CN112542584A - Carbon fluoride nanohorn material for lithium primary battery positive electrode material and preparation method thereof - Google Patents
Carbon fluoride nanohorn material for lithium primary battery positive electrode material and preparation method thereof Download PDFInfo
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- CN112542584A CN112542584A CN201910898497.6A CN201910898497A CN112542584A CN 112542584 A CN112542584 A CN 112542584A CN 201910898497 A CN201910898497 A CN 201910898497A CN 112542584 A CN112542584 A CN 112542584A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- C01B32/15—Nano-sized carbon materials
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a carbon fluoride nanohorn material for a lithium primary battery positive electrode material and a preparation method thereof. The preparation method is simple and easy to implement, and the prepared carbon fluoride nanohorn material can be used for the positive electrode of the lithium primary battery and shows relatively good performance.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a method for preparing carbon fluoride nanohorns by using fluorine gas as a fluorine source, in particular to a method for preparing carbon fluoride nanohorns used as a lithium primary battery cathode material by fluorine gas fluorination.
Background
Lithium primary batteries have become the leading product in the primary battery field due to their superior characteristics of light weight, high voltage and energy output, and their superior storage time, covering almost all markets, from medical implant devices to high performance military applications such as space sensors and missile power supplies. In all the solid positive electrode materials of the lithium primary battery, the carbon fluoride has the highest mass specific energy and has obvious advantages compared with other positive electrode materials, and the excellent electrochemical performance of the lithium carbon fluoride battery enables the lithium carbon fluoride battery to have very wide application prospects in the field of future power supplies, and meanwhile, the lithium carbon fluoride battery has good safety, high utilization rate and wide temperature application range. The battery system is very suitable for military use, can be used for portable small-sized weapon equipment, can also provide stable power for large-scale sea, land and air equipment, such as a space sensor and a missile power supply, and obviously improves the comprehensive level of modernization, informatization and digitization of the weapon equipment system.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a carbon fluoride nanohorn material for a lithium primary battery positive electrode material and a preparation method thereof, wherein a curvature structure at one end of a carbon nanohorn is favorable for generation of a fluorocarbon semi-ionic bond, discharge voltage and power density are improved, and the carbon nanohorn is used as a carbon source to prepare a carbon fluoride material for the lithium primary battery positive electrode material.
The technical purpose of the invention is realized by the following technical scheme.
A carbon fluoride nanohorn material for a lithium primary battery positive electrode material and a preparation method thereof are carried out according to the following steps: placing the carbon nanohorn in a reaction vessel, pumping to a vacuum state, heating to 100-300 ℃, and introducing fluorine-containing reaction gas into the reaction vessel for reaction to obtain the carbon fluoride nanohorn material.
Further, the fluorination reaction temperature is 200 to 250 ℃.
Further, the fluorination reaction time is 1 to 10 hours, preferably 3 to 8 hours.
Further, in the fluorine-containing reaction gas, the percentage by volume of fluorine gas is 10 to 40%, preferably 20 to 30%.
And introducing fluorine-containing reaction gas until the gas pressure reaches 0-0.1 MPa.
In the technical scheme of the invention, the raw material carbon nanohorn is put into a vacuum drying oven at 60-100 ℃, anhydrous phosphorus pentoxide is put into the bottom of the vacuum drying oven, and the carbon nanohorn is taken out and sealed for standby after 4-8 hours and then is subjected to fluorination treatment; in the fluorination reaction, after the reaction container is pumped to a vacuum state, the vacuum state is close to 0MPa, then heating and introducing reaction gas are carried out, the gas pressure reaches the range of 0-0.1MPa, and the reaction is carried out in the whole reaction process by adopting a low-pressure state.
The carbon fluoride nanohorn material prepared by the invention is applied to the anode material of a lithium (primary) battery, and the carbon fluoride nanohorn material is prepared by the following steps of: carbon black: binder (PVDF) ═ 8: 1: 1, uniformly coating the ground slurry on a carbon-attached aluminum foil, placing the carbon-attached aluminum foil in a blast oven for 2-8h for drying, placing the dried material in a vacuum drying oven for vacuum drying for 8-24h, and cutting and weighing according to needs to obtain the corresponding anode material.
The carbon nanohorn is a novel carbon nanomaterial similar to a carbon nanotube, and is formed by defining a conical vertex by a pentagonal ring and expanding a large conical structure by a hexagonal graphite structure. One end of the single-walled carbon nanohorn is a closed cap end structure, and the rest part is a graphite tube. Because of the unique geometric configuration of the carbon nanohorn, the carbon nanohorn is adopted as the raw material to carry out fluorination treatment in the technical scheme of the invention, the curvature structure at one end of the carbon nanohorn is favorable for the generation of fluorocarbon semi-ionic bond, the discharge voltage and the power density are improved, and the carbon nanohorn is adopted as the carbon source to prepare the carbon fluoride material which is used as the anode material of the lithium primary battery.
Drawings
Fig. 1 is a scanning electron micrograph of carbon fluoride nanohorns according to the present invention.
