CN109148850A - A kind of preparation method of fluorinated graphene capsule and the application in lithium primary battery - Google Patents
A kind of preparation method of fluorinated graphene capsule and the application in lithium primary battery Download PDFInfo
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Abstract
A kind of preparation method of fluorinated graphene capsule and the application in lithium primary battery, belong to one-shot battery technical field.The following steps are included: firstly, preparing three-dimensional grapheme capsule;Then it is placed in tube furnace using graphene capsule obtained as presoma carbon source, is heated to 400~600 DEG C under inert gas atmosphere, 2~6h is kept the temperature at 400~600 DEG C;Then temperature is reduced to 200~350 DEG C, fluorine gas is passed through with the rate of 100~200mL/min, 2~6h of fluorination reaction is carried out, obtains the fluorinated graphene capsule.The fluorinated graphene capsule that the present invention obtains is applied in lithium primary battery as positive electrode, improves voltage delay effect, promotes depth and hangs lithium (Li2F+) mode, the specific capacity and energy density of battery are effectively increased, is of great significance to the popularization and application of lithium/fluorination carbon battery.
Description
Technical field
The invention belongs to one-shot battery technical fields, and in particular to a kind of preparation method of fluorinated graphene capsule and
Application in lithium primary battery.
Background technique
Lithium/fluorination carbon battery is with high energy electrode material fluorocarbons (CFx) it is positive electrode active materials, lithium metal is cathode material
Expect the one-shot battery of composition.Currently, on the market common lithium battery have lithium/manganese dioxide battery, lithium/sulfur dioxide battery, lithium/
Thionyl chloride battery, lithium/fluorination carbon battery etc..Relative to other solid positive electrode batteries, lithium/fluorination carbon battery theoretical energy
Density highest (up to 2180Wh/kg), practical specific energy may be up to 250~800Wh/kg, while be easily achieved miniaturization, light
Type, and there are the spies such as discharge platform is stable, self discharge is small, storage life is long, wide temperature range, safe green is pollution-free
Point can meet the application requirement of high-end civilian instrument, military equipment and aerospace backup power source, have huge market latent
Power, by the extensive concern of researcher.However, still having many limitation lithiums/widely applied problem of fluorination carbon battery at present:
First, fluorinated carbon material because its degree of fluorination causes electric conductivity poor, influences the defeated electric discharge under its discharge performance, especially high current
Ability;Second, there are hysteresis effects for voltage, the defects of platform is low, at high cost is existed simultaneously.And fluorine is carried out using different carbon sources
Change, the performance of fluorocarbons can be improved.Chinese patent 201711435109.8 discloses one kind using Ketjen black as presoma carbon
It is low to efficiently solve fluorocarbons voltage platform using the good electric conductivity of Ketjen black for the fluorination Ketjen black material that source is fluorinated
With the problem of electric conductivity difference, but its specific capacity does not get a promotion, and voltage delay effect still has.
Summary of the invention
In view of the defects in the background art, the present invention proposes a kind of preparation method of fluorinated graphene capsule and in lithium
Application in one-shot battery.The fluorinated graphene capsule that the present invention obtains is applied in lithium primary battery as positive electrode, has
Effect improves the specific capacity and energy density of battery, improves voltage delay effect.
Technical scheme is as follows:
A kind of preparation method of fluorinated graphene capsule, comprising the following steps:
Step 1 takes 10~20g nano ZnO particles to be placed in CVD revolving burner, is passed through inert gas as protective gas, rotation
Converter revolving speed is 5~10 turns/min, logical while keeping inert gas to be passed through after revolving burner is then warming up to 450~800 DEG C
Entering to be catalyzed carbon-source gas as reaction gas and carries out catalysis reaction, reaction temperature is 450~800 DEG C, the reaction time is 5~
60min, cooled to room temperature, takes out product after the completion, can grow coated graphite alkene nanometer on nano ZnO particles surface
Layer, obtains graphene/zinc oxide composite material;
Step 2, the product for obtaining step 1 impregnate 12~48h in nitric acid, to remove nano ZnO particles, separate, do
After dry, in CVD furnace inert gas atmosphere, 2~4h is kept the temperature at 900~1500 DEG C, obtain graphene capsule (GC);
The graphene capsule that step 2 obtains is placed in tube furnace by step 3 as presoma carbon source, in inert gas gas
It is heated to 400~600 DEG C under atmosphere, 2~6h is kept the temperature at 400~600 DEG C;Then temperature is reduced to 200~350 DEG C, with 100
The rate of~200mL/min is passed through fluorine gas, carries out 2~6h of fluorination reaction, the fluorinated graphene capsule can be obtained.
Further, the flow that carbon-source gas is catalyzed in step 1 is 20~50mL/min, the flow of protective gas is 5~
50mL/min。
Further, catalysis carbon-source gas described in step 1 is acetylene;The protective gas is argon gas or nitrogen etc..
