CN109461923B - Composite carbon fluoride positive electrode material for lithium primary battery and preparation method and application thereof - Google Patents
Composite carbon fluoride positive electrode material for lithium primary battery and preparation method and application thereof Download PDFInfo
- Publication number
- CN109461923B CN109461923B CN201811348641.0A CN201811348641A CN109461923B CN 109461923 B CN109461923 B CN 109461923B CN 201811348641 A CN201811348641 A CN 201811348641A CN 109461923 B CN109461923 B CN 109461923B
- Authority
- CN
- China
- Prior art keywords
- carbon
- composite
- carbon fluoride
- primary battery
- lithium primary
- 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.)
- Active
Links
Images
Classifications
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/582—Halogenides
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of lithium primary battery anode materials, particularly relates to the field of preparation of fluorocarbon battery anode materials, and particularly relates to a composite carbon fluoride anode material for a lithium primary battery as well as a preparation method and application thereof. The composite material is prepared by ball-milling, mixing and re-fluorinating a porous carbon fluoride material with high tap density and a carbon fluoride material with high graphitization degree, wherein the content of carbon element in the composite material is 38-60%, the content of fluorine element is 40-62%, the tap density is more than 0.8g/ml, the mixing mass ratio range is 1:0.1-1:10, and the composite material has high specific surface area, high tap density and high graphitization degree. The integral tap density of the material is high, so that the integral high volumetric specific energy of the material is ensured; the ion diffusion channel formed by the porous carbon fluoride effectively improves the voltage hysteresis phenomenon at the initial discharge stage of the battery and improves the overall discharge performance of the material.
Description
Technical Field
The invention belongs to the technical field of lithium primary battery anode materials, particularly relates to the field of preparation of fluorocarbon battery anode materials, and particularly relates to a composite carbon fluoride anode material for a lithium primary battery as well as a preparation method and application thereof.
Background
The lithium primary battery has irreplaceable effects in the aspects of aerospace, medical equipment, military equipment, daily life and the like, wherein the lithium/carbon fluoride battery is taken as the lithium primary battery with the highest theoretical specific energy at present, and the theoretical specific energy of mass can reach 2180Wh/Kg (lithium/thionyl chloride battery: 1470 Wh/Kg, lithium/manganese dioxide battery: 1005 Wh/Kg), so the lithium/carbon fluoride battery is greatly concerned. The high-temperature-resistant high-voltage cable has good high-temperature performance (the self-discharge rate is 0.5%/year) and excellent safety and environmental protection performance, can meet working conditions under various severe environments, and particularly has important application in the fields of national defense, military industry, aerospace, navigation and the like.
The carbon fluoride material as the positive electrode active material of the lithium/carbon fluoride battery has a decisive influence on the performance of the lithium/carbon fluoride battery. The preparation method of the carbon fluoride material comprises the following steps: the method comprises a plurality of methods such as a high-temperature fluorination method, a low-temperature fluorination method, a plasma method, an electrolysis method and the like, wherein the plasma method and the electrolysis method have high process requirements and great industrialization difficulty and are only applied to laboratory-scale preparation.
Common are high temperature fluorination and low temperature fluorination:
(1) high temperature fluorination: the carbon fluoride material prepared by the high-temperature method has higher specific energy, but the conductivity is poor, the whole discharge platform is only about 2.5V, and obvious voltage lag appears at the initial stage of discharge. However, the carbon fluoride material in the current market is mostly a high-temperature fluorination method product due to the simple preparation process.
(2) Low temperature fluorination: the carbon fluoride material prepared by the low-temperature method has the advantages that the graphite structure is kept relatively complete, the conductivity is relatively good, the discharge voltage is high, and the specific energy is lower than that of the carbon fluoride prepared by the high-temperature method.
The carbon fluoride material is used as the positive electrode material of the lithium primary battery, and the problem that the high specific capacity and the high discharge voltage are difficult to combine is caused, so that the ultrahigh theoretical specific energy is difficult to fully release. Therefore, the preparation of carbon fluoride materials having both high specific capacity and high discharge voltage has long been an important subject of research in this field.
