CN109148850B - Preparation method of fluorinated graphene capsule and application of fluorinated graphene capsule in lithium primary battery - Google Patents
Preparation method of fluorinated graphene capsule and application of fluorinated graphene capsule in lithium primary battery Download PDFInfo
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Abstract
A preparation method of a fluorinated graphene capsule and application of the fluorinated graphene capsule in a lithium primary battery belong to the technical field of primary batteries. The method comprises the following steps: firstly, preparing a three-dimensional graphene capsule; then placing the prepared graphene capsule serving as a precursor carbon source in a tube furnace, heating to 400-600 ℃ under an inert gas atmosphere, and preserving heat for 2-6 h at 400-600 ℃; and then reducing the temperature to 200-350 ℃, introducing fluorine gas at the speed of 100-200 mL/min, and carrying out fluorination reaction for 2-6 h to obtain the fluorinated graphene capsule. The fluorinated graphene capsule obtained by the invention is used as a positive electrode material to be applied to a lithium primary battery, so that the voltage hysteresis effect is improved, and deep lithium hanging (Li) is promoted2F+) The mode effectively improves the specific capacity and the energy density of the battery, and has important significance for popularization and application of the lithium/carbon fluoride battery.
Description
Technical Field
The invention belongs to the technical field of primary batteries, and particularly relates to a preparation method of a fluorinated graphene capsule and application of the fluorinated graphene capsule in a lithium primary battery.
Background
The lithium/carbon fluoride battery is a high energy electrode material of Carbon Fluoride (CF)x) Is a positive active material, and lithium metal is a negative material. Currently, lithium batteries on the market include lithium/manganese dioxide batteries, lithium/sulfur dioxide batteries, lithium/thionyl chloride batteries, lithium/carbon fluoride batteries, and the like. Compared with other solid anode material batteries, the lithium/carbon fluoride battery has the highest theoretical energy density (up to 2180Wh/kg), the practical specific energy can be up to 250-800 Wh/kg, the miniaturization and the light weight are easily realized, and the lithium/carbon fluoride battery has the advantages of stable discharge platform, small self-discharge, long storage life, wide temperature range, safety, greenness, no pollution and no pollutionPollution and the like, can meet the application requirements of high-end civil instruments, military equipment and aerospace standby power supplies, has huge market potential, and is greatly concerned by researchers. However, there are still a number of challenges that limit the widespread use of lithium/fluorocarbon batteries: firstly, the carbon fluoride material has poor conductivity due to the fluorination degree, and the discharge performance of the carbon fluoride material is influenced, particularly the discharge capacity under large current; secondly, the voltage has hysteresis effect, and the defects of low platform, high cost and the like exist at the same time. And the performance of the carbon fluoride can be improved by utilizing different carbon sources for fluorination. Chinese patent 201711435109.8 discloses a fluorinated ketjen black material obtained by fluorination using ketjen black as a precursor carbon source, which effectively solves the problems of low voltage platform and poor conductivity of carbon fluoride by utilizing the good conductivity of ketjen black, but the specific capacity is not improved, and the voltage hysteresis effect still exists.
Disclosure of Invention
The invention provides a preparation method of a fluorinated graphene capsule and application of the fluorinated graphene capsule in a lithium primary battery, aiming at the defects in the background technology. The fluorinated graphene capsule obtained by the invention is used as a positive electrode material to be applied to a lithium primary battery, so that the specific capacity and the energy density of the battery are effectively improved, and the voltage hysteresis effect is improved.
The technical scheme of the invention is as follows:
a preparation method of a fluorinated graphene capsule comprises the following steps:
step 1, placing 10-20 g of nano ZnO particles in a CVD (chemical vapor deposition) rotary furnace, introducing inert gas as protective gas, wherein the rotation speed of the rotary furnace is 5-10 revolutions per minute, heating the rotary furnace to 450-800 ℃, keeping the introduction of the inert gas and introducing catalytic carbon source gas as reaction gas for catalytic reaction, wherein the reaction temperature is 450-800 ℃, the reaction time is 5-60 minutes, naturally cooling to room temperature after the reaction is finished, taking out a product, and growing a graphene-coated nano layer on the surface of the nano ZnO particles to obtain a graphene/zinc oxide composite material;
step 3, placing the graphene capsules obtained in the step 2 as a precursor carbon source in a tube furnace, heating to 400-600 ℃ under an inert gas atmosphere, and preserving heat for 2-6 hours at 400-600 ℃; and then reducing the temperature to 200-350 ℃, introducing fluorine gas at the speed of 100-200 mL/min, and carrying out fluorination reaction for 2-6 h to obtain the fluorinated graphene capsule.
