CN114628670A - Application of nitrogen-doped carbon-coated carbon fluoride in lithium/carbon fluoride battery - Google Patents
Application of nitrogen-doped carbon-coated carbon fluoride in lithium/carbon fluoride battery Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 36
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 32
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001690 polydopamine Polymers 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
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- 238000003756 stirring Methods 0.000 claims description 20
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- 239000002120 nanofilm Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011247 coating layer Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 7
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 229960003638 dopamine Drugs 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 239000007853 buffer solution Substances 0.000 abstract description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 description 14
- 239000011267 electrode slurry Substances 0.000 description 14
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- 230000000052 comparative effect Effects 0.000 description 10
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 7
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- 239000002904 solvent Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
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- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 1
- GJCNZQUZWSHFHP-UHFFFAOYSA-N [Li].O=S=O Chemical compound [Li].O=S=O GJCNZQUZWSHFHP-UHFFFAOYSA-N 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- 238000003763 carbonization Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- -1 polyoxyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01M4/36—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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The invention provides the use of nitrogen-doped-carbon-coated carbon fluoride in lithium/carbon fluoride batteries. The method adopts aqueous solution of tris (hydroxymethyl) aminomethane as buffer solution, firstly obtains poly-dopamine fluorocarbon composite material through dopamine hydrochloride autopolymerization, and finally calcines the composite material in inert atmosphere to obtain the nitrogen-doped-carbon-coated fluorocarbon electrode material. The preparation method is simple in preparation process, the carbon coating layer is N-doped carbon (N atoms are derived from the amino group of dopamine) and is uniform, the conductivity of the carbon fluoride material is improved, and further the rate capability of the battery is improved, in addition, the self-discharge phenomenon of the carbon fluoride battery is reduced due to the uniform nitrogen-doped carbon coating layer on the surface of the carbon fluoride, and further the high-temperature shelf performance of the carbon fluoride battery is improved.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to application of a nitrogen-doped carbon-coated carbon fluoride electrode material in a lithium/carbon fluoride battery.
Background
With the technical progress in the fields of mobile communication, aerospace, transportation, military equipment and the like, the development of various high-specific-energy power batteries is an urgent need for national economic development. Because metal lithium has the characteristics of light weight and negative electrode potential, the development of a lithium primary battery taking lithium as a negative electrode has received great attention. The primary lithium battery consists essentially of lithium-manganese dioxide (Li/MnO)2) Lithium-sulfur dioxide (Li/SO)2) Lithium thionyl chloride (Li/SOCl)2) And lithium-carbon fluoride (Li/CF)x) And the like. Compared with other primary batteries, the Li/CFx battery has the highest theoretical specific energy value (2180Wh/kg) and the Li/CFxThe battery also has the advantages of high safety, stable discharge voltage, environmental friendliness and the like, and is particularly suitable for being used as a power supply of instrument equipment used in an unmanned or closed environment. Such as a cardiac pacemaker, a missile ignition system, a radio transmitter, an underwater electronic detector and the like, and particularly has great application potential as a military remote detection and communication power supply carried by soldiers.
As the primary chemical power source with the highest theoretical specific energy, Li/CFxThe batteries inevitably need to be stored and shelved during practical use, particularly in aeronautical and military applications. During storage, in particular at elevated temperatures, Li/CFxThe self-discharge of the battery is serious, the discharge capacity and the discharge voltage platform of the battery are reduced, the voltage hysteresis phenomenon is more obvious, and the voltage hysteresis phenomenon is further aggravated along with the rise of the external temperature and the increase of the storage time. In addition, the poor conductivity of the carbon fluoride material itself results in Li/CFxThe battery has small discharge power, serious polarization and low voltage platform. For this reason, researchers have tried various methods of modifying carbon fluoride materials. Yong Pan et al (see reference)The carbon-coated carbon fluoride material is prepared by a polyurea carbonization method so as to improve the voltage platform and the rate discharge performance of the battery. The voltage platform of the prepared lithium fluorocarbon battery is improved, and the rate capability is improved. However, the preparation process involved in the method needs to use a surfactant and a catalyst, is complex and is not suitable for large-scale application; the coating layer on the surface of the carbon fluoride is not uniform; when the carbon-coated carbon fluoride material prepared by the method is used for a lithium/carbon fluoride battery, the high-rate discharge (such as 2C) capacity is still not ideal and needs to be improved.
