated carbon material CF obtained in example 2 x -3 discharge performance comparison curves at 1C for the assembled lithium fluorocarbon primary cells; CF (compact flash) x -1 is the original carbon fluoride material, CF x -2 is the ball milled and air plasma treated carbon fluoride material obtained in example 1, CF x -3 is the carbon fluoride material obtained in example 2 after modification treatment by combining silver oxide doping and air plasma technology;
FIG. 6 shows the original carbon fluoride material CF x -1 carbon fluoride Material CF obtained in example 1 x -2 and fluorinated carbon material CF obtained in example 2 x -3 EIS curve of the assembled lithium fluorocarbon primary cell; CF (compact flash) x -1 is the original carbon fluoride material, CF x -2 is the ball milled and air plasma treated carbon fluoride material obtained in example 1, CF x -3 is the carbon fluoride material obtained in example 2 after modification treatment by combining silver oxide doping and air plasma technology;
Detailed Description
The technical scheme of the invention is further detailed in the following by combining the drawings and the specific examples.
Example 1
A method for modifying treated carbon fluoride using a combination of silver oxide doping and air plasma induced techniques, comprising the steps of:
step 4, weighing 0.5g of ball-milled carbon fluoride material, placing the ball-milled carbon fluoride material in a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, starting a vacuum pump, vacuumizing the cavity in an air atmosphere to maintain the vacuum degree in the cavity within 10Pa for 10min, starting a plasma excitation source, performing plasma induction treatment for 10min under the power of 50W to obtain the ball-milled and air plasma treated carbon fluoride material, wherein the mark is CF x -2。
Example 2
A method for modifying treated carbon fluoride using a combination of silver oxide doping and air plasma induced techniques, comprising the steps of:
step 4, weighing 10g of ball-milled carbon fluoride material, placing the material in a tubular furnace cavity of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, starting a vacuum pump, vacuumizing the cavity in air atmosphere to maintain the vacuum degree in the cavity for 30min within the range of 30Pa, starting a plasma excitation source, and performing plasma induction treatment for 30min under the power of 200W to obtain the carbon fluoride material which is subjected to combined silver oxide doping and air plasma technology modification treatment and marked as CF x -3。
Example 3
A method for modifying treated carbon fluoride using a combination of silver oxide doping and air plasma induced techniques, comprising the steps of:
and 4, weighing 50g of ball-milled carbon fluoride material, placing the ball-milled carbon fluoride material in a cavity of a tubular furnace of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, starting a vacuum pump, vacuumizing the cavity in an air atmosphere to maintain the vacuum degree in the cavity within the range of 20Pa for 20min, starting a plasma excitation source, and performing plasma induction treatment for 20min under the power of 200W to obtain the carbon fluoride material subjected to combined silver oxide doping and air plasma technology modification treatment.
Example 4
A method for modifying treated carbon fluoride by using a combined ball milling, silver oxide doping and air plasma induction technology is characterized by comprising the following steps:
and 4, weighing 100g of ball-milled carbon fluoride material, placing the ball-milled carbon fluoride material in a cavity of a tubular furnace of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, starting a vacuum pump, vacuumizing the cavity in an air atmosphere to maintain the vacuum degree in the cavity within the range of 10-30 Pa for 30min, starting a plasma excitation source, and performing plasma induction treatment for 20min under the power of 100W to obtain the carbon fluoride material subjected to combined silver oxide doping and air plasma technology modification treatment.
Assembling the battery:
preparing slurry from a carbon fluoride raw material and the carbon fluoride material obtained in the embodiments 1 to 4 and subjected to modification treatment by combining silver oxide doping and an air plasma technology, SP and a binder PVDF according to a mass ratio of 8. And then assembling the button cell in a glove box by taking the metal lithium as a negative electrode and the fluorocarbon electrode plate as a positive electrode, and standing for 24h for testing. Labelling the fluorocarbon starting Material as CF x -1, labeling the carbon fluoride material obtained in example 1 as CF x -2, labeling the carbon fluoride material obtained in example 2 as CF x -3。
FIG. 1 shows a carbon fluoride material CF obtained in example 2 x -3 SEM images at different magnifications; it can be seen that the carbon fluoride material is in the form of a bulk layer and has a smooth surface. The carbon fluoride material after the combined silver oxide doping and air plasma technology modification treatment produces a plurality of exfoliated lamellar carbon fluorides.