Further, the flow rate of the catalytic carbon source gas in the step 1 is 20-50 mL/min, and the flow rate of the protective gas is 5-50 mL/min.
Further, the catalytic carbon source gas in the step 1 is acetylene; the protective gas is argon or nitrogen, etc.
Furthermore, in the nitric acid solution in the step 2, the volume ratio of the concentrated nitric acid to the water is (1-3): 1.
The invention also provides application of the fluorinated graphene capsule as a lithium primary battery anode material.
The invention has the beneficial effects that:
the invention provides a preparation method of fluorinated graphene capsules, which utilizes a high-curvature graphene capsule three-dimensional network structure containing a large number of defects to induce generation of C-F with a half-ion bond effect in a fluorination process to obtain F, C>Non-integer ratio CF of 1:1xThe material, x is 1-2. The substrate of the fluorinated graphene capsule provided by the invention has certain recoverability, so that the fluorinated graphene capsule generates a graphene capsule with good crystallinity in the discharging process to serve as a conductive network, the generation of polarization in the discharging process is reduced, and a high-discharge-voltage platform is maintained; meanwhile, the voltage hysteresis effect is reduced, and the graphene capsule structure can promote deep lithium (Li) hanging2F+) The method improves the specific energy of battery discharge, and can be applied to the anode material of the lithium primary battery. Therefore, the fluorinated graphene capsule obtained by the invention is used as a positive electrode material to be applied to a lithium primary battery, so that the specific capacity and the energy density of the battery are effectively improved, the voltage hysteresis effect is improved, and the fluorinated graphene capsule has important significance for popularization and application of lithium/carbon fluoride batteries.
Drawings
Fig. 1 is a TEM image of graphene capsules obtained in step 2 of example 1;
FIG. 2 is an SEM image of the fluorinated graphene capsules obtained in examples 1 to 5; wherein (a) is example 1, (b) is example 2, (c) is example 3, (d) is example 4, and (e) is example 5;
FIG. 3 shows example 5 (CF)x-350) TEM images of the resulting fluorinated graphene capsules;
FIG. 4 shows example 4 (CF)x-325) and example 5 (CF)x-350) an XRD pattern of the obtained fluorinated graphene capsules;
FIG. 5 shows example 4 (CF)x-325) and example 5 (CF)x-350) the discharge curve at 0.01C rate of the resulting fluorinated graphene capsule assembled battery;
FIG. 6 shows example 4 (CF)x-325) and example 5 (CF)x-350) EIS curve of the resulting fluorinated graphene capsule assembled battery.
Detailed Description
The technical scheme of the invention is detailed below by combining the accompanying drawings and the embodiment.
A preparation method of a fluorinated graphene capsule comprises the following steps:
step 1, taking 10-20 g of nano ZnO particles, placing the nano ZnO particles in a CVD rotary furnace, heating the rotary furnace to 450-800 ℃ at a heating rate of 5-15 ℃/min under an argon atmosphere, introducing acetylene gas as reaction gas at a gas flow rate of 20-50 mL/min, reacting for 5-60 min, naturally cooling to room temperature after the reaction is finished, taking out a product, and growing a graphene-coated nano layer on the surface of the nano ZnO particles to obtain a graphene/zinc oxide composite material;
step 3, placing the graphene capsules obtained in the step 2 as a precursor carbon source in a tube furnace, heating to 400-600 ℃ at the speed of 5-15 ℃/min in a nitrogen atmosphere, and preserving heat for 2-6 h at the temperature of 400-600 ℃; and then reducing the temperature to 200-350 ℃, stabilizing, and introducing fluorine gas at the speed of 100-200 mL/min to perform a fluorination reaction for 2-6 h to obtain the fluorinated graphene capsule.
Furthermore, in the nitric acid solution in the step 2, the volume ratio of the concentrated nitric acid to the water is (1-3): 1.
The invention also provides application of the fluorinated graphene capsule as a lithium primary battery anode material.
The invention also provides a lithium/carbon fluoride battery using the fluorinated graphene capsule as a positive active material, which comprises a fluorinated graphene capsule positive electrode, a lithium metal negative electrode, electrolyte and a diaphragm.
Further, the fluorinated graphene capsule positive electrode is formed by coating the mixed slurry of the fluorinated graphene capsule, the conductive carbon black and the PVDF obtained by the method on an aluminum foil current collector.
