CN109390551A - A kind of preparation method of nanometer-material-modified fluorination carbon electrode material - Google Patents
A kind of preparation method of nanometer-material-modified fluorination carbon electrode material Download PDFInfo
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- CN109390551A CN109390551A CN201811406302.3A CN201811406302A CN109390551A CN 109390551 A CN109390551 A CN 109390551A CN 201811406302 A CN201811406302 A CN 201811406302A CN 109390551 A CN109390551 A CN 109390551A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 70
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 60
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 35
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims description 28
- 238000000703 high-speed centrifugation Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000011268 mixed slurry Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000003273 ketjen black Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000005030 aluminium foil Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 125000001153 fluoro group Chemical class F* 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 16
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a kind of preparation methods of nanometer-material-modified fluorination carbon electrode material, medium and fluorocarbons are mixed, after nano material reaction is added, after being dried, be dried in vacuo, being ground, it calcines under an argon atmosphere, it is cooled to room temperature, then after ground, 100~200 meshes excessively, the nanometer-material-modified fluorination carbon electrode material is made；The nano material and fluorocarbons are according to mass ratio=(0.5~5): 100 compositions.The application carries out modification to fluorinated carbon material using nano material, nano material is uniformly coated on fluorinated carbon material surface, increase the electric conductivity of fluorinated carbon material, the problem of effectively improving the voltage delay and cryogenic property of fluorinated carbon material, improves the high rate performance of lithium fluorocarbon battery.
Description
Technical field
The invention belongs to lithium primary batteries to produce and process technical field, more particularly to a kind of nanometer-material-modified fluorocarbons
The preparation method of electrode material.
Background technique
Lithium primary battery (primary lithium battery), is a kind of high-energy chemistry primary battery, is commonly called as lithium battery.
Using lithium metal as cathode, solid salt or the salt for being dissolved in organic solvent are electrolyte, metal oxide or other solids, liquid
Oxidant is positive electrode active material.General round lithium-manganese dioxide (Li/MnO2) battery and lithium fluorocarbon (Li/ (CFx) n) battery
It is indicated respectively with letter C R and BR, the model of digital representation battery thereafter.Lithium primary battery is this kind to use lithium metal
For the general name of the electrochmical power source series of negative electrode material.
Lithium fluorocarbon battery is high-energy density one-shot battery, and it is dry that practical specific energy, which can achieve 250~700Wh/kg,
The several times of battery, and battery is easily done miniaturization and lightness.Since fluorinated carbon material is highly stable, thus lithium fluorocarbon
Capacity retention ratio is higher under battery high-temperature, will not decay substantially.Fluorocarbons is that the carbon of various forms and fluorine gas reaction are formed by
Compound, although this substance has electro-chemical activity, the chemical stability in organic bath is very high, and temperature is up to
It will not be thermally decomposed at 500 DEG C, thus there is long storage life and good high-temperature behavior.Furthermore the system battery has work
Make that voltage is steady, self-discharge rate is low, safety is good, the series of advantages such as environmentally protective.At present by the advanced state such as the U.S., Japan
Family is applied to military industry field.
Patent application CN104577107A discloses a kind of surface modification method of fluorinated carbon material；The preparation of this method
Step includes: to mix Nanometer Copper and fluorocarbons, forms mixed slurry after adding solvent ball milling；Mixed slurry is dry, is formed
Mixture；Mixture is sieved, mix powder is obtained；Mixture is sieved, mix powder is obtained；Mix powder is set
Enter in atmosphere furnace and calcines；Calcined mix powder is taken out, is cooled to room temperature, is sieved, that is, forms the fluorine modified through Nanometer Copper
Change carbon material.This method by by fluorocarbons with have after good conductive nanometer copper mix, inert atmosphere high temperature is calcined
Afterwards, Nanometer Copper is in fluorination carbon surface reaction, hence it is evident that improves fluorocarbons voltage delay phenomenon, improves big high rate performance and low temperature
Performance.Although the patent improves the voltage delay of fluorocarbons, but the battery 0.1C multiplying power prepared is only by the first of fluorinated carbon material
Beginning discharge voltage is increased to 2.49V by 2.35V, and platform voltage is increased to 2.52V by 2.49V, and improvement is unobvious.