The novel carbon fluoride materials such as carbon fluoride nanotubes and fluorinated graphene have higher discharge platform and mass specific energy, but the volume specific energy is lower due to the low tap density of the material.
How to obtain a carbon fluoride material without voltage hysteresis and with high specific energy (both mass specific energy and volume specific energy) becomes a problem which needs to be solved urgently in the application of the carbon fluoride material in batteries.
Disclosure of Invention
The invention aims to provide a carbon fluoride material with excellent comprehensive performance, no voltage hysteresis, high specific energy and adjustable discharge performance and a preparation method thereof.
The technical scheme of the invention is as follows:
a composite carbon fluoride anode material for a lithium primary battery is a composite material prepared by ball-milling and mixing a porous carbon fluoride material with high tap density and a carbon fluoride material with high graphitization degree and then fluorinating, wherein the composite material contains 38-60% of carbon element, 40-62% of fluorine element and has tap density of more than 0.8g/ml, has an adjustable double discharge platform, has initial discharge voltage of more than 2.8V at 0.1 ℃, and has volumetric specific energy of more than 1500 Wh/L.
The high tap density in the invention means that the density is higher than 0.70 g/ml; the high graphitization degree means that the graphitization degree is higher than 80% (note: calculated according to Mering-Maire formula).
Another object of the present invention is to provide a method for preparing a composite fluorocarbon positive electrode material for a lithium primary battery, comprising the steps of:
(1) selecting a porous carbon material, and preparing a porous carbon fluoride material by adopting a low-temperature gas phase fluorination method;
(2) selecting a high-graphitization-degree carbon material, and preparing the high-graphitization-degree carbon fluoride material by adopting a high-temperature gas phase fluorination method;
(3) ball-milling and mixing the porous carbon fluoride material and the high-graphitization-degree carbon fluoride material according to a certain proportion to obtain a uniformly mixed composite carbon fluoride material;
(4) and (4) carrying out secondary fluorination treatment on the composite carbon fluoride material obtained in the step (3) to obtain the composite carbon fluoride anode material.
The composite carbon fluoride anode material is a carbon fluoride material with discharge voltage and specific energy designed according to the use requirement.
The invention also has the following characteristics:
in the porous carbon fluoride material in the step (1), the fluorine-carbon atomic ratio (F/C) is not less than 0.5, namely F/C is not less than 0.5.
The density of the porous carbon material in the step (1) is more than or equal to 0.5 g/ml.
The porous carbon material in the step (1) can be activated carbon, mesoporous carbon, activated carbon fiber, modified materials prepared from the activated carbon, the mesoporous carbon and the activated carbon fiber, and composite materials.
The low-temperature gas phase fluorination method in the step (1) is that the porous carbon material is F2F in a volume fraction of 2-100%2In the mixed atmosphere, the diluent gas is nitrogen, argon, helium, carbon tetrafluoride and the like; reacting for 2-12h at the temperature of 100-350 ℃.
Further preferably, the low-temperature gas phase fluorination in the step (1) is carried out by subjecting the porous carbon material to F2F with the volume fraction of 3-10%2In the mixed atmosphere, the diluent gas is nitrogen, argon, helium, carbon tetrafluoride and the like; reacting for 3-6 h at 200-300 ℃.
In the high graphitization degree carbon fluoride material in the step (2), the fluorine-carbon atomic ratio (F/C) is not less than 0.5, namely F/C is not less than 0.5.
The high graphitization degree carbon material in the step (2) can be artificial graphite, spherical graphite, graphitized coke (including needle coke, green coke, petroleum coke, coal coke and the like), calcined coke, carbon fiber, graphitized carbon material, and modified materials and composite materials prepared from the materials.
The high-temperature gas phase fluorination method in the step (2) is to perform high graphitization degree carbon material F on the carbon material2F in a volume fraction of 2-100%2/N2In the mixed atmosphere, the diluent gas is nitrogen, argon, helium, carbon tetrafluoride and the like; reacting for 4-48h at the temperature of 100-600 ℃; preferably, the high-temperature gas-phase fluorination in the step (2) is carried out by reacting the highly graphitized carbon material in F2F with volume fraction of 5-10%2/N2In the mixed atmosphere, the diluent gas is nitrogen, argon, helium, carbon tetrafluoride and the like; reacting at 400-500 DEG C6~12h。
According to the mixing method in the step (3), the mixing mass ratio of the porous carbon fluoride material to the high-graphitization-degree carbon fluoride material is 1:0.1-1:10, and the ball milling time is 0.5-12 h.