Example 1
A preparation method of a fluorinated graphene capsule comprises the following steps:
step 1, taking 20g of nano ZnO particles, putting the quartz tube into a rotary CVD furnace, heating the quartz tube to 650 ℃ at the speed of 10 ℃/min under the argon atmosphere, introducing acetylene gas as reaction gas at the speed of 30mL/min, reacting for 30min, naturally cooling the quartz tube to room temperature under the argon atmosphere after the reaction is finished, taking out the product, and growing a graphene-coated nano layer on the surface of the nano ZnO particles to obtain the graphene/zinc oxide composite material;
and 3, putting the graphene capsule obtained in the step 2 as a precursor carbon source into a tubular furnace, heating to 600 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere, preserving the heat for 2 hours at 600 ℃, then reducing the temperature to 200 ℃ at the cooling speed of 10 ℃/min, introducing fluorine gas at the speed of 100mL/min after stabilization, and carrying out fluorination reaction for 2 hours to obtain the black fluorinated graphene capsule.
Fig. 1 is a TEM image of graphene capsules obtained in step 2 of example 1; FIG. 1 shows that the obtained graphene capsule has a smooth surface and different growth thicknesses of carbon layers, wherein the thicknesses are about 5nm to 20 nm.
Example 2
This example is different from example 1 in that:
the specific process of the step 3 is as follows: and (3) putting the graphene capsule obtained in the step (2) as a precursor carbon source into a tubular furnace, heating to 600 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere, preserving the heat for 2h at 600 ℃, then reducing the temperature to 225 ℃ at the cooling speed of 10 ℃/min, introducing fluorine gas at the speed of 160mL/min after stabilization, and carrying out fluorination reaction for 3h to obtain the black and gray fluorinated graphene capsule.
Example 3
This example is different from example 1 in that:
the specific process of the step 3 is as follows: and (3) putting the graphene capsule obtained in the step (2) as a precursor carbon source into a tubular furnace, heating to 600 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere, preserving the heat for 2h at 600 ℃, then reducing the temperature to 250 ℃ at the cooling speed of 10 ℃/min, introducing fluorine gas at the speed of 160mL/min after stabilization, and carrying out fluorination reaction for 4h to obtain the gray fluorinated graphene capsule.
Example 4
This example is different from example 1 in that:
the specific process of the step 3 is as follows: and (3) putting the graphene capsule obtained in the step (2) as a precursor carbon source into a tubular furnace, heating to 600 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere, preserving the heat for 2h at 600 ℃, then reducing the temperature to 325 ℃ at the cooling speed of 10 ℃/min, introducing fluorine gas at the speed of 180mL/min after stabilization, and carrying out fluorination reaction for 5h to obtain the off-white fluorinated graphene capsule.
Example 5
This example is different from example 1 in that:
the specific process of the step 3 is as follows: and (3) putting the graphene capsule obtained in the step (2) as a precursor carbon source into a tubular furnace, heating to 600 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere, preserving the heat for 2h at 600 ℃, then reducing the temperature to 350 ℃ at the cooling speed of 10 ℃/min, introducing fluorine gas at the speed of 200mL/min after stabilization, and carrying out fluorination reaction for 6h to obtain the off-white fluorinated graphene capsule.
FIG. 2 is an SEM image of the fluorinated graphene capsules obtained in examples 1 to 5; as can be seen from fig. 2, the fluorinated graphene still retains the morphology of the graphene capsule, and when the fluorination temperature reaches 350 ℃, the fluorinated graphene capsule has more gaps and the conductivity is deteriorated, which is caused by too much fluorination. FIG. 3 is a TEM image of the fluorinated graphene capsule obtained in example 5; as can be seen from fig. 3, the fluorinated graphene capsules after fluorination have an increased capsule wall thickness compared to those before fluorination, and the capsules have openings, even some carbon has been peeled off from the capsule wall.
Table 1 shows example 4 (CF)x-325) and example 5 (CF)x-350) elemental analysis results of the obtained fluorinated graphene capsules; as can be seen from Table 1, the fluorocarbon ratio of the capsules obtained by fluorination at 325 ℃ in example 4 reached 1.05, whereas the fluorocarbon ratio of the capsules obtained by fluorination at 350 ℃ in example 5 was even as high as 1.91.
