CN112158832A - Method for improving specific capacity of carbon fluoride and discharge voltage through boron-doped graphene - Google Patents
Method for improving specific capacity of carbon fluoride and discharge voltage through boron-doped graphene Download PDFInfo
- Publication number
- CN112158832A CN112158832A CN202011068139.1A CN202011068139A CN112158832A CN 112158832 A CN112158832 A CN 112158832A CN 202011068139 A CN202011068139 A CN 202011068139A CN 112158832 A CN112158832 A CN 112158832A
- Authority
- CN
- China
- Prior art keywords
- boron
- doped graphene
- graphene
- furnace
- carbon fluoride
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 22
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000037303 wrinkles Effects 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/061—Halides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- 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
Abstract
The invention relates to a method for improving specific capacity of carbon fluoride and discharge voltage by boron-doped graphene, which comprises the following steps: 1) mixing boric acid serving as a boron source with graphene in an ethanol solution, uniformly mixing, and evaporating ethanol to obtain a mixture; 2) placing the mixture into a furnace, and introducing sufficient inert gas to remove air in the furnace; 3) raising the temperature of the furnace to 650-850 ℃; 4) keeping the reaction time for a period of time to obtain a product boron-doped graphene; 5) heating the boron-doped graphene product to a certain temperature, and introducing fluorine gas for fluorination; 6) keeping the reaction time for 12 hours to obtain boron fluoride doped graphene; 7) assembling to obtain the lithium-carbon fluoride battery.
Description
Technical Field
The invention relates to a method for improving specific capacity and discharge voltage of carbon fluoride by boron-doped graphene, namely preparing the boron-doped graphene by a high-temperature annealing method, and performing fluorination by taking the boron-doped graphene as a precursor to prepare the carbon fluoride. Due to the existence of boron atoms, the binding energy of the carbon fluoride material and lithium is improved, so that the discharge voltage and the specific capacity of the prepared carbon fluoride material are improved.
Background
The specific energy of the lithium-carbon fluoride battery is high and far higher than that of other primary batteries; the working voltage is high; the discharge performance is stable, and the discharge voltage can be kept stable in most of the working time; long storage life, small self-discharge and less than 1% of annual capacity loss; is green and environment-friendly. Therefore, the fluorinated carbon material is one of the international research hotspots for high-tech and high-performance novel carbon-based materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for improving the specific capacity of carbon fluoride and the discharge voltage by boron-doped graphene, and the method is simple and effective to operate. The prepared carbon fluoride material shows excellent discharge voltage and specific capacity, and the invention adopts the following technical scheme:
a method for improving specific capacity of carbon fluoride and discharge voltage by boron-doped graphene comprises the following steps:
1) mixing boric acid serving as a boron source with graphene in an ethanol solution, uniformly mixing, and evaporating ethanol to obtain a mixture;
2) placing the mixture into a furnace, and introducing sufficient inert gas to remove air in the furnace;
3) raising the temperature of the furnace to 650-850 ℃;
4) keeping the reaction time for a period of time to obtain a product boron-doped graphene;
5) heating the boron-doped graphene product to a certain temperature, and introducing fluorine gas for fluorination;
6) keeping the reaction time for 12 hours to obtain boron fluoride doped graphene;
7) assembling to obtain the lithium-carbon fluoride battery.
In the step 1), the mass ratio of boric acid to graphene is (8-12): 1.
in step 3), the furnace temperature is increased from room temperature to 650-850 ℃ within 150 minutes.
In step 4), the reaction time was kept for 4 hours.
In the step 5), the boron-doped graphene product is heated to 200-220 ℃.
In step 6), the reaction time was kept for 12 hours.
The method needs proper fluorination temperature to find the maximum discharge voltage, and has the advantages of simple operation, low cost, high yield, simple post-treatment and low preparation cost. The discharge voltage and specific capacity of the fluorinated graphene can be improved by doping the graphene boron. The properties of the resulting carbon fluoride material may vary depending on the fluorination temperature and the amount of boron doping.
Drawings
FIG. 1 SEM image of untreated graphene
FIG. 2 SEM image of graphene after boron doping
FIG. 3 TEM image of untreated graphene
FIG. 4 TEM image of graphene after boron doping
FIG. 5 XPS spectra of pristine graphene
FIG. 6 XPS spectra of boron doped graphene
FIG. 7 is a graph of fluorinated graphene discharge curves prepared from untreated graphene
FIG. 8 is a graph of discharge curves for fluorinated graphene prepared in example 1
FIG. 9 is a graph of discharge curves for fluorinated graphene prepared in example 2
Detailed Description
According to the invention, the method for preparing the lithium-carbon fluoride battery by doping boron into the graphene and taking the boron as a precursor is used for improving the discharge voltage and the specific capacity of the lithium-carbon fluoride battery. Due to the introduction of boron atoms, an electron cloud structure in the graphene is changed, p-type conductivity is induced in the graphene due to the electricity shortage of boron, the conductivity of the carbon fluoride is enhanced, and the binding energy of the carbon fluoride material and lithium is improved after boron doping. Therefore, the carbon fluoride material prepared and formed by the method can realize compatibility of high specific capacity and high discharge potential, and has great commercial application prospect due to high yield of the method. The excellent energy density of CFx may replace the commercial graphene fluoride to develop a high-performance lithium primary battery.