With the rapid development of the fields technologies such as mancarried electronic aid, accurate medical treatment, aerostatics and aerospace, compel to be essential
Seek electrochmical power source of lithium of high power, high-energy-density, high security.There is serious voltage is stagnant for lithium fluorocarbon battery at present
Technical problem afterwards.Because conducting polymer is with good stability and electric conductivity, domestic and foreign scholars use conductive poly- pyrrole one after another
Cough up, polyaniline and polythiophene etc. are modified fluorinated carbon material, but effect is all less fully up to expectations.
Summary of the invention
The present invention is in order to solve the above technical problems, provide a kind of preparation of nanometer-material-modified fluorination carbon electrode material
Method.The application carries out modification to fluorinated carbon material using nano material, and nano material is uniformly coated on fluorination carbon materials
Expect surface, increase the electric conductivity of fluorinated carbon material, effectively improves the voltage delay and cryogenic property of fluorinated carbon material
Problem improves the high rate performance of lithium fluorocarbon battery；Carbon materials are fluorinated with conducting polymers coating modifications such as polyaniline, polythiophenes
The method of material is compared, and technical solution of the present invention does not use poisonous and hazardous substance, environmental-friendly.
In order to reach purpose described above, the invention adopts the following technical scheme:
A kind of preparation method of nanometer-material-modified fluorination carbon electrode material, this method is dispersion-calcination method, including with
Lower step:
Step 1: by medium and fluorocarbons according to mass ratio=(2~3): 1 ratio is added in high speed centrifugation dispersion tank, allows
Material disperses 10~30min in high speed centrifugation dispersion tank with the revolving speed of 2000~3000r/min；
Step 2: nano material is added into high speed centrifugation dispersion tank, allow material in high speed centrifugation dispersion tank with 3000~
The revolving speed of 3500r/min disperses 1~2h, obtains slurry；
Step 3: after the slurry room temperature that step 2 obtains is dried, then under 30~40 DEG C of vacuum environment vacuum drying 8~
12h obtains mixture；
Step 4: the resulting mixture of step 3 being ground to 100~200 meshes, obtains mix powder；
Step 5: the resulting mix powder of step 4 being calcined into 1~12h under an argon atmosphere, heating rate is 5~10
DEG C/min, calcination temperature is 300~450 DEG C；
Step 6: the material after the completion of step 5 calcining being cooled to room temperature with the speed of 10~20 DEG C/min, ground, mistake
After 100~200 meshes, the nanometer-material-modified fluorination carbon electrode material is obtained.
Further, in step 1, the medium is ethyl alcohol, acetone.
Further, in step 2, the nano material is nano silver.
Further, in step 2, mass ratio=(0.5~5) of the nano material and fluorinated carbon material: 100；In step
Rapid 2, the diameter of the nano material is 10~100nm.
Further, in step 3, the vacuum drying vacuum degree is -0.08kPa~-0.09kPa.
Further, a kind of preparation method of nanometer-material-modified fluorination carbon electrode, comprising the following steps:
(1) and slurry: weighing superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified according to mass ratio
Fluorination carbon electrode material, all raw materials are mixed, are stirred evenly, mixed slurry is made；
(2) it coats: above-mentioned gained mixed slurry is coated uniformly on aluminium foil two sides, be placed in 70~90 DEG C of baking ovens dry 30
~60min obtains nanometer-material-modified fluorocarbons pole piece；
(3) heat rolls: above-mentioned nanometer-material-modified fluorocarbons pole piece being carried out heat and is rolled, the nano material is obtained and repairs
The fluorination carbon electrode of decorations.
Further, the superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified fluorocarbons
The mass ratio of electrode material=(0.02~0.03): (0.01~0.02): (0.02~0.03): (0.02~0.03): (0.03~
0.04): (1.8~2.2): (0.85~0.90).
Further, in step (1), the speed of the stirring is 300~500r/min, and the time is 65~100min.