The method adopts aqueous solution of tris (hydroxymethyl) aminomethane as buffer solution, firstly obtains poly-dopamine fluorocarbon composite material through dopamine hydrochloride autopolymerization, and finally calcines the composite material in inert atmosphere to obtain the nitrogen-doped-carbon-coated fluorocarbon electrode material. The preparation method is simple in preparation process, the carbon coating layer is N-doped carbon (N atoms are derived from the amino group of dopamine) and is uniform, the conductivity of the carbon fluoride material is improved, the rate capability of the battery is further improved, in addition, the existence of the uniform nitrogen-doped carbon coating layer on the surface of the carbon fluoride reduces the self-discharge phenomenon of the carbon fluoride battery, and the high-temperature shelf performance of the carbon fluoride battery is further improved.
Disclosure of Invention
The invention aims to improve the electronic conductivity of the carbon fluoride material, improve the actual specific discharge capacity of the carbon fluoride material and improve the discharge rate of the carbon fluoride battery; the self-discharge phenomenon of the carbon fluoride battery is reduced, and the high-temperature shelf stability of the carbon fluoride battery is further improved (along with the increase of the storage temperature and the extension of the storage time, a CFx cathode in the carbon fluoride battery can continuously generate self-discharge reaction with a metal lithium cathode, and the active substances of the battery are continuously consumed, so that the discharge specific capacity of the Li/CFx battery is gradually reduced, and the discharge platform is gradually lowered).
The invention aims to improve the discharge power of a carbon fluoride battery, and mainly coats a high-conductivity nitrogen-doped carbon layer on the surface of carbon fluoride by improving the conductivity of a fluorinated material; in addition, the invention also aims to improve the high-temperature shelf stability of the carbon fluoride battery, and a dense carbon protective layer is uniformly coated on the surface of the carbon fluoride mainly by a method of isolating the carbon fluoride active material, so that the self-discharge reaction of the carbon fluoride material in the high-temperature shelf process is reduced.
The technical scheme of the invention is as follows:
the invention provides an application of a nitrogen-doped carbon-coated carbon fluoride material, wherein the nitrogen-doped carbon-coated carbon fluoride material is used as a positive electrode active material in a lithium/carbon fluoride battery, and the nitrogen-doped carbon-coated carbon fluoride refers to a method of coating a nitrogen-doped carbon layer on the surface of carbon fluoride. The lithium/carbon fluoride battery takes metal lithium as a negative electrode.
Preferably, the nitrogen-doped carbon layer has a thickness of 20-40 nm.
Preferably, the carbon fluoride is one or more of fluorinated KB, fluorinated graphite, fluorinated carbon nanotubes, fluorinated carbon nanofibers, fluorinated graphene and fluorinated mesoporous carbon materials, and the molar ratio of fluorine to carbon in the carbon fluoride is 0.5-95, preferably 0.7-0.85.
Preferably, the nitrogen-doped carbon-coated carbon fluoride is prepared by the following steps:
1) dissolving tris (hydroxymethyl) aminomethane in water to obtain a solution A;
2) adjusting the pH value of the solution A to 8-10 by using concentrated hydrochloric acid (the concentration is 36% -38%) to obtain a solution B;
3) adding a carbon fluoride material into the solution B, and stirring the mixture until the mixture is fully dispersed to obtain a solution C;
4) dissolving dopamine hydrochloride in water to obtain a solution D, dropwise adding the solution C, carrying out self-polymerization reaction under the stirring condition, and after the reaction is finished, centrifugally separating and drying a reaction product to obtain carbon fluoride coated by a polydopamine nano-film;
5) calcining the carbon fluoride coated with the polydopamine nano-film obtained in the step 4) for 1-5h under the inert environment at the temperature of 800-900 ℃ to obtain the nitrogen-doped carbon-coated carbon fluoride material.
Preferably, the mass fraction of dopamine hydrochloride in the solution D is (0.5-10) wt%, and the mass ratio of dopamine hydrochloride to carbon fluoride is (1-5): (10-50).