Further, in nitric acid solution described in step 2, the volume ratio of concentrated nitric acid and water is (1~3): 1.
Application the present invention also provides above-mentioned fluorinated graphene capsule as lithium primary battery positive electrode.
The invention has the benefit that
The present invention provides a kind of preparation methods of fluorinated graphene capsule, utilize the higher curvature graphite for containing a large amount of defects
Alkene capsule three-dimensional net structure, the C-F that half ionic bond of inductive formation acts in fluorination process, has obtained the non-whole of F:C > 1:1
Number compares CFxMaterial, x=1~2.The substrate of fluorinated graphene capsule provided by the invention has certain restorability, so that fluorine
Graphite alkene capsule generates the good graphene capsule of crystallinity as conductive network during discharge, reduces discharge process
In polarized generation, maintain high discharge voltage plateau;Meanwhile voltage delay effect is reduced, graphene capsule structure can be with
Depth is promoted to hang lithium (Li2F+), battery discharge specific energy is improved, can be applied in lithium primary battery positive electrode.Therefore, originally
It invents obtained fluorinated graphene capsule to be applied in lithium primary battery as positive electrode, effectively increases the specific capacity of battery
And energy density, voltage delay effect is improved, is of great significance to the popularization and application of lithium/fluorination carbon battery.
Detailed description of the invention
Fig. 1 is the TEM figure for the graphene capsule that 1 step 2 of embodiment obtains;
Fig. 2 is the SEM figure for the fluorinated graphene capsule that Examples 1 to 5 obtains;Wherein, (a) is embodiment 1, (b) is real
Example 2 is applied, (c) is embodiment 3, (d) is embodiment 4, (e) is embodiment 5;
Fig. 3 is 5 (CF of embodimentx- 350) TEM of the fluorinated graphene capsule obtained schemes;
Fig. 4 is 4 (CF of embodimentx- 325) and 5 (CF of embodimentx- 350) XRD spectrum of the fluorinated graphene capsule obtained;
Fig. 5 is 4 (CF of embodimentx- 325) and 5 (CF of embodimentx- 350) battery of the fluorinated graphene capsule assembling obtained
Discharge curve under 0.01C multiplying power;
Fig. 6 is 4 (CF of embodimentx- 325) and 5 (CF of embodimentx- 350) battery of the fluorinated graphene capsule assembling obtained
EIS curve.
Specific embodiment
With reference to the accompanying drawings and examples, technical solution of the present invention is described in detail.
A kind of preparation method of fluorinated graphene capsule, comprising the following steps:
Step 1 takes 10~20g nano ZnO particles to be placed in CVD revolving burner, and revolving burner revolving speed is 5~10 turns/min,
Under argon atmosphere revolving burner is warming up to 450~800 DEG C under the heating rate of 5~15 DEG C/min after, with throughput be 20~
The rate of 50mL/min is passed through acetylene gas as reaction gas, 5~60min of reaction time, after the completion cooled to room temperature,
Product is taken out, coated graphite alkene nanometer layer can be grown on nano ZnO particles surface, obtain graphene/zinc oxide composite wood
Material;
Step 2, the product for obtaining step 1 impregnate 12~48h in nitric acid, to remove nano ZnO particles, separate, do
After dry, in CVD revolving burner inert gas atmosphere, 2~4h is kept the temperature at 900~1500 DEG C, obtain graphene capsule (GC);
The graphene capsule that step 2 obtains is placed in tube furnace by step 3 as presoma carbon source, in a nitrogen atmosphere
400~600 DEG C are heated to the rate of 5~15 DEG C/min, 2~6h is kept the temperature at 400~600 DEG C;Then temperature is reduced to
200~350 DEG C, fluorine gas is passed through with the rate of 100~200mL/min after stablizing, 2~6h of fluorination reaction is carried out, can be obtained
The fluorinated graphene capsule.
Further, in nitric acid solution described in step 2, the volume ratio of concentrated nitric acid and water is (1~3): 1.
Application the present invention also provides above-mentioned fluorinated graphene capsule as lithium primary battery positive electrode.
The present invention also provides a kind of using fluorinated graphene capsule as the lithium of positive electrode active materials/fluorination carbon battery, including
Fluorinated graphene capsule anode, lithium an- ode, electrolyte and diaphragm.
Further, the fluorinated graphene capsule anode be by by fluorinated graphene capsule obtained by the above method,
The mixed slurry of conductive black and PVDF is coated in aluminum foil current collector and is formed.