Further, in step (2), it is 2.0~3.3g/100cm that the mixed slurry, which is coated in the density on aluminium foil,2。
Further, in step (3), the temperature that the heat rolls is 35~50 DEG C, with a thickness of 0.15~0.19mm.
Further, the superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified fluorocarbons
Mass ratio=0.03:0.01:0.02:0.02:0.03:(1.9~2.1 of electrode material): (0.86~0.89).
Further, the superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified fluorocarbons
Mass ratio=0.02:0.02:0.03:0.03:0.04:2.0:0.87 of electrode material.
Since present invention employs above technical schemes, have the advantages that
(1) the application carries out modification to fluorinated carbon material using the preferable nano material of electric conductivity, and nano material is equal
Even is coated on fluorinated carbon material surface, increases the electric conductivity of fluorinated carbon material, effectively improves the voltage of fluorinated carbon material
Lag issues improve the high rate performance of fluorinated carbon material.
(2) the nanometer-material-modified fluorination carbon electrode material of the application and common manganese dioxide, silver metavanadate are modified
Be fluorinated carbon electrode material the difference is that, manganese dioxide, silver metavanadate modification fluorination carbon electrode improve electric conductivity mode
It is equivalent to the concerted reaction of combination electrode, and the application is increased by coating a small amount of nano material on fluorinated carbon material surface
The electric conductivity of fluorinated carbon material, to solve the problems, such as that fluorocarbons electrode voltage lags.
(3) the nanometer-material-modified fluorination carbon electrode material of the application is applied in lithium fluorocarbon battery, is effectively changed
It has been apt to be fluorinated the voltage delay of carbon electrode, has improved the platform voltage of electrode, significant effect.The low wave voltage of carbon electrode will be fluorinated
By 2.35V, it is increased to 2.5V, improves 6%；Platform voltage is increased to 2.8V or more by 2.5V, improves 12%.It is relatively existing
The fluorination carbon electrode of technology, voltage delay and platform voltage greatly improve, and significantly improve the discharge performance of fluorinated carbon material.
Detailed description of the invention
In order to illustrate more clearly of present example or technical solution in the prior art, to embodiment or will show below
There is in technical description required attached drawing do simply to introduce, it should be apparent that, the accompanying drawings in the following description is only the present invention
Some examples to those skilled in the art, can also be attached according to these under the premise of not paying creativeness
Figure obtains other attached drawings:
Fig. 1 be the resulting nanometer-material-modified fluorination carbon electrode material of the embodiment of the present application 1 at 25 DEG C with comparative example 1
Discharge curve；
Specific embodiment
Specific embodiments of the present invention will be described in further detail below, but the invention is not limited to these realities
Mode is applied, it is claimed to still fall within the claims in the present invention for any improvement or replacement on the present embodiment essence spirit
Range.
Embodiment 1
A kind of preparation method of nanometer-material-modified fluorination carbon electrode material, this method is dispersion-calcination method, including with
Lower step:
Step 1: medium and fluorocarbons being added in high speed centrifugation dispersion tank according to mass ratio=2:1 ratio, allow material
20min is dispersed with the revolving speed of 2500r/min in high speed centrifugation dispersion tank；The medium is ethyl alcohol, acetone；
Step 2: nano material is added into high speed centrifugation dispersion tank, allows material in high speed centrifugation dispersion tank with 3000r/
The revolving speed of min disperses 1.5h, obtains slurry；The nano material is nano silver；The matter of the nano material and fluorinated carbon material
Measure ratio=0.5:100；The diameter of the nano material is 50nm；
Step 3: after the slurry room temperature that step 2 obtains is dried, then under 35 DEG C of vacuum environment being dried in vacuo 10h, obtain
To mixture；The vacuum drying vacuum degree is -0.08kPa；
Step 4: the resulting mixture of step 3 being ground to and is sieved with 100 mesh sieve, mix powder is obtained；
Step 5: the resulting mix powder of step 4 being calcined into 5h under an argon atmosphere, heating rate is 5 DEG C/min, is forged
Burning temperature is 300 DEG C；
Step 6: the material after the completion of step 5 calcining being cooled to room temperature with the speed of 10 DEG C/min, ground, mistake 100
After mesh, the nanometer-material-modified fluorination carbon electrode material is obtained.