TABLE 1
FIG. 4 shows example 4 (CF)x-325) and example 5 (CF)x-350) an XRD pattern of the obtained fluorinated graphene capsules; as can be seen from fig. 4, the diffraction peaks of the fluorinated graphene capsules obtained in examples 4 and 5 both exist in the (12.2 °, 25.6 °, and 41 ° diffraction peaks of 2 θ 12.2 ° and 41 ° respectively corresponding to the (001) plane and the (100) plane of the fluorocarbon, and the (002) plane diffraction peak exists in the case of 2 θ 25.6 ° which is a random diffraction peak of the graphene capsuleThe greater the degree of irregularity, the less distinct the diffraction peak.
Assembling the battery:
preparing slurry from the fluorinated graphene capsules obtained in the embodiments 4 and 5, conductive agent Keqin black and binder PVDF according to the mass ratio of 8:1:1, uniformly coating the slurry on a current collector aluminum foil, and performing vacuum drying at 80 ℃ for 12 hours to obtain a positive plate; and then, assembling the button cell in a glove box by taking the metal lithium as a negative electrode and the fluorinated graphene capsule electrode plate as a positive electrode, and standing for 24 hours to wait for testing.
FIG. 5 shows example 4 (CF)x-325) and example 5 (CF)x-350) the discharge curve at 0.01 magnification of the resulting fluorinated graphene capsule assembled battery; as can be seen from FIG. 5, the voltage platform of the sample obtained in example 4 is high, the specific capacity is 890.5mAh/g, and the specific energy is 1880.21 Wh/kg; the voltage platform of the sample obtained in the embodiment 5 is relatively stable, the specific capacity is 1303.4mAh/g, and the specific energy is 2547.05 Wh/kg; and the samples obtained in example 4 and example 5 have no obvious voltage hysteresis effect.
FIG. 6 shows example 4 (CF)x-325) and example 5 (CF)x-350) EIS curve of fluorinated graphene capsules obtained, the half circle in the curve representing Li+The slope of the straight line represents Li+The diffusion resistance of (1); as can be seen from FIG. 6, as the fluorination temperature increased, the degree of fluorination increased, and Li+Both the embedded resistance and the diffused resistance of (2) are increased.
Claims (5)
1. A preparation method of a fluorinated graphene capsule serving as a positive electrode material of a lithium primary battery is characterized by comprising the following steps:
step 1, placing nano ZnO particles in a rotary furnace, introducing inert gas as protective gas, heating the rotary furnace to 450-800 ℃, introducing catalytic carbon source gas as reaction gas for catalytic reaction at 450-800 ℃ for 5-60 min while keeping the introduction of the inert gas, naturally cooling to room temperature after the catalytic reaction is finished, and taking out a product to obtain the graphene/zinc oxide composite material;
step 2, soaking the product obtained in the step 1 in nitric acid for 12-48 hours to remove nano ZnO particles, separating, drying, and then preserving heat for 2-4 hours at 900-1500 ℃ in an inert gas atmosphere in a CVD furnace to obtain a graphene capsule;
step 3, placing the graphene capsules obtained in the step 2 into a tube furnace, heating to 400-600 ℃ under an inert gas atmosphere, and preserving heat for 2-6 hours at 400-600 ℃; and then reducing the temperature to 200-350 ℃, introducing fluorine gas at the speed of 100-200 mL/min, and carrying out fluorination reaction for 2-6 h to obtain the fluorinated graphene capsule.
2. The method for preparing the fluorinated graphene capsule as the positive electrode material of the lithium primary battery according to claim 1, wherein the flow rate of the catalytic carbon source gas in the step 1 is 20-50 mL/min, and the flow rate of the protective gas is 5-50 mL/min.
3. The method for preparing the fluorinated graphene capsule as the positive electrode material of the lithium primary battery according to claim 1, wherein the catalytic carbon source gas in the step 1 is acetylene; the protective gas is argon.
4. The method for preparing the fluorinated graphene capsule serving as the positive electrode material of the lithium primary battery according to claim 1, wherein the volume ratio of concentrated nitric acid to water in the nitric acid solution in the step 2 is (1-3): 1.
5. Use of the fluorinated graphene capsules obtained by the method of any one of claims 1 to 4 as a positive electrode material for lithium primary batteries.
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| 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 |
| CN112234191B (en) * | 2020-09-14 | 2021-09-10 | 方大炭素新材料科技股份有限公司 | Electrode active material, preparation method and lithium primary battery |
| CN112687873B (en) * | 2020-12-23 | 2021-12-07 | 湖南永盛新材料股份有限公司 | Preparation method of high-specific-energy lithium battery |
| CN113233443A (en) * | 2021-04-22 | 2021-08-10 | 电子科技大学 | Preparation method of fluorinated spiral carbon nanotube and application of fluorinated spiral carbon nanotube in lithium primary battery |
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