Preferably, the inert environment refers to an atmosphere environment of one or more of argon, nitrogen or helium;
preferably, in the step 1), the mass percentage of the trihydroxymethyl aminomethane in the aqueous solution is 0.05-5%; in the step 2), the concentration of the hydrochloric acid is 36-38%; in the step 4), the stirring time is 20-48 h.
Advantageous effects
1. The carbon coating layer on the surface of the carbon fluoride is N-doped carbon (N atoms are derived from the amino group of dopamine), is uniform and compact, obviously improves the conductivity of the carbon fluoride material, and improves the discharge power (rate capability) of a battery.
2. The nitrogen-doped-carbon coating (about 20-40nm) uniformly exists on the surface of the carbon fluoride, so that the self-discharge phenomenon of the carbon fluoride battery is reduced, and the high-temperature shelf performance of the carbon fluoride battery is improved.
3. The preparation process is simple and is easy to realize large-scale production and application.
Drawings
Fig. 1 is a graph of rate performance for a fluorocarbon cell with fluorinated KB without carbon capping treatment (comparative example 2) as the positive electrode;
fig. 2 is a graph of rate performance of a fluorocarbon cell with nitrogen-doped-carbon-coated fluorinated KB (example 1) as the positive electrode.
Detailed Description
Comparative example 1 prior art
Adding 0.05g of alkylphenol polyoxyethylene and 0.05g of polyvinyl alcohol as surfactants into 100mL of distilled water, stirring uniformly by using a glass rod, adding 2g of graphite fluoride, and stirring uniformly; adding 1g of isophorone diisocyanate into the solution, stirring for 15min (1500r/min), placing the solution into a constant-temperature water bath at 45 ℃, stirring at 400rpm, simultaneously adding 0.05g of dibutyltin dilaurate catalyst, reacting for 8h, filtering, washing and drying for 12h to obtain polyurea-coated graphite fluoride, and finally performing high-temperature treatment (350 ℃ for 3h under argon atmosphere) on the polyurea-coated graphite fluoride to obtain the carbon-coated fluorinated KB material. The prepared carbon-coated fluorinated KB positive electrode material, Super P and sodium carboxymethylcellulose (CMC) are mixed according to the mass ratio of 8:1:1 to prepare positive electrode slurry by using distilled water as a homogenizing solvent, the positive electrode slurry is coated on an aluminum foil current collector and dried to prepare a positive electrode, a lithium/carbon fluoride battery is assembled by using metal lithium as a negative electrode and using cellgard2400 as a diaphragm, and the discharge performance of the lithium/carbon fluoride battery is evaluated by different discharge multiplying factors (0.1C-5C, the theoretical capacity is calculated according to 600 mAh/g).
The carbon-coated fluorinated KB material prepared in the above way is taken as a positive active material, metal lithium is taken as a negative electrode, a button cell is assembled, and the charge and discharge performance and the stability performance of the button cell when placed at high temperature (60 ℃ for 30 days) are tested.
Comparative example 2.
The method comprises the steps of assembling a battery by taking uncoated fluorinated KB as a positive active substance and metallic lithium as a negative electrode, preparing an uncoated fluorinated KB positive electrode material, Super P and sodium carboxymethyl cellulose (CMC) according to a mass ratio of 8:1:1, preparing positive electrode slurry by taking distilled water as a homogenizing solvent, coating the positive electrode slurry on an aluminum foil current collector, drying to prepare a positive electrode, assembling a lithium/carbon fluoride battery by taking metallic lithium as the negative electrode and cellgard2400 as a diaphragm, and evaluating the discharge performance and the high-temperature (60 ℃, 30 days) standing stability of the lithium/carbon fluoride battery by using different discharge multiplying factors (0.1C-5C, the theoretical capacity is calculated according to 600 mAh/g).
Example 1.