Carrying out secondary fluorination treatment on the composite carbon fluoride material in the step (4), wherein the treatment conditions are as follows: the concentration of fluorine gas is 1-100%, and the diluent gas is nitrogen, argon, helium, carbon tetrafluoride, etc.; the fluorination treatment temperature is 150-500 ℃; the fluorination treatment time is 1-10 hours; more preferably, the composite carbon fluoride material in the step (4) is subjected to a secondary fluorination treatment under the following conditions: the concentration of fluorine gas is 3-10%, and the diluent gas is nitrogen, argon, helium, carbon tetrafluoride and the like; the fluorination treatment temperature is 200-350 ℃; the fluorination treatment time is 3 to 6 hours.
The discharge voltage and the specific capacity of the composite carbon fluoride material can be regulated and controlled according to the use requirement, and the use purpose of the final battery is met.
The invention also aims to provide application of the composite carbon fluoride positive electrode material for the lithium primary battery as a positive electrode material or a positive electrode active material of the lithium primary battery.
The invention has the beneficial effects that:
according to the composite carbon fluoride anode material for the lithium primary battery, disclosed by the invention, porous carbon fluoride is a carbon skeleton source, and a porous structure of the porous carbon fluoride provides a lithium ion diffusion channel in a discharging process, so that the effects of improving discharging voltage and eliminating voltage hysteresis are achieved; the high graphitization carbon fluoride material is uniformly dispersed on the surface of the porous carbon fluoride, and the functions of improving the integral specific capacity and tap density of the material are achieved. The high volume specific energy of the material is ensured by high voltage, high specific capacity and high tap density, and the specific advantages are as follows:
1. the composite carbon fluoride anode material provided by the invention has no voltage hysteresis and high initial discharge voltage; (discharge curves with initial voltage > 2.8V, no voltage lag, as shown in FIG. 1).
2. According to the invention, the porous carbon fluoride material with high tap density is selected, so that the overall high tap density of the composite carbon fluoride anode material is ensured, and the overall high volumetric specific energy of the material is ensured, which can be seen in Table 1.
3. The carbon fluoride composite material provided by the invention has double discharge platforms, and the electrochemical property can be regulated and controlled according to the mixing proportion and the secondary fluorination treatment process.
4. The preparation method is simple, environment-friendly and convenient for large-scale production.
In a word, the composite carbon fluoride anode material has the advantages of no voltage hysteresis, high specific energy, adjustable discharge performance, excellent comprehensive performance, outstanding substantive characteristics and obvious progress.
Drawings
FIG. 1 is a discharge curve of the composite fluorocarbon positive electrode material of example 2 at 0.1C;
FIG. 2 is a discharge curve of the composite fluorocarbon positive electrode material of example 4 at 0.1C;
fig. 3 is an electrical discharge curve of the composite fluorocarbon positive electrode material of example 5 at 0.1C.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions of the present invention will be clearly and completely described below with reference to the present embodiments, and it should be apparent that the embodiments described below are only a part of embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of this patent.
Example 1:
selecting active carbon (purity is more than or equal to 99.5 percent, D)50Less than or equal to 50 mu m) 200g of the mixture is put into a reaction furnace, the temperature is raised to 350 ℃, and F is introduced2Volume fraction 2% of F2/N2The mixed gas reacts for 12 hours to obtain the fluorinated activated carbon, and the F/C of the fluorinated activated carbon is 0.76 and the tap density of the fluorinated activated carbon is 0.82 g/ml.
Selecting 200g of carbon fiber (200 meshes), placing the carbon fiber in a reaction furnace, heating to 100 ℃, and introducing F2Volume fraction 100% of F2The reaction time is 24 hours, and the fluorinated carbon fiber is tested to have the F/C of 0.92 and the tap density of 0.94 g/ml.