A kind of preparation method of nanometer-material-modified fluorination carbon electrode, comprising the following steps:
(1) and slurry: weighing superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified according to mass ratio
Fluorination carbon electrode material, all raw materials are mixed, are stirred evenly, mixed slurry is made；The speed of the stirring be 300~
500r/min, time are 65~100min；
(2) it coats: above-mentioned gained mixed slurry is coated uniformly on aluminium foil two sides, be placed in 70~90 DEG C of baking ovens dry 30
~60min obtains nanometer-material-modified fluorocarbons pole piece；The mixed slurry be coated in aluminium foil on density be 2.0~
3.3g/100cm2；
(3) heat rolls: above-mentioned nanometer-material-modified fluorocarbons pole piece being carried out heat and is rolled, the nano material is obtained and repairs
The fluorination carbon electrode of decorations；The temperature that the heat rolls is 35~50 DEG C, with a thickness of 0.15~0.19mm.
Further, the superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified fluorocarbons
The mass ratio of electrode material=(0.02~0.03): (0.01~0.02): (0.02~0.03): (0.02~0.03): (0.03~
0.04): (1.8~2.2): (0.85~0.90).
Embodiment 2
A kind of preparation method of nanometer-material-modified fluorination carbon electrode material, this method is dispersion-calcination method, including with
Lower step:
Step 1: medium and fluorocarbons being added in high speed centrifugation dispersion tank according to mass ratio=3:1 ratio, allow material
30min is dispersed with the revolving speed of 3000r/min in high speed centrifugation dispersion tank；The medium is ethyl alcohol, acetone；
Step 2: nano material is added into high speed centrifugation dispersion tank, allows material in high speed centrifugation dispersion tank with 3500r/
The revolving speed of min disperses 2h, obtains slurry；The nano material is nano silver；The quality of the nano material and fluorinated carbon material
Than=5:100；The diameter of the nano material is 100nm；
Step 3: after the slurry room temperature that step 2 obtains is dried, then being dried in vacuo under 30~40 DEG C of vacuum environment
12h obtains mixture；The vacuum drying vacuum degree is -0.09kPa；
Step 4: the resulting mixture of step 3 being ground to 200 meshes, obtains mix powder；
Step 5: the resulting mix powder of step 4 is calcined into 12h under an argon atmosphere, heating rate is 10 DEG C/min,
Calcination temperature is 450 DEG C；
Step 6: the material after the completion of step 5 calcining being cooled to room temperature with the speed of 20 DEG C/min, ground, mistake 200
After mesh, the nanometer-material-modified fluorination carbon electrode material is obtained.
Nanometer-material-modified fluorination carbon electrode is prepared using the nanometer-material-modified fluorination carbon electrode material of the present embodiment
Method it is same as Example 1.
Embodiment 3
A kind of preparation method of nanometer-material-modified fluorination carbon electrode material, this method is dispersion-calcination method, including with
Lower step:
Step 1: medium and fluorocarbons being added in high speed centrifugation dispersion tank according to mass ratio=2:1 ratio, allow material
10min is dispersed with the revolving speed of 2000r/min in high speed centrifugation dispersion tank；The medium is ethyl alcohol, acetone；
Step 2: nano material is added into high speed centrifugation dispersion tank, allows material in high speed centrifugation dispersion tank with 3000r/
The revolving speed of min disperses 1h, obtains slurry；The nano material is nano silver；The quality of the nano material and fluorinated carbon material
Than=0.5:100；The diameter of the nano material is 10nm；
Step 3: after the slurry room temperature that step 2 obtains is dried, then under 30 DEG C of vacuum environment being dried in vacuo 8h, obtain
Mixture；The vacuum drying vacuum degree is -0.08kPa；
Step 4: the resulting mixture of step 3 being ground to and is sieved with 100 mesh sieve, mix powder is obtained；
Step 5: the resulting mix powder of step 4 being calcined into 1h under an argon atmosphere, heating rate is 5 DEG C/min, is forged
Burning temperature is 300 DEG C；
Step 6: the material after the completion of step 5 calcining being cooled to room temperature with the speed of 10 DEG C/min, ground, mistake 100
After mesh, the nanometer-material-modified fluorination carbon electrode material is obtained.