1. Weighing 0.12g of tris (hydroxymethyl) aminomethane and adding the tris (hydroxymethyl) aminomethane into a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid (the mass concentration is 37 percent);
3. adding 1g of fluorinated KB material (carbon fluoride, the molar ratio of fluorine to carbon is 0.8) into the solution obtained in the step 2, and stirring the mixture until the mixture is fully dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the dopamine hydrochloride into the mixed solution obtained in the step (3) after full dissolution, stirring for 24 hours (full autopolymerization), carrying out centrifugal separation on the dopamine hydrochloride, and drying to obtain the carbon fluoride coated by the polydopamine nano-film;
5. and (4) calcining the carbon fluoride coated with the polydopamine nano-film obtained in the step (4) for 2h at 850 ℃ in a nitrogen environment to obtain the nitrogen-doped carbon-coated fluorinated KB material, wherein the thickness of the coating layer is 25 nm. The prepared nitrogen-doped-carbon-coated fluorinated KB positive electrode material, Super P and sodium carboxymethylcellulose (CMC) are mixed according to the mass ratio of 8:1:1 to prepare positive electrode slurry by using distilled water as a homogenizing solvent, the positive electrode slurry is coated on an aluminum foil current collector and dried to prepare a positive electrode, a lithium/carbon fluoride battery is assembled by using metal lithium as a negative electrode and using cellgard2400 as a diaphragm, and the discharge performance and the high-temperature (0.1C, 60 ℃ and 30 days) standing stability performance of the lithium/carbon fluoride battery are evaluated by different discharge rates (0.1C-5C, the theoretical capacity is calculated according to 600 mAh/g).
Example 2.
1. Weighing 0.08g of tris (hydroxymethyl) aminomethane and adding the tris (hydroxymethyl) aminomethane into a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. adding 1g of graphite fluoride material (the molar ratio of fluorocarbon is 0.85) into the solution in the step 2 while stirring the mixture until the graphite fluoride material is fully dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the dopamine hydrochloride into the mixed solution in the step 3 after the dopamine hydrochloride is fully dissolved, stirring for 24 hours (full autopolymerization), and performing centrifugal separation and drying on the dopamine hydrochloride to obtain the carbon fluoride coated by the polydopamine nano film;
5. and (3) calcining the carbon fluoride coated with the polydopamine nano-film obtained in the step (4) for 2 hours at 850 ℃ in an inert environment to obtain the nitrogen-doped carbon-coated graphite fluoride material, wherein the thickness of the coating layer is 30 nm. The prepared nitrogen-doped carbon-coated graphite fluoride positive electrode material, Super P and sodium carboxymethylcellulose (CMC) are mixed according to the mass ratio of 8:1:1 to prepare positive electrode slurry by using distilled water as a homogenizing solvent, the positive electrode slurry is coated on an aluminum foil current collector and dried to prepare a positive electrode, a lithium/carbon fluoride battery is assembled by using metal lithium as a negative electrode and using cellgard2400 as a diaphragm, and the discharge performance and the high-temperature (0.1C, 60 ℃ and 30 days) standing stability performance of the lithium/carbon fluoride battery are evaluated by different discharge rates (0.1C-5C, the theoretical capacity is calculated according to 600 mAh/g).
Example 3.
1. Weighing 0.12g of tris (hydroxymethyl) aminomethane and adding the tris (hydroxymethyl) aminomethane into a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. adding 1g of graphite fluoride material (with a fluorocarbon molar ratio of 0.7) into the solution in the step 2 while stirring until the graphite fluoride material is fully dispersed;
4. weighing 0.12g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the dopamine hydrochloride into the mixed solution in the step 3 after the dopamine hydrochloride is fully dissolved, stirring for 24 hours (full autopolymerization), and performing centrifugal separation and drying on the dopamine hydrochloride to obtain the carbon fluoride coated by the polydopamine nano film;
6. and (3) calcining the carbon fluoride coated with the polydopamine nano film obtained in the step (4) for 2 hours at 850 ℃ in an inert environment, and then bringing the carbon fluoride coated with the nitrogen-doped carbon graphite fluoride material, wherein the thickness of the coating layer is 20 nm. The prepared nitrogen-doped carbon-coated graphite fluoride positive electrode material, Super P and sodium carboxymethylcellulose (CMC) are mixed according to the mass ratio of 8:1:1 to prepare positive electrode slurry by using distilled water as a homogenizing solvent, the positive electrode slurry is coated on an aluminum foil current collector and dried to prepare a positive electrode, a lithium/carbon fluoride battery is assembled by using metal lithium as a negative electrode and using cellgard2400 as a diaphragm, and the discharge performance and the high-temperature (0.1C, 60 ℃ and 30 days) standing stability performance of the lithium/carbon fluoride battery are evaluated by different discharge rates (0.1C-5C, the theoretical capacity is calculated according to 600 mAh/g).