Putting the obtained fluorinated activated carbon and fluorinated carbon fibers into a ball milling tank according to the mass ratio of 1:10, performing ball milling for 12 hours to obtain a composite fluorinated carbon material, and performing secondary fluorination treatment on the mixed fluorinated carbon material for 5 hours at 500 ℃ in a fluorine-nitrogen mixed gas with the fluorine gas concentration of 1% to obtain a secondary fluorinated composite fluorinated carbon anode material, wherein the tap density is 0.92g/ml, and the discharge performance is shown in table 1.
Example 2:
selecting active carbon (purity is more than or equal to 99.5 percent, D)50Less than or equal to 50 mu m) 200g of the mixture is put into a reaction furnace, the temperature is raised to 250 ℃, and F is introduced2Volume fraction of 10% of F2/N2Reacting the mixed gas for 6 hours to obtain fluorinated activated carbon; it was tested to have an F/C of 0.74 and a tap density of 0.81 g/ml.
Selecting 200g of carbon fiber (200 meshes), putting the carbon fiber into a reaction furnace, heating to 400 ℃, and introducing F2Volume fraction of 10% of F2/N2The mixed gas reacts for 16 hours to obtain the fluorinated carbon fiber, and the F/C of the fluorinated carbon fiber is 0.95 and the tap density of the fluorinated carbon fiber is 0.96 g/ml.
Putting the obtained fluorinated activated carbon and fluorinated carbon fiber into a ball milling tank according to the mass ratio of 1:1, performing ball milling for 6h to obtain a composite fluorinated carbon material, and performing secondary fluorination treatment on the mixed fluorinated carbon material for 5h at 350 ℃ in a fluorine-nitrogen mixed gas with the concentration of 5% of fluorine gas to obtain a secondary fluorinated mixed fluorinated carbon cathode material, wherein the tap density is 0.91g/ml, the discharge performance is shown in table 1, and the discharge curve is shown in fig. 1.
Example 3:
selecting active carbon (purity is more than or equal to 99.5 percent, D)50Less than or equal to 50 mu m) 200g of the mixture is put into a reaction furnace, the temperature is raised to 100 ℃, and F is introduced2 Volume fraction 100% of F2Reacting for 2 hours to obtain fluorinated activated carbon; it was found to have an F/C of 0.80 and a tap density of 0.85 g/ml.
Selecting 200g of carbon fiber (200 meshes), putting the carbon fiber into a reaction furnace, heating to 600 ℃, and introducing F2Volume fraction 2% of F2/N2The mixed gas reacts for 4 hours to obtain the fluorinated carbon fiber, and the F/C and tap density of the fluorinated carbon fiber are respectively 0.96 and 0.98 g/ml.
Putting the obtained fluorinated activated carbon and fluorinated carbon fibers into a ball milling tank according to the mass ratio of 1:0.1, performing ball milling for 0.5h to obtain a mixed carbon fluoride material, and performing secondary fluorination treatment on the mixed carbon fluoride material for 1 h at the temperature of 150 ℃ in the presence of fluorine gas with the concentration of 100% to obtain a secondary fluorinated mixed carbon fluoride cathode material, wherein the tap density is 0.84g/ml, and the discharge performance is shown in table 1.
Example 4:
selecting active carbon (purity is more than or equal to 99.5 percent, D)50Less than or equal to 50 mu m) 200g of the mixture is put into a reaction furnace, the temperature is raised to 250 ℃, and F is introduced2Volume fraction 5% of F2/N2Reacting the mixed gas for 6 hours to obtain fluorinated activated carbon; it was tested to have an F/C of 0.73 and a tap density of 0.81 g/ml.
200g of needle coke (200 meshes) is selected and put into a reaction furnace, the temperature is raised to 380 ℃, and F is introduced2Volume fraction of 10% of F2/N2The mixed gas reacts for 16 hours to obtain the fluorinated needle coke, and the F/C of the fluorinated needle coke is tested to be 0.94, and the tap density is 0.95 g/ml.