The technical solution of the present invention is explained below by specific examples.
The various starting materials used in the examples are commercially available products which can be used.
Example 1
1) Using 50g of boric acid as a boron source, blending 5g of graphene in an ethanol solution for 12h, and evaporating ethanol.
2) And (3) placing the blended boric acid and graphene into a heating area of a tubular furnace, installing and checking the air tightness of the tubular furnace, and introducing sufficient argon into the tube to remove air in the tubular furnace.
3) The tube furnace was warmed from room temperature to 700 ℃ over 150 minutes.
4) Keeping the reaction time for 4 hours, and taking out the furnace hearth after the reaction is finished and the temperature of the furnace hearth is reduced to room temperature to obtain the product of boron-doped graphene.
5) And (3) putting the product nitrogen-doped graphene into a reaction kettle, heating to 210 ℃, and introducing fluorine gas.
6) Keeping the reaction time for 12 hours, cooling to room temperature after the reaction is finished, taking out, and doping boron fluoride with graphene.
7) And finally assembling to obtain the lithium-carbon fluoride battery, and performing a discharge test to obtain a discharge voltage of 3.02V.
Example 2
1) Using 50g of boric acid as a boron source, blending 5g of graphene in an ethanol solution for 12h, and evaporating ethanol.
2) And (3) placing the blended boric acid and graphene into a heating area of a tubular furnace, installing and checking the air tightness of the tubular furnace, and introducing sufficient argon into the tube to remove air in the tubular furnace.
3) The tube furnace was warmed from room temperature to 800 ℃ over 150 minutes.
4) Keeping the reaction time for 4 hours, and taking out the furnace hearth after the reaction is finished and the temperature of the furnace hearth is reduced to room temperature to obtain the product of boron-doped graphene.
5) And (3) putting the product nitrogen-doped graphene into a reaction kettle, heating to 210 ℃, and introducing fluorine gas.
6) Keeping the reaction time for 12 hours, cooling to room temperature after the reaction is finished, taking out, and doping boron fluoride with graphene.
7) And finally assembling to obtain the lithium-carbon fluoride battery, and performing a discharge test to obtain a discharge voltage of 3.02V.
Fig. 1 to 4 are SEM and TEM images before and after boron doping, from which it can be found that the sample surface before calcination is less smooth and wrinkled, wrinkles begin to become more wrinkled after calcination with boric acid, and many defects are generated, which facilitate the introduction of boron atoms, thereby affecting the electrochemical performance.
As can be seen from comparison of the XPS spectra in fig. 5 and fig. 6, the boron-doped graphene has an obvious B1s peak, which indicates that boron atoms successfully enter the graphene, and the boron-doped graphene is obtained.
As can be seen from FIG. 7, the discharge voltage platform of the carbon fluoride material prepared by using the original graphene as the carbon source is about 2.62V, and the specific capacity is 708mAh g-1。
Although the method and the preparation technique of the present invention have been described by way of preferred embodiments, it is obvious to those skilled in the art that the method and the technical route described herein can be modified or recombined to realize the final preparation technique without departing from the content, spirit and scope of the present invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (6)
1. A method for improving specific capacity of carbon fluoride and discharge voltage by boron-doped graphene comprises the following steps:
1) mixing boric acid serving as a boron source with graphene in an ethanol solution, uniformly mixing, and evaporating ethanol to obtain a mixture;
2) placing the mixture into a furnace, and introducing sufficient inert gas to remove air in the furnace;
3) raising the temperature of the furnace to 650-850 ℃;
4) keeping the reaction time for a period of time to obtain a product boron-doped graphene;
5) heating the boron-doped graphene product to a certain temperature, and introducing fluorine gas for fluorination;
6) keeping the reaction time for 12 hours to obtain boron fluoride doped graphene;
7) assembling to obtain the lithium-carbon fluoride battery.
2. The method according to claim 1, wherein in the step 1), the mass ratio of the boric acid to the graphene is (8-12): 1.
3. the method of claim 1, wherein in step 3), the temperature of the furnace is increased from room temperature to 650 ℃ to 850 ℃ within 150 minutes.