FIG. 2 shows the original carbon fluoride material CF x -1 discharge curves of the assembled lithium fluorocarbon primary cell at different discharge rates; it can be seen that the specific capacity is lower as the discharge rate is increased. Under the high discharge rate of 6C, the specific capacity is less than 200mAh g -1 . And the original carbon fluoride material CF x -1 the assembled lithium fluorocarbon primary battery has the defects of unstable voltage platform, poor rate performance and incapability of discharging at a large rate. Under the discharge rate of 1C, the cut-off voltage is 1.5V, and the specific capacity is 673.54 mAh.g -1 。
FIG. 3 shows a fluorinated carbon material CF obtained in example 1 after silver oxide recombination and air plasma treatment x -2 assembled lithium fluorinationThe discharge curves of the carbon primary battery under different discharge rates; by comparison, it can be seen that the original carbon fluoride material CF x The problem of unstable-1 voltage plateau is obviously improved after ball milling and air plasma treatment. Carbon fluoride material CF after ball milling and air plasma treatment x The cut-off voltage of the lithium fluorocarbon primary battery assembled by-2 is 1.5V under the discharge rate of 1C, and the specific capacity of the lithium fluorocarbon primary battery is increased to 703.38 mAh.g -1 . Under the discharge rate of 6C at most, the cut-off voltage is 1.5V, and the specific capacity is increased to 569.74 mAh.g -1 。
FIG. 4 shows CF carbon fluoride material obtained in example 2 after silver oxide doping and modification treatment by air plasma technology x -3 discharge curves of the assembled lithium fluorocarbon primary cell at different discharge rates; as can be seen by comparison with FIGS. 2 and 3, the CF is further doped with silver oxide x The voltage platform of the discharge curve of the assembled lithium fluorocarbon primary battery is obviously more stable and higher, the cut-off voltage is 1.5V under the discharge rate of 1C, the voltage platform is increased to 2.74V, and the specific capacity is increased to 755.51mAh g -1 . Under the condition of high discharge rate of 8C, the cut-off voltage is 1.5V, the voltage platform reaches 2.27V, and the specific capacity is increased to 592.14 mAh.g -1 。
FIG. 5 shows the original carbon fluoride material CF x -1 carbon fluoride Material CF obtained in example 1 x -2 and fluorinated carbon material CF obtained in example 2 x -3 discharge performance comparison curve at 1C for the assembled lithium fluorocarbon primary cell; virgin carbon fluoride material CF x -1 assembled lithium fluorocarbon primary battery with 1.5V cut-off voltage and 673.54mAh g specific capacity under 1C discharge rate -1 Carbon fluoride material CF after ball milling and air plasma treatment x The cut-off voltage of the lithium fluorocarbon primary battery assembled by the lithium fluorocarbon primary battery 2 is 1.5V under the discharge rate of 1C, and the specific capacity of the lithium fluorocarbon primary battery is increased to 703.38 mAh.g -1 CF is more original than the carbon fluoride material x 1, the specific capacity of the assembled lithium fluorocarbon primary battery is improved by 4.43 percent. Carbon fluoride material CF subjected to silver oxide doping and air plasma technology modification treatment x -3 discharge of assembled lithium fluorocarbon primary cells at 1CUnder the condition of electric multiplying power, the cut-off voltage is 1.5V, the voltage platform is increased to 2.74V, and the specific capacity is increased to 755.51 mAh.g -1 CF, compared with the original carbon fluoride material x The specific capacity of the lithium fluorocarbon primary battery assembled by-1 is improved by 12.17%.
FIG. 6 shows the original carbon fluoride material CF x -1, carbon fluoride material CF obtained in example 1 x -2 and fluorinated carbon material CF obtained in example 2 x -3 EIS curve of assembled lithium fluorocarbon primary cells; charge transfer resistance R ct The slope of the straight line in the EIS curve indicates Li corresponding to the semicircle in the EIS curve + The diffusion resistance of (2). Analysis of carbon fluoride Material CF x -1 Rct of 185.50 Ω, carbon fluoride material CF subsequently subjected to AgO and air plasma treatment x -2 Rct is reduced to 126.00 omega, and the carbon fluoride material CF is modified by combining silver oxide doping and air plasma technology x Rct of-3 decreased again, down to 44.49 Ω. The analysis result proves that not only the modification of the silver oxide doped silver oxide is beneficial to reducing the Rct by combining with the induction of air plasma, but also the Rct can be further reduced by doping the silver oxide. Lower Rct is more favorable for charge transfer and ion transport, thus CF x -3 performance is improved when the lithium fluorocarbon primary battery positive electrode material is used.