Embodiment 1
A kind of preparation method of fluorinated graphene capsule, comprising the following steps:
Step 1 takes 20g nano ZnO particles to be put into quartz ampoule, and quartz ampoule is placed in rotation CVD furnace, revolving burner
Revolving speed is 5 turns/min, is 30mL/min's with throughput after being heated to 650 DEG C under an argon atmosphere with the rate of 10 DEG C/min
Rate is passed through acetylene gas as reaction gas, and reaction time 30min naturally cools to room under an argon atmosphere after the reaction was completed
Temperature takes out product, can grow coated graphite alkene nanometer layer on nano ZnO particles surface, it is compound to obtain graphene/zinc oxide
Material;
(in nitric acid solution, the volume ratio of concentrated nitric acid and water the is 1:1) leaching in nitric acid of step 2, the product for obtaining step 1
For 24 hours, impregnate number is 3 times to bubble, to remove nano ZnO particles, after separating, adopting and be washed with deionized, dry, in CVD furnace
Nitrogen atmosphere keeps the temperature 2h at 900 DEG C, and cooled to room temperature is taken out, obtains graphene capsule (GC);
The graphene capsule that step 2 obtains is placed in tube furnace by step 3 as presoma carbon source, in a nitrogen atmosphere
600 DEG C are heated to the rate of 10 DEG C/min, 2h is kept the temperature at 600 DEG C, is then dropped temperature with the rate of temperature fall of 10 DEG C/min
To 200 DEG C, fluorine gas is passed through with the rate of 100mL/min after stablizing, fluorination reaction 2h is carried out, the fluorination stone of black can be obtained
Black alkene capsule.
Fig. 1 is the TEM figure for the graphene capsule that 1 step 2 of embodiment obtains;The graphene capsule surface that Fig. 1 shows
Smooth, the thickness of carbon-coating growth is different, and thickness is about 5nm~20nm.
Embodiment 2
Compared with Example 1, difference is the present embodiment:
The detailed process of step 3 are as follows: the graphene capsule that step 2 obtains is placed in tube furnace as presoma carbon source,
600 DEG C are heated to the rate of 10 DEG C/min in a nitrogen atmosphere, 2h is kept the temperature at 600 DEG C, then with the cooling of 10 DEG C/min
Rate cools the temperature to 225 DEG C, is passed through fluorine gas after stablizing with the rate of 160mL/min, carries out fluorination reaction 3h, can be obtained
The fluorinated graphene capsule of black gray expandable.
Embodiment 3
Compared with Example 1, difference is the present embodiment:
The detailed process of step 3 are as follows: the graphene capsule that step 2 obtains is placed in tube furnace as presoma carbon source,
600 DEG C are heated to the rate of 10 DEG C/min in a nitrogen atmosphere, 2h is kept the temperature at 600 DEG C, then with the cooling of 10 DEG C/min
Rate cools the temperature to 250 DEG C, is passed through fluorine gas after stablizing with the rate of 160mL/min, carries out fluorination reaction 4h, can be obtained
The fluorinated graphene capsule of grey.
Embodiment 4
Compared with Example 1, difference is the present embodiment:
The detailed process of step 3 are as follows: the graphene capsule that step 2 obtains is placed in tube furnace as presoma carbon source,
600 DEG C are heated to the rate of 10 DEG C/min in a nitrogen atmosphere, 2h is kept the temperature at 600 DEG C, then with the cooling of 10 DEG C/min
Rate cools the temperature to 325 DEG C, is passed through fluorine gas after stablizing with the rate of 180mL/min, carries out fluorination reaction 5h, can be obtained
Linen fluorinated graphene capsule.
Embodiment 5
Compared with Example 1, difference is the present embodiment:
The detailed process of step 3 are as follows: the graphene capsule that step 2 obtains is placed in tube furnace as presoma carbon source,
600 DEG C are heated to the rate of 10 DEG C/min in a nitrogen atmosphere, 2h is kept the temperature at 600 DEG C, then with the cooling of 10 DEG C/min
Rate cools the temperature to 350 DEG C, is passed through fluorine gas after stablizing with the rate of 200mL/min, carries out fluorination reaction 6h, can be obtained
Linen fluorinated graphene capsule.
Fig. 2 is the SEM figure for the fluorinated graphene capsule that Examples 1 to 5 obtains;As shown in Figure 2, the fluorination stone after perfluorinated
Black alkene still retains the pattern of graphene capsule, and when fluorination temperature reaches 350 DEG C, fluorinated graphene capsule occurs more
Notch, electric conductivity is deteriorated, this is caused by degree of fluorination is too big.Fig. 3 is the fluorinated graphene capsule that embodiment 5 obtains
TEM figure;From the figure 3, it may be seen that capsule wall thickness of the fluorinated graphene capsule after perfluorinated compared with before fluorination increases, capsule is opened
Mouth or even some carbon are peeled off from capsule wall.