Fig. 2 is a constant current discharge graph of the carbon fluoride nanohorns of the present invention (1, example 1 corresponding to a fluorination temperature of 150 ℃).
Fig. 3 is a constant current discharge graph of the carbon fluoride nanohorns of the present invention (2, corresponding to example 2 in which the fluorination temperature is 200 ℃).
Fig. 4 is a constant current discharge graph of the carbon fluoride nanohorns of the present invention (3, example 4 corresponding to a fluorination temperature of 250 ℃).
Detailed Description
The technical scheme of the invention is illustrated by specific examples below, wherein the carbon nanohorns are purchased from Nanjing Xiancheng nanomaterial science and technology Limited company with particle size of 80-100 nm.
Example 1
(1) Putting the carbon nanohorn into a vacuum drying oven at 60 ℃, putting anhydrous phosphorus pentoxide at the bottom of the vacuum drying oven, taking out after 8 hours, and sealing for later use;
(2) placing the carbon nanohorn in a reaction kettle, pumping to vacuum, heating the reaction kettle to 150 ℃, introducing 20% of mixed gas of fluorine gas and nitrogen gas to 0.01Mpa, and reacting for 4h to obtain the carbon fluoride nanohorn;
(3) grinding the carbon fluoride nanohorn according to the proportion of 64mg of the carbon fluoride nanohorn, 8mg of carbon black and 8mg of a binder (PVDF), uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for 2h for drying. And (5) putting the dried material into a vacuum drying oven, and performing vacuum drying for 10 hours. The cut positive electrode materials were weighed to 12.4mg, 13.5mg, and 12.8mg, respectively.
Example 2
(1) Putting the carbon nanohorn into a vacuum drying oven at 60 ℃, putting anhydrous phosphorus pentoxide at the bottom of the vacuum drying oven, taking out after 8 hours, and sealing for later use;
(2) placing the carbon nanohorn in a reaction kettle, vacuumizing to vacuum, heating the reaction kettle to 200 ℃, introducing 20% of mixed gas of fluorine gas and nitrogen gas to 0MPa, and reacting for 4 hours to obtain the carbon fluoride nanohorn;
(3) grinding the carbon fluoride nanohorn according to the proportion of 64mg of the carbon fluoride nanohorn, 8mg of carbon black and 8mg of a binder (PVDF), uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for 3h for drying. And (5) placing the dried material in a vacuum drying oven, and performing vacuum drying for 12 hours. The cut positive electrode materials were weighed to be 11.4mg, 12.5mg, and 13.8mg, respectively.
Example 3
(1) Putting the carbon nanohorn into a vacuum drying oven at 60 ℃, putting anhydrous phosphorus pentoxide at the bottom of the vacuum drying oven, taking out after 8 hours, and sealing for later use;
(2) placing the carbon nanohorn in a reaction kettle, vacuumizing to vacuum, heating the reaction kettle to 100 ℃, introducing a mixed gas of 20% fluorine gas and nitrogen gas to 0MPa, and reacting for 4 hours to obtain the carbon fluoride nanohorn;
(3) grinding the carbon fluoride nanohorn according to the proportion of 64mg of the carbon fluoride nanohorn, 8mg of carbon black and 8mg of a binder (PVDF), uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for 2h for drying. And (5) putting the dried material into a vacuum drying oven, and performing vacuum drying for 10 hours. The cut positive electrode materials were weighed to 12.5mg, 13.8mg, and 12.0mg, respectively.
Example 4
(1) Putting the carbon nanohorn into a vacuum drying oven at 60 ℃, putting anhydrous phosphorus pentoxide at the bottom of the vacuum drying oven, taking out after 8 hours, and sealing for later use;
(2) placing the carbon nanohorn in a reaction kettle, pumping to vacuum, heating the reaction kettle to 250 ℃, introducing 20% of mixed gas of fluorine gas and nitrogen gas to 0.02Mpa, and reacting for 4h to obtain the carbon fluoride nanohorn;
(3) grinding the carbon fluoride nanohorn according to the proportion of 80mg of the carbon fluoride nanohorn, 10mg of carbon black and 10mg of a binder (PVDF), uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for 2h for drying. And (5) putting the dried material into a vacuum drying oven, and performing vacuum drying for 10 hours. The cut positive electrode materials were weighed to 12.5mg, 14.9mg, and 13.0mg, respectively.
Example 5
(1) Putting the carbon nanohorn into a vacuum drying oven at 60 ℃, putting anhydrous phosphorus pentoxide at the bottom of the vacuum drying oven, taking out after 8 hours, and sealing for later use;
(2) placing the carbon nanohorn in a reaction kettle, pumping to vacuum, heating the reaction kettle to 200 ℃, introducing 20% of mixed gas of fluorine gas and nitrogen gas to 0.1Mpa, and reacting for 6h to obtain the carbon fluoride nanohorn;
(3) grinding the carbon fluoride nanohorn according to the proportion of 64mg of the carbon fluoride nanohorn, 8mg of carbon black and 8mg of a binder (PVDF), uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for 2h for drying. And (5) placing the dried material in a vacuum drying oven, and performing vacuum drying for 12 hours. The cut positive electrode materials were weighed to 12.2mg, 13.7mg, and 11.5mg, respectively.