Claims (2)
1. A method for modifying carbon fluoride by combining silver oxide doping and air plasma technology is characterized by comprising the following steps:
step 1, according to the mass ratio of the silver oxide to the carbon fluoride powder being (0.1-0.9): 1, weighing silver oxide and carbon fluoride powder and placing the silver oxide and the carbon fluoride powder into absolute ethyl alcohol to form a mixture;
step 2, placing the mixture into a ball milling tank, adding zirconia balls with the specification of 5/8/10mm =5/3/2, and performing ball milling at the rotating speed of 200-400r/min for 0.5-4h to obtain mixed slurry;
step 3, drying the mixed slurry in an oven at 40-60 ℃ for 6-12h, and sieving the dried mixed slurry with a 200-mesh sieve to obtain a silver oxide-doped carbon fluoride material;
and 4, weighing 0.1-100 g of silver oxide-doped carbon fluoride material, placing the carbon fluoride material in a cavity of a tubular furnace of Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, starting a vacuum pump, vacuumizing the cavity in air atmosphere to maintain the vacuum degree in the cavity within the range of 10-30 Pa for 10-30 min, starting a plasma excitation source, and performing plasma induction treatment at the power of 50-150W for 1-120 min to obtain the carbon fluoride anode material modified by combining silver oxide doping and air plasma induction technology.
2. Use of the carbon fluoride material modified by the combined silver oxide doping and air plasma technique obtained by the method of claim 1 as a positive electrode material for lithium fluorocarbon primary cells.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211404404.8A CN115893471A (en) | 2022-11-10 | 2022-11-10 | Method for compounding silver oxide and carbon fluoride through plasma induction and application of lithium primary battery |
| GB2217501.2A GB2624256A (en) | 2022-11-10 | 2022-11-23 | Method for compounding carbon fluoride with silver oxide by plasma induction, and use of primary lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211404404.8A CN115893471A (en) | 2022-11-10 | 2022-11-10 | Method for compounding silver oxide and carbon fluoride through plasma induction and application of lithium primary battery |
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| CN115893471A true CN115893471A (en) | 2023-04-04 |
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| CN202211404404.8A Pending CN115893471A (en) | 2022-11-10 | 2022-11-10 | Method for compounding silver oxide and carbon fluoride through plasma induction and application of lithium primary battery |
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| CN (1) | CN115893471A (en) |
| GB (1) | GB2624256A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2624256A (en) * | 2022-11-10 | 2024-05-15 | Yangtze Delta Region Institute Of Univ Of Electronic Science And Technology Of China Huzhou | Method for compounding carbon fluoride with silver oxide by plasma induction, and use of primary lithium battery |
| CN118083956A (en) * | 2024-04-26 | 2024-05-28 | 中国矿业大学 | Carbon fluoride with high-conductivity structural defect on surface and preparation method and application thereof |
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| CN112209362A (en) * | 2020-09-27 | 2021-01-12 | 电子科技大学 | Method for activating carbon fluoride by plasma induction and preparation of lithium primary battery |
| CN113363494A (en) * | 2021-06-28 | 2021-09-07 | 贵州梅岭电源有限公司 | Method for modifying carbon fluoride anode material by using chromium oxide or compound thereof |
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| CN115893471A (en) * | 2022-11-10 | 2023-04-04 | 电子科技大学长三角研究院(湖州) | Method for compounding silver oxide and carbon fluoride through plasma induction and application of lithium primary battery |
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2022
- 2022-11-10 CN CN202211404404.8A patent/CN115893471A/en active Pending
- 2022-11-23 GB GB2217501.2A patent/GB2624256A/en active Pending
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| CN113363494A (en) * | 2021-06-28 | 2021-09-07 | 贵州梅岭电源有限公司 | Method for modifying carbon fluoride anode material by using chromium oxide or compound thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2624256A (en) * | 2022-11-10 | 2024-05-15 | Yangtze Delta Region Institute Of Univ Of Electronic Science And Technology Of China Huzhou | Method for compounding carbon fluoride with silver oxide by plasma induction, and use of primary lithium battery |
| CN118083956A (en) * | 2024-04-26 | 2024-05-28 | 中国矿业大学 | Carbon fluoride with high-conductivity structural defect on surface and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB202217501D0 (en) | 2023-01-04 |
| GB2624256A (en) | 2024-05-15 |
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