Table 1 is 4 (CF of embodimentx- 325) and 5 (CF of embodimentx- 350) elemental analysis of the fluorinated graphene capsule obtained
As a result;As shown in Table 1, the fluorine carbon ratio for the capsule that embodiment 4 is fluorinated at 325 DEG C reaches 1.05, and embodiment 5 is 350
The fluorine carbon ratio for the capsule being fluorinated at DEG C is even as high as 1.91.
Table 1
Fig. 4 is 4 (CF of embodimentx- 325) and 5 (CF of embodimentx- 350) XRD spectrum of the fluorinated graphene capsule obtained;
As shown in Figure 4, the diffraction maximum for the fluorinated graphene capsule that embodiment 4 and embodiment 5 obtain is present in 2 θ=12.2 °,
25.6 °, 41 °, wherein 2 θ=12.2 ° and 41 ° of diffraction maximum correspond respectively to (001) face and (100) face of fluorocarbons, 2 θ=
There are one than wider (002) face diffraction maximum at 25.6 °, this is the random stacking formation of graphene capsule, random
Degree is bigger, and the diffraction maximum is more unobvious.
The assembling of battery:
The fluorinated graphene capsule and conductive agent Ketjen black, binder PVDF that embodiment 4 and embodiment 5 are obtained are with quality
Ratio than 8:1:1 prepares slurry, is evenly applied in current collector aluminum foil, and is dried in vacuo 12h at 80 DEG C and obtains positive plate;
Then, using lithium metal as cathode, fluorinated graphene capsule electrode slice is anode, button cell is assembled into glove box, then put
It sets for 24 hours etc. to be tested.
Fig. 5 is 4 (CF of embodimentx- 325) and 5 (CF of embodimentx- 350) battery of the fluorinated graphene capsule assembling obtained
Discharge curve under 0.01 multiplying power;As shown in Figure 5, the sample voltage platform that embodiment 4 obtains is higher, and specific capacity is
890.5mAh/g specific energy 1880.21Wh/kg;And the sample voltage platform that embodiment 5 obtains is more steady, specific capacity is up to
1303.4mAh/g, specific energy are more up to 2547.05Wh/kg;And the sample that embodiment 4 and embodiment 5 obtain is without obvious
Voltage delay effect.
Fig. 6 is 4 (CF of embodimentx- 325) and 5 (CF of embodimentx- 350) the EIS curve of the fluorinated graphene capsule obtained,
Semicircle in curve indicates Li+Insertion resistance, the slope of straight line indicates Li+Diffusion resistance;It will be appreciated from fig. 6 that with fluorination temperature
The raising of degree, the increase of degree of fluorination, Li+Insertion resistance and diffusion resistance all increased.
Claims (5)
1. a kind of preparation method of fluorinated graphene capsule, which comprises the following steps:
Step 1 takes nano ZnO particles to be placed in revolving burner, is passed through inert gas as protective gas, then revolving burner heats up
To after 450~800 DEG C, keeps inert gas to be passed through catalysis carbon-source gas while being passed through as reaction gas and be catalyzed instead
It answers, reaction temperature is 450~800 DEG C, and the reaction time is 5~60min, after the completion cooled to room temperature, takes out product, obtains
Graphene/zinc oxide composite material;
Step 2, the product for obtaining step 1 impregnate 12~48h in nitric acid, to remove nano ZnO particles, separation, and after dry,
In CVD furnace inert gas atmosphere, 2~4h is kept the temperature at 900~1500 DEG C, obtain graphene capsule;
The graphene capsule that step 2 obtains is placed in tube furnace by step 3, is heated to 400~600 under inert gas atmosphere
DEG C, 2~6h is kept the temperature at 400~600 DEG C;Then temperature is reduced to 200~350 DEG C, with the rate of 100~200mL/min
It is passed through fluorine gas, 2~6h of fluorination reaction is carried out, the fluorinated graphene capsule can be obtained.
2. the preparation method of fluorinated graphene capsule according to claim 1, which is characterized in that be catalyzed carbon source in step 1
The flow of gas is 20~50mL/min, and the flow of protective gas is 5~50mL/min.
3. the preparation method of fluorinated graphene capsule according to claim 1, which is characterized in that be catalyzed described in step 1
Carbon-source gas is acetylene;The protective gas is argon gas or nitrogen.
4. the preparation method of fluorinated graphene capsule according to claim 1, which is characterized in that nitric acid described in step 2 is molten
In liquid, the volume ratio of concentrated nitric acid and water is (1~3): 1.
5. the fluorinated graphene capsule that any one of claims 1 to 4 the method obtains is as lithium primary battery positive electrode
Application.
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CN112234191A (en) * | 2020-09-14 | 2021-01-15 | 方大炭素新材料科技股份有限公司 | Electrode active material, preparation method and lithium primary battery |
CN112687873A (en) * | 2020-12-23 | 2021-04-20 | 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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