Nanometer-material-modified fluorination carbon electrode is prepared using the nanometer-material-modified fluorination carbon electrode material of the present embodiment
Method it is same as Example 1.
Embodiment 4
A kind of preparation method of nanometer-material-modified fluorination carbon electrode material, this method is dispersion-calcination method, including with
Lower step:
Step 1: medium and fluorocarbons being added in high speed centrifugation dispersion tank according to mass ratio=2.2:1 ratio, allow object
Expect to disperse 15min in high speed centrifugation dispersion tank with the revolving speed of 2200r/min；The medium is ethyl alcohol, acetone；
Step 2: nano material is added into high speed centrifugation dispersion tank, allows material in high speed centrifugation dispersion tank with 3100r/
The revolving speed of min disperses 1.2h, obtains slurry；The nano material is nano silver；The matter of the nano material and fluorinated carbon material
Measure ratio=1:100；The diameter of the nano material is 20nm；
Step 3: after the slurry room temperature that step 2 obtains is dried, then under 32 DEG C of vacuum environment being dried in vacuo 9h, obtain
Mixture；The vacuum drying vacuum degree is -0.09kPa；
Step 4: the resulting mixture of step 3 being ground to 120 meshes, obtains mix powder；
Step 5: the resulting mix powder of step 4 being calcined into 3h under an argon atmosphere, heating rate is 6 DEG C/min, is forged
Burning temperature is 350 DEG C；
Step 6: the material after the completion of step 5 calcining being cooled to room temperature with the speed of 12 DEG C/min, ground, mistake 120
After mesh, the nanometer-material-modified fluorination carbon electrode material is obtained.
Nanometer-material-modified fluorination carbon electrode is prepared using the nanometer-material-modified fluorination carbon electrode material of the present embodiment
Method it is same as Example 1.
Embodiment 5
A kind of preparation method of nanometer-material-modified fluorination carbon electrode material, this method is dispersion-calcination method, including with
Lower step:
Step 1: medium and fluorocarbons being added in high speed centrifugation dispersion tank according to mass ratio=2.9:1 ratio, allow object
Expect to disperse 25min in high speed centrifugation dispersion tank with the revolving speed of 2900r/min；The medium is ethyl alcohol, acetone；
Step 2: nano material is added into high speed centrifugation dispersion tank, allows material in high speed centrifugation dispersion tank with 3400r/
The revolving speed of min disperses 1.9h, obtains slurry；The nano material is nano silver；The matter of the nano material and fluorinated carbon material
Measure ratio=4.5:100；The diameter of the nano material is 90nm；
Step 3: after the slurry room temperature that step 2 obtains is dried, then under 39 DEG C of vacuum environment being dried in vacuo 11h, obtain
To mixture；The vacuum drying vacuum degree is -0.09kPa；
Step 4: the resulting mixture of step 3 being ground to 190 meshes, obtains mix powder；
Step 5: the resulting mix powder of step 4 being calcined into 9h under an argon atmosphere, heating rate is 9 DEG C/min, is forged
Burning temperature is 400 DEG C；
Step 6: the material after the completion of step 5 calcining being cooled to room temperature with the speed of 19 DEG C/min, ground, mistake 180
After mesh, the nanometer-material-modified fluorination carbon electrode material is obtained.
Nanometer-material-modified fluorination carbon electrode is prepared using the nanometer-material-modified fluorination carbon electrode material of the present embodiment
Method it is same as Example 1.
Comparative example 1
With the embodiment of the present application 1 the difference is that: fluorination carbon electrode material do not contain nano material, wherein modification fluorination
Carbon material is replaced using common fluorination carbon electrode material, and other conditions are constant.
Using fluorination carbon electrode made from 1 method of embodiment 1 and comparative example as cell positive electrode, using lithium metal as negative
Electrode is assembled into lithium battery in the drying shed that relative air humidity is 1%, adopts electrode LiPF6/ EC:DMC:EMC=1:1:
1 and concentration be 1mol/L electrolyte carry out electrolytic experiment.