4. The method of claim 1, wherein in step 4), the reaction time is maintained for 4 hours.
5. The method as claimed in claim 1, wherein in step 5), the boron-doped graphene product is heated to 200-220 ℃.
6. The method of claim 1, wherein in step 6), the reaction time is maintained for 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011068139.1A CN112158832A (en) | 2020-10-08 | 2020-10-08 | Method for improving specific capacity of carbon fluoride and discharge voltage through boron-doped graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011068139.1A CN112158832A (en) | 2020-10-08 | 2020-10-08 | Method for improving specific capacity of carbon fluoride and discharge voltage through boron-doped graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112158832A true CN112158832A (en) | 2021-01-01 |
Family
ID=73861532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011068139.1A Pending CN112158832A (en) | 2020-10-08 | 2020-10-08 | Method for improving specific capacity of carbon fluoride and discharge voltage through boron-doped graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112158832A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113346077A (en) * | 2021-05-17 | 2021-09-03 | 上海超碳石墨烯产业技术有限公司 | Phosphorus-modified carbon fluoride material and preparation method and application thereof |
| CN114927672A (en) * | 2022-06-20 | 2022-08-19 | 燕山大学 | Preparation method of boron-doped carbon fluoride anode material with high specific capacity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170303A (en) * | 2020-01-16 | 2020-05-19 | 厦门稀土材料研究所 | Preparation method and application of carbon fluoride material |
| CN111646459A (en) * | 2020-06-12 | 2020-09-11 | 北京航空航天大学 | Preparation method and application of boron-doped graphene material |
-
2020
- 2020-10-08 CN CN202011068139.1A patent/CN112158832A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170303A (en) * | 2020-01-16 | 2020-05-19 | 厦门稀土材料研究所 | Preparation method and application of carbon fluoride material |
| CN111646459A (en) * | 2020-06-12 | 2020-09-11 | 北京航空航天大学 | Preparation method and application of boron-doped graphene material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113346077A (en) * | 2021-05-17 | 2021-09-03 | 上海超碳石墨烯产业技术有限公司 | Phosphorus-modified carbon fluoride material and preparation method and application thereof |
| CN114927672A (en) * | 2022-06-20 | 2022-08-19 | 燕山大学 | Preparation method of boron-doped carbon fluoride anode material with high specific capacity |
| CN114927672B (en) * | 2022-06-20 | 2023-04-07 | 燕山大学 | Preparation method of boron-doped carbon fluoride anode material with high specific capacity |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10847798B2 (en) | Tellurium-doped MXene composite material, and preparation method and use thereof | |
| CN108011105B (en) | Carbon nanosheet material, preparation thereof and application thereof in sodium-ion battery | |
| EP3128585A1 (en) | Composite cathode material and preparation method thereof, cathode pole piece of lithium ion secondary battery, and lithium ion secondary battery | |
| CN107946576B (en) | High-rate graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN109786743B (en) | Tellurium-doped MXene material and preparation method and application thereof | |
| CN109148883A (en) | Anode material of lithium-ion battery and its preparation method and application based on pitch | |
| CN109817918B (en) | Sulfur-doped MXene composite material and preparation method and application thereof | |
| CN109888279B (en) | Selenium-doped MXene material and preparation method and application thereof | |
| CN104900864A (en) | Manganese dioxide/graphene lithium ion battery cathode material and preparation method thereof | |
| KR101790555B1 (en) | Boron doped silicon oxide based anode active material and Method of preparing for the same and Lithium secondary battery using the same | |
| CN112158832A (en) | Method for improving specific capacity of carbon fluoride and discharge voltage through boron-doped graphene | |
| WO2020147295A1 (en) | Se-doped mxene battery cathode material and preparation method and use thereof | |
| CN110155983B (en) | Preparation method of cotton-based porous biomass carbon | |
| CN111244414A (en) | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction | |
| CN111430697A (en) | Carbon-coated modified silicon composite lithium ion battery cathode material and preparation method thereof | |
| CN111293308A (en) | Negative electrode material, negative electrode, potassium ion battery and preparation method | |
| CN109888280B (en) | Sulfur-doped MXene negative electrode material of potassium ion battery and preparation method thereof | |
| CN113461016B (en) | Silicon-carbon negative electrode material and preparation method and application thereof | |
| CN116002660B (en) | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery | |
| CN112018383A (en) | Boron-phosphorus co-doped MXene material and preparation method thereof | |
| CN115947336A (en) | Sodium ion battery and modified hard carbon cathode thereof | |
| CN113130879B (en) | Preparation method of high-adsorption catalytic performance cathode material of lithium-sulfur battery | |
| CN109285996A (en) | A kind of preparation method of ternary composite cathode material of lithium ion battery | |
| CN110459737B (en) | Preparation method and application of carbon-coated ferrous borate with core-shell structure | |
| CN113265246A (en) | Carbon quantum dot doped hard carbon composite material and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210101 |