Example 4.
1. Weighing 0.12g of tris (hydroxymethyl) aminomethane and adding the tris (hydroxymethyl) aminomethane into a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. adding 0.5g of fluorinated KB material (with the molar ratio of fluorine to carbon being 0.95) into the solution in the step 2 while stirring until the mixture is fully dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the dopamine hydrochloride into the mixed solution in the step 3 after the dopamine hydrochloride is fully dissolved, stirring for 24 hours (full autopolymerization), and performing centrifugal separation and drying on the dopamine hydrochloride to obtain the carbon fluoride coated by the polydopamine nano film;
5. and (3) calcining the polydopamine nano-film coated carbon fluoride obtained in the step (4) for 2h at 850 ℃ in an inert environment to obtain the nitrogen-doped carbon-coated fluorinated KB material, wherein the thickness of the coating layer is 40 nm. The prepared nitrogen-doped carbon-coated graphite fluoride positive electrode material, Super P and sodium carboxymethylcellulose (CMC) are mixed according to the mass ratio of 8:1:1 to prepare positive electrode slurry by using distilled water as a homogenizing solvent, the positive electrode slurry is coated on an aluminum foil current collector and dried to prepare a positive electrode, a lithium/carbon fluoride battery is assembled by using metal lithium as a negative electrode and using cellgard2400 as a diaphragm, and the discharge performance and the high-temperature (0.1C, 60 ℃ and 30 days) standing stability performance of the lithium/carbon fluoride battery are evaluated by different discharge rates (0.1C-5C, the theoretical capacity is calculated according to 600 mAh/g).
Example 5.
1. Weighing 0.12g of tris (hydroxymethyl) aminomethane and adding the tris (hydroxymethyl) aminomethane into a beaker containing 100mL of distilled water;
2. adjusting the pH value of the solution in the step 1 to 8.5 by using concentrated hydrochloric acid;
3. adding 3g of fluorinated KB material (fluorocarbon molar ratio is 0.6) into the solution in the step 2 while stirring the mixture till the mixture is fully dispersed;
4. weighing 0.16g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 10mL of water, dropwise adding the dopamine hydrochloride into the mixed solution in the step 3 after the dopamine hydrochloride is fully dissolved, stirring for 24 hours (full autopolymerization), and performing centrifugal separation and drying on the dopamine hydrochloride to obtain the carbon fluoride coated by the polydopamine nano film;
5. and (3) calcining the polydopamine nano-film coated carbon fluoride obtained in the step (4) for 2h at 850 ℃ in an inert environment to obtain the nitrogen-doped carbon-coated fluorinated KB material, wherein the thickness of the coating layer is 20 nm. The prepared nitrogen-doped carbon-coated graphite fluoride positive electrode material, Super P and sodium carboxymethylcellulose (CMC) are mixed according to the mass ratio of 8:1:1 to prepare positive electrode slurry by using distilled water as a homogenizing solvent, the positive electrode slurry is coated on an aluminum foil current collector and dried to prepare a positive electrode, a lithium/carbon fluoride battery is assembled by using metal lithium as a negative electrode and using cellgard2400 as a diaphragm, and the discharge performance and the high-temperature (0.1C, 60 ℃ and 30 days) standing stability performance of the lithium/carbon fluoride battery are evaluated by different discharge rates (0.1C-5C, the theoretical capacity is calculated according to 600 mAh/g).
TABLE 1
TABLE 2 high-temperature shelf life of fluorocarbon batteries having the fluorocarbon material as the positive electrode in each of examples and comparative examples
Table 1 is a rate performance (discharge specific capacity value at each rate) of a fluorocarbon battery in which the fluorocarbon material in each example and comparative example was a positive electrode;
table 2 shows the high-temperature shelf life (specific capacity value before and after shelf life at 60 ℃ at a discharge rate of 0.1C) of the fluorocarbon batteries using the fluorocarbon materials of the respective examples and comparative examples as the positive electrodes.