1 two groups of lithium batteries of embodiment 1 and comparative example are carried out to the discharge test of 25 DEG C, 0.2C multiplying power, experimental result simultaneously
As shown in Figure 1.It is obviously observed from Fig. 1, in 25 DEG C, 0.2C multiplying power, the low wave electricity of the fluorination carbon electrode obtained of comparative example 1
Pressure is 2.35V；And the low wave voltage of the fluorination carbon electrode obtained of the embodiment of the present application 1 is 2.45V, low wave voltage obtains significantly
It improves, and 2.8V or more is increased to by 2.5V using the discharge voltage plateau of nanometer-material-modified fluorination carbon electrode, improve
About 0.3V, low wave voltage and working voltage platform have all obtained apparent improvement, significantly improve the discharge property of electrode
Energy.
In conclusion the application carries out modification, nanometer to fluorinated carbon material using the preferable nano material of electric conductivity
Material is uniformly coated on fluorinated carbon material surface, increases the electric conductivity of fluorinated carbon material, effectively improves fluorinated carbon material
Voltage delay problem, improve the high rate performance of fluorinated carbon material.By the nanometer-material-modified fluorination carbon electrode material of the application
Material is applied in lithium fluorocarbon battery, effectively improves the voltage delay of fluorination carbon electrode, improves the platform voltage of electrode,
Significant effect.By the low wave voltage for being fluorinated carbon electrode by 2.35V, it is increased to 2.5V, improves 6%；Platform voltage is mentioned by 2.5V
Height improves 12% to 2.8V or more.Fluorination carbon electrode compared with the prior art, voltage delay and platform voltage greatly improve,
Significantly improve the discharge performance of electrode.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, nothing
By from the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended
Claim rather than above description limit, it is intended that by the institute in the meaning and scope for the equivalent loins for falling in claim
It changes and includes within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nanometer-material-modified fluorination carbon electrode material, this method is dispersion-calcination method, and feature exists
In, comprising the following steps:
Step 1: by medium and fluorocarbons according to mass ratio=(2~3): 1 ratio is added in high speed centrifugation dispersion tank, allows material
10~30min is dispersed with the revolving speed of 2000~3000r/min in high speed centrifugation dispersion tank；
Step 2: nano material is added into high speed centrifugation dispersion tank, allow material in high speed centrifugation dispersion tank with 3000~
The revolving speed of 3500r/min disperses 1~2h, obtains slurry；
Step 3: after the slurry room temperature that step 2 obtains is dried, then 8~12h is dried in vacuo under 30~40 DEG C of vacuum environment,
Obtain mixture；
Step 4: the resulting mixture of step 3 being ground to 100~200 meshes, obtains mix powder；
Step 5: the resulting mix powder of step 4 is calcined into 1~12h under an argon atmosphere, heating rate is 5~10 DEG C/
Min, calcination temperature are 300~450 DEG C；
Step 6: the material after the completion of step 5 calcining being cooled to room temperature with the speed of 10~20 DEG C/min, ground, mistake 100
After~200 meshes, the nanometer-material-modified fluorination carbon electrode material is obtained.
2. the preparation method of the nanometer-material-modified fluorination carbon electrode material of one kind according to claim 1, feature exist
In: in step 1, the medium is ethyl alcohol, acetone.
3. the preparation method of the nanometer-material-modified fluorination carbon electrode material of one kind according to claim 1, feature exist
In: in step 2, the nano material is nano silver.
4. the preparation method of the nanometer-material-modified fluorination carbon electrode material of one kind according to claim 1, feature exist
In: in step 2, mass ratio=(0.5~5) of the nano material and fluorinated carbon material: 100；The diameter of the nano material
For 10~100nm.
5. the preparation method of the nanometer-material-modified fluorination carbon electrode material of one kind according to claim 1, feature exist
In: in step 3, the vacuum drying vacuum degree is -0.08kPa~-0.09kPa.