Putting the obtained fluorinated activated carbon and the fluorinated needle coke into a ball milling tank according to the mass ratio of 1:1, performing ball milling for 2 hours to obtain a mixed carbon fluoride material, and performing secondary fluorination treatment on the mixed carbon fluoride material for 5 hours at 350 ℃ in a fluorine-nitrogen mixed gas with the fluorine gas concentration of 5% to obtain a secondary fluorinated mixed carbon fluoride cathode material, wherein the tap density is 0.90g/ml, and the discharge curve is shown in figure 2. The discharge properties are shown in Table 1.
Example 5:
selecting active carbon (purity is more than or equal to 99.5 percent, D)50Less than or equal to 50 mu m) is oxidized by adopting a modified hummers method, the treated modified activated carbon is put into a reaction furnace, the temperature is raised to 100 ℃, and F is introduced2Volume fraction 2% of F2/N2The mixed gas reacts for 12 hours to obtain the fluorinated activated carbon, and the F/C of the fluorinated activated carbon is 0.84 and the tap density of the fluorinated activated carbon is 0.80 g/ml.
Selecting 200g of carbon fiber, placing the carbon fiber into a reaction furnace, heating the carbon fiber to 600 ℃, and introducing F2Volume fraction 2% of F2/N2The mixed gas reacts for 16 hours to obtain the fluorinated carbon fiber, and the F/C of the fluorinated carbon fiber is 0.98 and the tap density of the fluorinated carbon fiber is 1.01 g/ml.
Placing fluorinated activated carbon and fluorinated carbon fiber in a ball milling tank according to the mass ratio of 1:1, performing ball milling for 6h to obtain a mixed carbon fluoride material, and performing secondary fluorination treatment on the mixed carbon fluoride material for 10 hours at 250 ℃ in a fluorine-nitrogen mixed gas with the fluorine gas concentration of 1% to obtain a secondary fluorinated mixed carbon fluoride cathode material, wherein the tap density is 0.92g/ml, the discharge performance is shown in table 1, and the discharge curve is shown in fig. 3.
Table 1 shows the properties of the composite fluorocarbon materials of examples 1 to 5.
TABLE 1 composite fluorocarbon positive electrode Material Properties
Claims (11)
1. A composite carbon fluoride anode material for a lithium primary battery is a composite material prepared by ball-milling and mixing a porous carbon fluoride material with high tap density and a carbon fluoride material with high graphitization degree, wherein the high tap density is higher than 0.70g/ml, the high graphitization degree is higher than 80%, the carbon element content of the composite material is 38-60%, the fluorine element content is 40-62%, the tap density is higher than 0.8g/ml, the composite material is provided with an adjustable double discharge platform, the initial discharge voltage is higher than 2.8V at 0.1 ℃, and the volumetric specific energy is higher than 1500 Wh/L;
the porous carbon fluoride material is obtained from a porous carbon material by a low-temperature gas-phase fluorination method, wherein the low-temperature gas-phase fluorination method is that the porous carbon material is fluorinated in F2F in a volume fraction of 2-100%2In the mixed atmosphere, the diluent gas is nitrogen, argon, helium and carbon tetrafluoride, the reaction is carried out for 2 to 12 hours at the temperature of 100 to 350 ℃, and the porous carbon material is selected from activated carbon, mesoporous carbon, activated carbon fiber, and modified materials and composite materials prepared from the materials.
2. The method for preparing the composite fluorocarbon positive electrode material for a lithium primary battery according to claim 1, comprising the steps of:
(1) selecting a porous carbon material, and preparing a porous carbon fluoride material by adopting a low-temperature gas phase fluorination method, wherein the porous carbon material is prepared in the step F2F in a volume fraction of 2-100%2In the mixed atmosphere, diluting gas is nitrogen, argon, helium and carbon tetrafluoride, and the reaction is carried out for 2 to 12 hours at the temperature of 100 to 350 ℃;
(2) selecting a high-graphitization-degree carbon material, and preparing the high-graphitization-degree carbon fluoride material by adopting a high-temperature gas-phase fluorination method, wherein the high-graphitization-degree carbon material is prepared in F2F in a volume fraction of 2-100%2/N2Reacting for 4-48h at 380-600 ℃ in mixed atmosphere;
(3) ball-milling and mixing the porous carbon fluoride material and the high-graphitization-degree carbon fluoride material according to a certain proportion to obtain a uniformly mixed composite carbon fluoride material;
(4) and (4) carrying out secondary fluorination treatment on the composite carbon fluoride material obtained in the step (3) to obtain the composite carbon fluoride anode material.