Comparing fig. 1 and fig. 2, it can be seen that: the rate performance of the fluorocarbon cell with the nitrogen-doped-carbon-coated fluorinated KB in example 1 as the positive electrode is significantly better than that of the fluorocarbon cell with the fluorinated KB without carbon coating treatment as the positive electrode in comparative example 2; compared with fluorinated KB which is not subjected to carbon coating treatment in the comparative example 2, the discharge platform and discharge capacity of the nitrogen-doped carbon-coated fluorinated KB in the example 1 are obviously improved under the same rate, and in addition, the specific capacity of the fluorinated KB still reaches 638mAh/g under the high rate of 5C, which shows that the intrinsic conductivity of the fluorinated KB is obviously improved after the fluorinated KB is coated by carbon, and particularly, the carbon coating layer prepared by the method is nitrogen-doped, so that the conductivity of the fluorinated carbon is more favorably improved, and the rate performance of the fluorinated carbon is further improved (as shown in FIG. 2 and Table 2);
as can be seen from Table 2: compared with carbon-coated fluorocarbon (comparative example 1) and fluorinated KB (comparative example 2) which is not subjected to carbon coating treatment in the prior art, the fluorocarbon battery taking the nitrogen-doped carbon-coated fluorinated KB as the positive electrode prepared by the invention has better high-temperature shelf stability (under 0.1C multiplying power, the fluorocarbon battery still has higher specific discharge capacity after being shelved for 30 days at 60 ℃, and has better discharge capacity retention rate compared with the fluorocarbon battery before being shelved).
Claims (8)
1. The application of the nitrogen-doped carbon-coated carbon fluoride material is characterized in that the nitrogen-doped carbon-coated carbon fluoride material is used as a positive electrode active material in a lithium/carbon fluoride battery, and the nitrogen-doped carbon-coated carbon fluoride refers to that a nitrogen-doped carbon layer is coated on the surface of carbon fluoride.
2. Use according to claim 1, wherein the nitrogen-doped-carbon layer has a thickness of 20-40 nm.
3. Use according to claim 1, characterized in that: the carbon fluoride is one or more than two of fluorinated KB, fluorinated graphite, fluorinated carbon nanotubes, fluorinated carbon nanofibers, fluorinated graphene and fluorinated mesoporous carbon materials, and the molar ratio of fluorine to carbon in the carbon fluoride is 0.5-95.
4. Use according to claim 3, characterized in that: the molar ratio of fluorine to carbon in the carbon fluoride is 0.7-0.85.
5. The use according to claim 1, wherein the nitrogen-doped-carbon-coated fluorocarbon is prepared by the following process:
1) dissolving trihydroxymethyl aminomethane in water to obtain a solution A;
2) adjusting the pH value of the solution A to 8-10 by using hydrochloric acid to obtain a solution B;
3) adding a carbon fluoride material into the solution B and stirring the mixture till the mixture is dispersed to obtain a solution C;
4) dissolving dopamine hydrochloride in water to obtain a solution D, dropwise adding the solution C, carrying out self-polymerization reaction under the stirring condition, and after the reaction is finished, centrifugally separating and drying a reaction product to obtain carbon fluoride coated by a polydopamine nano-film;
5) calcining the carbon fluoride coated with the polydopamine nano-film obtained in the step 4) for 1-5h under the inert environment at the temperature of 800-900 ℃ to obtain the nitrogen-doped carbon-coated carbon fluoride material.
6. Use according to claim 5, characterized in that:
the mass fraction of the dopamine hydrochloride in the solution D is (0.5-10) wt%, and the mass ratio of the dopamine hydrochloride to the carbon fluoride is (1-5): (10-50).
7. Use according to claim 5, characterized in that: the inert environment refers to one or more atmosphere environments in argon, nitrogen or helium;
8. use according to claim 5, characterized in that: in the step 1), the mass percent of the trihydroxymethyl aminomethane in the aqueous solution is 0.05-5%; in the step 2), the concentration of the hydrochloric acid is 36-38%; in the step 4), the stirring time is 20-48 h.
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