6. a kind of preparation method of nanometer-material-modified fluorination carbon electrode, which comprises the following steps:
(1) it and starches: weighing superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified fluorine according to mass ratio
Change carbon electrode material, all raw materials are mixed, are stirred evenly, mixed slurry is made；
(2) it coats: above-mentioned gained mixed slurry is coated uniformly on aluminium foil two sides, it is placed in 70~90 DEG C of baking ovens dry 30~
60min obtains nanometer-material-modified fluorocarbons pole piece；
(3) heat rolls: above-mentioned nanometer-material-modified fluorocarbons pole piece being carried out heat and is rolled, is obtained described nanometer-material-modified
It is fluorinated carbon electrode.
7. the preparation method of the nanometer-material-modified fluorination carbon electrode of one kind according to claim 6, it is characterised in that: institute
State the mass ratio of superconduction carbon, graphene, Ketjen black, CMC, SBR, solvent and nanometer-material-modified fluorination carbon electrode material=
(0.02~0.03): (0.01~0.02): (0.02~0.03): (0.02~0.03): (0.03~0.04): (1.8~2.2):
(0.85~0.90).
8. the preparation method of the nanometer-material-modified fluorination carbon electrode of one kind according to claim 6, it is characterised in that:
Step (1), the speed of the stirring are 300~500r/min, and the time is 65~100min.
9. the preparation method of the nanometer-material-modified fluorination carbon electrode of one kind according to claim 6, it is characterised in that:
Step (2), it is 2.0~3.3g/100cm that the mixed slurry, which is coated in the density on aluminium foil,2。
10. the preparation method of the nanometer-material-modified fluorination carbon electrode of one kind according to claim 6, it is characterised in that:
In step (3), the temperature that the heat rolls is 35~50 DEG C, with a thickness of 0.15~0.19mm.
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| CN109888290A (en) * | 2019-03-19 | 2019-06-14 | 郑州中科新兴产业技术研究院 | A kind of high rate lithium ion battery, aging and chemical forming method |
| CN110783522A (en) * | 2018-11-23 | 2020-02-11 | 贵州梅岭电源有限公司 | Preparation method of nanomaterial-modified carbon fluoride electrode material |
| CN113346077A (en) * | 2021-05-17 | 2021-09-03 | 上海超碳石墨烯产业技术有限公司 | Phosphorus-modified carbon fluoride material and preparation method and application thereof |
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| CN111969188B (en) * | 2020-08-20 | 2022-06-17 | 贵州梅岭电源有限公司 | Low-temperature graphene/graphite fluoride cathode material |
| CN113363496A (en) * | 2021-06-28 | 2021-09-07 | 贵州梅岭电源有限公司 | Cr (chromium)8O21Preparation method of @ C modified carbon fluoride cathode material |
| CN113972355A (en) * | 2021-10-22 | 2022-01-25 | 陕西科技大学 | ZnNi/C composite material modified lithium/carbon fluoride battery positive plate and preparation method thereof |
| CN113972377A (en) * | 2021-10-22 | 2022-01-25 | 陕西科技大学 | Nickel-based high-entropy alloy/carbon nanotube modified lithium-carbon fluoride battery positive plate and preparation method thereof |
| CN114311177B (en) * | 2022-01-06 | 2023-05-26 | 南京林业大学 | Preparation method of low-carbon formaldehyde-free ecological plate |
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| CN104577107B (en) * | 2013-10-14 | 2018-01-16 | 中国电子科技集团公司第十八研究所 | A kind of surface modification method of fluorinated carbon material |
| CN109390551A (en) * | 2018-11-23 | 2019-02-26 | 贵州梅岭电源有限公司 | A kind of preparation method of nanometer-material-modified fluorination carbon electrode material |
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| CN110783522A (en) * | 2018-11-23 | 2020-02-11 | 贵州梅岭电源有限公司 | Preparation method of nanomaterial-modified carbon fluoride electrode material |
| CN109888290A (en) * | 2019-03-19 | 2019-06-14 | 郑州中科新兴产业技术研究院 | A kind of high rate lithium ion battery, aging and chemical forming method |
| CN113346077A (en) * | 2021-05-17 | 2021-09-03 | 上海超碳石墨烯产业技术有限公司 | Phosphorus-modified carbon fluoride material and preparation method and application thereof |
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