3. The method for preparing the composite carbon fluoride cathode material for the lithium primary battery according to claim 2, wherein the method comprises the following steps: the density of the porous carbon material in the step (1) is more than or equal to 0.5 g/ml.
4. The method for preparing the composite carbon fluoride cathode material for the lithium primary battery according to claim 2, wherein the method comprises the following steps: the low-temperature gas phase fluorination method in the step (1) is that the porous carbon material is F2F with the volume fraction of 3-10%2In the mixed atmosphere, the diluent gas is nitrogen, argon, helium or carbon tetrafluoride, and the reaction is carried out for 3-6 h at the temperature of 200-300 ℃.
5. The method for preparing the composite carbon fluoride cathode material for the lithium primary battery according to claim 2, wherein the method comprises the following steps: the high-graphitization-degree carbon material in the step (2) is selected from artificial graphite, spherical graphite, graphitized coke, carbon fiber, and modified materials and composite materials prepared from the materials; wherein the coke comprises needle coke, green coke, petroleum coke and coal coke.
6. According to claim 2The preparation method of the composite carbon fluoride anode material for the lithium primary battery is characterized by comprising the following steps of: the high-temperature gas phase fluorination method in the step (2) is to perform high graphitization degree carbon material F on the carbon material2F with volume fraction of 5-10%2/N2Reacting for 6-12 h at 400-500 ℃ in a mixed atmosphere.
7. The method for preparing the composite carbon fluoride cathode material for the lithium primary battery according to claim 2, wherein the method comprises the following steps: the fluorine-carbon atomic ratio of the porous carbon fluoride material is not less than 0.5; the carbon fluoride material with high graphitization degree has the fluorine-carbon atomic ratio of not less than 0.5.
8. The method for preparing the composite carbon fluoride cathode material for the lithium primary battery according to claim 2, wherein the method comprises the following steps: in the step (3), the mixing mass ratio of the porous carbon fluoride material to the high graphitization degree carbon fluoride material is 1:0.1-1:10, and the ball milling time is 0.5-12 h.
9. The method for preparing the composite carbon fluoride cathode material for the lithium primary battery according to claim 2, wherein the method comprises the following steps: carrying out secondary fluorination treatment on the composite carbon fluoride material in the step (4), wherein the treatment conditions are as follows: the fluorine gas concentration is 1-100%, the diluent gas is nitrogen, argon, helium or carbon tetrafluoride, the fluorination treatment temperature is 150-500 ℃, and the fluorination treatment time is 1-10 hours.
10. The method for preparing the composite carbon fluoride cathode material for the lithium primary battery according to claim 2, wherein the method comprises the following steps: carrying out secondary fluorination treatment on the composite carbon fluoride material in the step (4), wherein the treatment conditions are as follows: the fluorine gas concentration is 3-10%, the diluent gas is nitrogen, argon, helium or carbon tetrafluoride, the fluorination treatment temperature is 200-350 ℃, and the fluorination treatment time is 3-6 hours.