The prepared carbon fluoride nanohorn is used as a positive electrode material of a lithium primary battery to carry out performance test, as shown in attached figures 1-4, the carbon nanohorn keeps the original shape after fluorination treatment and does not have obvious change; from the discharge curve with the fluorination temperature of 150 ℃, the discharge medium voltage is 3.012V, the specific capacity is 710mAh/g, and the voltage platform is not obvious; obtaining a discharge medium voltage of 2.72V and a specific capacity of 590mAh/g from a discharge curve with the fluorination temperature of 200 ℃; from the discharge curve of the fluorination temperature of 250 ℃, the discharge medium voltage is 2.84V, and the specific capacity is 749 mAh/g. Has better discharge platform at 200 ℃ and 250 ℃, and has better voltage and specific capacity at the fluorination temperature of 250 ℃.
The carbon fluoride nanohorn material can be prepared by adjusting the process parameters according to the content of the invention, and the test shows that the performance is basically consistent with the invention, namely the carbon fluoride nanohorn material after the fluorination treatment is applied to the positive electrode material of the lithium primary battery, the discharge medium voltage is 2.8-2.9V, and the specific capacity is 740-760 mAh/g. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A carbon fluoride nanohorn material for a positive electrode material of a lithium primary battery, characterized by comprising the steps of: placing the carbon nanohorn in a reaction vessel, pumping to a vacuum state, heating to 100-300 ℃, and introducing fluorine-containing reaction gas into the reaction vessel for reaction to obtain the carbon fluoride nanohorn material.
2. The fluorinated carbon nanohorn material for a positive electrode material of a lithium primary battery as claimed in claim 1, wherein the carbon nanohorn particle size is 80 to 100 nm.
3. The fluorinated carbon nanohorn material for a positive electrode material of a lithium primary battery according to claim 1, wherein the fluorination reaction temperature is 200 to 250 ℃.
4. The fluorinated carbon nanohorn material for a positive electrode material of a lithium primary battery according to claim 1, wherein the fluorination reaction time is 1 to 10 hours, preferably 3 to 8 hours.
5. The fluorinated carbon nanohorn material for a positive electrode material of a lithium primary battery according to claim 1, wherein the percentage by volume of fluorine gas in the fluorine-containing reaction gas is 10 to 40%, preferably 20 to 30%; introducing fluorine-containing reaction gas until the gas pressure reaches 0-0.1 MPa.
6. A preparation method of carbon fluoride nanohorn material used for a positive electrode material of a lithium primary battery is characterized by comprising the following steps: placing the carbon nanohorn in a reaction container, vacuumizing to a vacuum state, heating to 100-300 ℃, introducing fluorine-containing reaction gas into the reaction container for reaction to obtain the carbon fluoride nanohorn material, wherein the volume percentage of fluorine gas in the fluorine-containing reaction gas is 10-40%.
7. The method of claim 6, wherein the carbon nanohorn particles have a diameter of 80 to 100 nm.
8. The method of claim 6, wherein the fluorination reaction temperature is 200-250 ℃ and the fluorination reaction time is 1-10 hours, preferably 3-8 hours.
9. The method of claim 6, wherein the fluorine gas is present in the fluorine-containing reaction gas in an amount of 20 to 30% by volume; introducing fluorine-containing reaction gas until the gas pressure reaches 0-0.1 MPa.
10. Use of the carbon fluoride nanohorn material as claimed in any one of claims 1 to 5 in a positive electrode material for a lithium (primary) battery, wherein the discharge medium voltage is 2.8 to 2.9V and the specific capacity is 740 to 760 mAh/g.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013075811A (en) * | 2011-09-30 | 2013-04-25 | Daikin Industries Ltd | Method for producing carbon nanohorn, fluorinated carbon nanohorn and production method thereof |
| CN109411752A (en) * | 2017-08-15 | 2019-03-01 | 天津大学 | A method of carbon fluoride nano-tube is prepared by Fluorine source of fluorine gas |
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- 2019-09-23 CN CN201910898497.6A patent/CN112542584A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013075811A (en) * | 2011-09-30 | 2013-04-25 | Daikin Industries Ltd | Method for producing carbon nanohorn, fluorinated carbon nanohorn and production method thereof |
| CN109411752A (en) * | 2017-08-15 | 2019-03-01 | 天津大学 | A method of carbon fluoride nano-tube is prepared by Fluorine source of fluorine gas |
Non-Patent Citations (3)
| Title |
|---|
| D. DAMIEN ET AL.: "Fluorinated graphene based electrodes for high performance primary lithium batteries", 《RSC ADVANCES》 * |
| HATTORI Y ET AL.: "Direct Thermal Fluorination of Single Wall Carbon Nanohorns", 《JOURNAL OF PHYSICAL CHEMISTRY B》 * |
| 马小娜等: "碳纳米角的共价功能化研究进展", 《广州化工》 * |
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