11. The use of the composite fluorinated carbon cathode material prepared by the preparation method according to any one of claims 2 to 10 as a cathode active material for a lithium primary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811348641.0A CN109461923B (en) | 2018-11-13 | 2018-11-13 | Composite carbon fluoride positive electrode material for lithium primary battery and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811348641.0A CN109461923B (en) | 2018-11-13 | 2018-11-13 | Composite carbon fluoride positive electrode material for lithium primary battery and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109461923A CN109461923A (en) | 2019-03-12 |
| CN109461923B true CN109461923B (en) | 2021-11-30 |
Family
ID=65610279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811348641.0A Active CN109461923B (en) | 2018-11-13 | 2018-11-13 | Composite carbon fluoride positive electrode material for lithium primary battery and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109461923B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110165210B (en) * | 2019-05-14 | 2021-12-24 | 中国民航大学 | Preparation method of carbon fluoride anode material with high specific capacity |
| CN112174110B (en) * | 2019-07-04 | 2022-06-07 | 上海大学 | Preparation method of porous carbon fluoride material |
| CN111224197B (en) * | 2020-01-06 | 2021-10-22 | 贵州梅岭电源有限公司 | Lithium fluorocarbon-supercapacitor quick response composite battery |
| CN111170303B (en) * | 2020-01-16 | 2023-03-31 | 厦门稀土材料研究所 | Preparation method and application of carbon fluoride material |
| CN111170302B (en) * | 2020-01-16 | 2021-08-17 | 厦门稀土材料研究所 | Preparation method and application of carbon fluoride material |
| CN111204735B (en) * | 2020-01-16 | 2021-07-27 | 厦门稀土材料研究所 | Preparation method and application of carbon fluoride material |
| CN112209362B (en) * | 2020-09-27 | 2021-12-03 | 电子科技大学 | Method for activating carbon fluoride by plasma induction and preparation of lithium primary battery |
| CN112635773A (en) * | 2020-12-21 | 2021-04-09 | 中国科学院长春应用化学研究所 | Positive pole piece for primary battery and primary battery |
| CN112635739B (en) * | 2020-12-25 | 2022-09-30 | 湖州凯金新能源科技有限公司 | Graphite material for lithium battery with long cycle characteristic and preparation method thereof |
| CN112786822B (en) * | 2020-12-30 | 2022-03-11 | 惠州亿纬锂能股份有限公司 | Lithium-carbon fluoride battery positive pole piece, preparation method thereof and lithium-carbon fluoride battery |
| CN114122358A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | Quick-filling graphite composite material and preparation method thereof |
| CN114975956A (en) * | 2022-06-21 | 2022-08-30 | 贵州梅岭电源有限公司 | Fluorinated graphene/fluorinated graphite composite positive electrode material and preparation method thereof |
| CN115010113B (en) * | 2022-06-24 | 2024-02-13 | 山东重山光电材料股份有限公司 | Fluorocarbon material and application thereof, and lithium battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0142113A2 (en) * | 1983-11-07 | 1985-05-22 | Daikin Kogyo Co., Ltd. | Active material for batteries |
| CN101632189A (en) * | 2007-03-14 | 2010-01-20 | 加州理工学院 | High discharge rate batteries |
| CN102361084A (en) * | 2011-10-10 | 2012-02-22 | 中国电子科技集团公司第十八研究所 | Carbon fluoride for lithium battery anode material |
| CN102509802A (en) * | 2011-10-10 | 2012-06-20 | 中国电子科技集团公司第十八研究所 | Preparation method of carbon fluoride serving as positive electrode material of lithium battery |
| CN102730663A (en) * | 2012-06-13 | 2012-10-17 | 西北核技术研究所 | Carbon fluoride and application thereof |
| CN103474695A (en) * | 2013-09-10 | 2013-12-25 | 复旦大学 | Sodium/perfluorocarbon secondary battery and preparation method thereof |
| CN108123133A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | Sandwich structure monoblock type self-supporting fluorination carbon electrode material and preparation method thereof |
| CN108473310A (en) * | 2015-10-02 | 2018-08-31 | 克莱蒙奥弗涅大学 | Manufacture method, material and the lithium battery of lithium battery material |
| CN108529589A (en) * | 2018-06-21 | 2018-09-14 | 山东重山光电材料股份有限公司 | A kind of method of industrialized production fluorinated carbon material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106941178A (en) * | 2017-05-12 | 2017-07-11 | 厦门希弗新能源科技有限公司 | A kind of fluorocarbons and its preparation method and application |
| CN107482187B (en) * | 2017-07-27 | 2020-07-03 | 天津巴莫科技股份有限公司 | Asphalt carbon-coated carbon fluoride anode material and preparation method thereof |
-
2018
- 2018-11-13 CN CN201811348641.0A patent/CN109461923B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0142113A2 (en) * | 1983-11-07 | 1985-05-22 | Daikin Kogyo Co., Ltd. | Active material for batteries |
| CN101632189A (en) * | 2007-03-14 | 2010-01-20 | 加州理工学院 | High discharge rate batteries |
| CN102361084A (en) * | 2011-10-10 | 2012-02-22 | 中国电子科技集团公司第十八研究所 | Carbon fluoride for lithium battery anode material |
| CN102509802A (en) * | 2011-10-10 | 2012-06-20 | 中国电子科技集团公司第十八研究所 | Preparation method of carbon fluoride serving as positive electrode material of lithium battery |
| CN102730663A (en) * | 2012-06-13 | 2012-10-17 | 西北核技术研究所 | Carbon fluoride and application thereof |
| CN103474695A (en) * | 2013-09-10 | 2013-12-25 | 复旦大学 | Sodium/perfluorocarbon secondary battery and preparation method thereof |
| CN108473310A (en) * | 2015-10-02 | 2018-08-31 | 克莱蒙奥弗涅大学 | Manufacture method, material and the lithium battery of lithium battery material |
| CN108123133A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | Sandwich structure monoblock type self-supporting fluorination carbon electrode material and preparation method thereof |
| CN108529589A (en) * | 2018-06-21 | 2018-09-14 | 山东重山光电材料股份有限公司 | A kind of method of industrialized production fluorinated carbon material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109461923A (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109461923B (en) | Composite carbon fluoride positive electrode material for lithium primary battery and preparation method and application thereof | |
| Liu et al. | Nitrogen-doped bamboo-like carbon nanotubes as anode material for high performance potassium ion batteries | |
| Yang et al. | Biomass-derived carbon from Ganoderma lucidum spore as a promising anode material for rapid potassium-ion storage | |
| Wang et al. | Ultrastable and high-capacity carbon nanofiber anodes derived from pitch/polyacrylonitrile for flexible sodium-ion batteries | |
| EP2657189A1 (en) | Fluorinated graphene oxide and preparation method thereof | |
| EP2657188A1 (en) | Fluorographene and preparation method thereof | |
| CN107634224B (en) | Preparation method of fluorinated multi-walled carbon nanotube containing outer wall of iron fluoride intercalation substance | |
| Yue et al. | Synthesis and characterization of fluorinated carbon nanotubes for lithium primary batteries with high power density | |
| CN109167025B (en) | Boron-doped modified soft carbon-coated negative electrode material with high stability in high and low temperature environments and preparation method thereof | |
| Zhao et al. | Micro-/nano-structured hybrid of exfoliated graphite and Co3O4 nanoparticles as high-performance anode material for Li-ion batteries | |
| Ha et al. | Fluorination methods and the properties of fluorinated carbon materials for use as lithium primary battery cathode materials | |
| Dang et al. | Facile synthesis of rod-like nickel-cobalt oxide nanostructure for supercapacitor with excellent cycling stability | |
| Yuan et al. | Pseudo-capacitance reinforced modified graphite for fast-charging potassium-ion batteries | |
| Lin et al. | 3D hybrid of Co9S8 and N-doped carbon hollow spheres as effective hosts for Li-S batteries | |
| Huang et al. | Enhanced electrochemical properties of SnO2–graphene–carbon nanofibers tuned by phosphoric acid for potassium storage | |
| GB2616100A (en) | Method for precise preparation of fluorinated soft carbon with adjustable crystallinity, and performance study of primary battery | |
| Yan et al. | Free-standing cross-linked activated carbon nanofibers with nitrogen functionality for high-performance supercapacitors | |
| CN111564610B (en) | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof | |
| Ding et al. | A three-dimensional hierarchical porous carbon network decorated with MnO2 nanoparticles (HPCM) as an efficient sulfur host for high-performance lithium-sulfur batteries (LSBs) | |
| CN109411738A (en) | A kind of doping FeF3Composite material and preparation method and application | |
| CN109148850A (en) | A kind of preparation method of fluorinated graphene capsule and the application in lithium primary battery | |
| Fang et al. | Binary graphene-based cathode structure for high-performance lithium-sulfur batteries | |
| Cai et al. | Preparation and performance of metal-organic-frameworks-derived activated mesoporous carbon polyhedron with sponge-like structure for lithium–sulfur batteries | |
| CN109148843A (en) | A kind of boron doping negative electrode material and its method for preparing solid phase with good properties at high temperature | |
| Luo et al. | Surface engineering of fluorinated graphene nanosheets enables ultrafast lithium/sodium/potassium primary batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |