CN108270003A - A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes - Google Patents
A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes Download PDFInfo
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- CN108270003A CN108270003A CN201810009463.2A CN201810009463A CN108270003A CN 108270003 A CN108270003 A CN 108270003A CN 201810009463 A CN201810009463 A CN 201810009463A CN 108270003 A CN108270003 A CN 108270003A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000007791 liquid phase Substances 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 45
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000013019 agitation Methods 0.000 claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkyl phenol Chemical compound 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000002572 peristaltic effect Effects 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of liquid phase method synthesis FeF3The method of/CNTs positive electrodes, belongs to technical field of lithium ion；Carbon nanotube is dispersed in by magnetic agitation in the mixed acid of nitric acid and sulfuric acid first, is made into mixed liquor A；Hydrofluoric acid is added in mixed liquor A again and is made into mixed liquid B；Surfactant and ferric acetyl acetonade are dissolved in ethanol water and are configured to mixed liquor C；Mixed liquor C is added drop-wise in mixed liquid B dropwise, is reacted while magnetic agitation, continues stirring 15~for 24 hours after dripping；Reaction product is filtered, washed, then is dried in vacuum drying chamber, roasting is to obtain FeF under the conditions of being then 300~500 DEG C in inert atmosphere, temperature3/ CNTs positive electrodes；The FeF that the method for the present invention is prepared3/ CNTs has the characteristics that granularity is small, particle dispersion is good, good conductivity, FeF3/ CNTs positive electrodes are used to prepare lithium ion battery, have higher charging and discharging capacity, cyclical stability and high rate performance.
Description
Technical field
The present invention relates to a kind of liquid phase methods to synthesize FeF3The method of/CNTs positive electrodes belongs to lithium ion battery technology neck
Domain.
Background technology
As the modern industry continues to develop, the living standard of the mankind is continuously improved, and the mankind are enjoying what industrial development was brought
When convenient, it is also faced with exhaustion and the problem of environmental pollution of traditional fossil energy.In order to protect nature for the survival of mankind
Resource, various countries researcher are being striven to find and developed with environmental protection, high energy, safe new energy materials.By the mankind
Continuous research and probe, miscellaneous primary, secondary new energy are developed and used.One side of appearance of lithium rechargeable battery
Face meets needs of the people for battery performance, on the one hand also complies with environmental protection and the security concepts of people, therefore, lithium
Ion battery has obtained great popularization and application in human lives.Lithium ion battery has been widely used in electronics production at present
Product field, electric vehicle field, space industry etc., this is the high working voltage based on it, high power capacity, of low pollution and long circulating longevity
The advantages that life.And the characteristic and price of lithium ion battery are all closely related with its positive electrode, so it is suitable to find one kind
Electrode material, to meet battery high voltage, large capacity and the requirement of long circulation life.Wherein, metal fluoride is a kind of non-
Normal promising anode material of lithium battery.
Metal fluoride can not only carry out lithium ion insertion abjection reaction, chemical conversioning reaction can also occur with lithium
Storing energy, the capacity released are significantly larger than lithium ion insertion/deintercalation reaction on traditional outline.Relative to traditional anode material
Material（LiCoO2、LiFePO4 Deng）For, FeF3Relative molecular mass it is smaller, so its theoretical specific capacity is larger；It is stronger
Fe-F ionic bonds both cause to there is higher electrochemical potential, therefore FeF3With higher theoretical specific energy density.But FeF3's
Ionic bond feature is strong, and band gap is wide, results in poorly conductive, belongs to electronic body, so as to make the chemical property of the material
Poor, if being directly used as anode material of lithium battery, chemical property cannot fully play, it is necessary to which it is modified
To improve its chemical property.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, this
Presoma is prepared by liquid phase method in inventive method, then roasting obtains FeF under an inert atmosphere3/ CNTs products, FeF3/CNTs
Have the characteristics that granularity is small, particle dispersion is good, good conductivity, FeF3/ CNTs positive electrodes are used to prepare lithium ion battery, tool
There are higher charging and discharging capacity, cyclical stability and high rate performance.
A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, the specific steps are：
（1）According to the ratio that mass volume ratio g ︰ mL are 3~5 ︰ 100, carbon nanotube is dispersed in mixed acid, mixed acid is matter
It according to volume ratio is that 1~3 ︰ 1 is mixed that the nitric acid and mass fraction that amount score is 68%, which are 98%, at room temperature magnetic agitation 3
~6h, obtains mixed liquor A；
（2）It is 30% hydrofluoric acid to measure with the isometric mass fraction of mixed liquor A, is slowly added into mixed liquor A, stirring is extremely
It is fully dispersed, obtain mixed liquid B；
（3）According to the ratio that the mass volume ratio g ︰ mL of ferric acetyl acetonade and ethanol water are 10~30 ︰ 100, by levulinic
Ketone iron and surfactant are added in ethanol water, and the amount of surfactant is the 5~8% of acetylacetone,2,4-pentanedione weight of iron, is matched
Mixed liquor C is made；
（4）By step（2）In mixed liquid B obtained as bottom liquid, while magnetic agitation, according to mixed liquid B and mixed liquor C
Volume ratio is the ratio of 1 ︰, 1~1 ︰ 3, and mixed liquor C is added drop-wise to dropwise in mixed liquid B and is reacted, is further continued for after being added dropwise to complete
Stirring 15~for 24 hours；
（5）By step（4）Gained reaction product filters, and is washed with deionized water and ethyl alcohol, then in 50~80 DEG C of vacuum drying chambers
Middle drying 12~for 24 hours, 1~3h is roasted under the conditions of being then 300~500 DEG C in inert atmosphere, temperature, up to FeF after cooling3/
CNTs positive electrodes.
Step（3）The surfactant is polyethylene glycol, alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether
Or polyoxyethylene carboxylate.
Step（3）The ethanol water is mixed to get in equal volume for second alcohol and water.
Step（4）The drop rate of the mixed liquid B is 2~5mL/min.
Step（4）The mixed liquid B is added dropwise using peristaltic pump.
Step（5）The inert atmosphere can be nitrogen atmosphere or argon gas atmosphere.
Beneficial effects of the present invention：
（1）Presoma is prepared by liquid phase method in the present invention, then roasting obtains FeF under an inert atmosphere3/ CNTs, technique letter
It is single, of low cost, and FeF3/ CNTs has the characteristics that granularity is small, particle dispersion is good, good conductivity；
（2）FeF of the present invention3/ CNTs positive electrodes are used to prepare lithium ion battery, have higher charging and discharging capacity, cycle
Stability and high rate performance.
Description of the drawings
Fig. 1 is the FeF that the embodiment of the present invention 1 obtains3The XRD diagram of/CNTs；
Fig. 2 is the FeF that the embodiment of the present invention 1 obtains3The transmission electron microscope picture of/CNTs；
Fig. 3 uses FeF for the embodiment of the present invention 13The first charge-discharge for the lithium ion battery that/CNTs positive electrodes are prepared is bent
Line；
Fig. 4 uses FeF for the embodiment of the present invention 13The cycle performance figure of lithium ion battery that/CNTs positive electrodes are prepared.
Specific embodiment
The present invention is described in further detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1
A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, the specific steps are：
（1）According to the ratio that mass volume ratio g ︰ mL are 3 ︰ 100, it is 68% that 1.5g carbon nanotubes are dispersed in 25mL mass fractions
Nitric acid and the mixed acid that mixes of sulfuric acid that 25mL mass fractions are 98% in, magnetic agitation 3h, is mixed at room temperature
Liquid A；
（2）It is 30% hydrofluoric acid to measure with the isometric mass fraction of mixed liquor A, is slowly added into mixed liquor A, stirring is extremely
It is fully dispersed, obtain mixed liquid B；
（3）Acetylacetone,2,4-pentanedione is weighed according to the ratio that the mass volume ratio g ︰ mL of ferric acetyl acetonade and ethanol water are 30 ︰ 100
60g ferric acetyl acetonades and 3g surfactant polyethylenes (PEG) are added in the ethanol water of 200mL, ethanol water by iron
Solution is mixed to get in equal volume for second alcohol and water, is configured to mixed liquor C；
（4）By step（2）In mixed liquid B obtained as bottom liquid, while magnetic agitation, according to mixed liquid B and mixed liquor C
Volume ratio is 1 ︰ 2, and mixed liquor C is added drop-wise to dropwise in mixed liquid B with peristaltic pump and is reacted, drop rate 2mL/min, drop
Stirring 18h is further continued for after the completion of adding；
（5）By step（4）Gained reaction product filters, and is washed respectively 5 times with deionized water and ethyl alcohol, then in 80 DEG C of vacuum drying
Dry 12h in case roasts 2h, up to FeF after cooling under the conditions of being then 400 DEG C in argon inert atmosphere, temperature3/ CNTs is just
Pole material.
The FeF that the present embodiment liquid phase method synthesizes3The XRD diagram of/CNTs positive electrodes as shown in Figure 1, from fig. 1, it can be seen that
Material is orthorhombic crystalline structure, and space group R3C shows that diffraction maximum all corresponds to FeF by PDF cards3, do not detect C peaks,
This may be since carbon is unformed；Diffraction maximum is more sharp, shows the better crystallinity degree of material.
The FeF that the present embodiment liquid phase method synthesizes3/ CNTs transmission electron microscope pictures are as shown in Fig. 2, as shown in Figure 2, this implementation
FeF prepared by example3/ CNTs particle dispersions are preferable, and particle size is about 50~100nm.
Electrochemical property test：
The FeF that the present embodiment is prepared3/ CNTs powder, acetylene black, Kynoar (PVDF) are 8 in mass ratio:1:1
Ratio be placed in agate mortar, it is uniform that appropriate n-methyl-2-pyrrolidone (NMP) grinding is added dropwise；It is then coated on Al foils,
The thickness being wherein coated on Al foils is 0.15mm, then is placed in drying in the vacuum drying chamber that temperature is 80 DEG C and for 24 hours, takes out conduct
Anode；Metal lithium sheet is as cathode and reference electrode, and microporous polypropylene membrane is diaphragm, with 1mol/LiPF6 + EC/DMC/EMC is
Electrolyte in the glove box of argon atmosphere, moisture less than 2ppm, is assembled into CR2025 stainless steel button cells；It stands
Test its charge-discharge performance afterwards for 24 hours.
The FeF that the present embodiment is synthesized with liquid phase method3The FeF that/CNTs is prepared3The charge and discharge for the first time of/CNTs lithium ion batteries
Electric curve is as shown in figure 3, from the figure 3, it may be seen that the present embodiment battery first discharge specific capacity is 307.011mA h g-1；The present embodiment
The FeF synthesized with liquid phase method3The FeF that/CNTs is prepared3The cycle performance of/CNTs lithium ion batteries is as shown in figure 4, by Fig. 4
It is found that the present embodiment battery specific discharge capacity after 40 cycles is 153.295mA h g-1。
Embodiment 2
A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, the specific steps are：
（1）According to the ratio that mass volume ratio g ︰ mL are 4 ︰ 100, it is 68% that 3.2g carbon nanotubes are dispersed in 60mL mass fractions
Nitric acid and the mixed acid that mixes of sulfuric acid that 20mL mass fractions are 98% in, magnetic agitation 4h, is mixed at room temperature
Liquid A；
（2）It is 30% hydrofluoric acid to measure with the isometric mass fraction of mixed liquor A, is slowly added into mixed liquor A, stirring is extremely
It is fully dispersed, obtain mixed liquid B；
（3）Acetylacetone,2,4-pentanedione is weighed according to the ratio that the mass volume ratio g ︰ mL of ferric acetyl acetonade and ethanol water are 10 ︰ 100
Iron, the ethyl alcohol that 48g ferric acetyl acetonades and 3.36g surfactant fatty acids polyoxyethylene ester (AE) are added to 480mL are water-soluble
In liquid, ethanol water is mixed to get in equal volume for second alcohol and water, is configured to mixed liquor C；
（4）By step（2）In mixed liquid B obtained as bottom liquid, while magnetic agitation, according to mixed liquid B and mixed liquor C
Volume ratio is 1 ︰ 3, and mixed liquor C is added drop-wise to dropwise in mixed liquid B with peristaltic pump and is reacted, drop rate 5mL/min, drop
Stirring 15h is further continued for after the completion of adding；
（5）By step（4）Gained reaction product filters, and is washed respectively 6 times with deionized water and ethyl alcohol, then in 60 DEG C of vacuum drying
Dry 18h in case roasts 1h, up to FeF after cooling under the conditions of being then 500 DEG C in nitrogen inert atmosphere, temperature3/ CNTs is just
Pole material.
Electrochemical property test：The FeF that the present embodiment is prepared3/ CNTs powder assembles in the way of embodiment 1
Into CR2025 button cells；Standing tests its charge-discharge performance afterwards for 24 hours；The FeF that the present embodiment is synthesized with liquid phase method3/ CNTs systems
Standby obtained FeF3/ CNTs lithium ion battery maximums specific discharge capacity is 287.08mA hg-1。
Embodiment 3
A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, the specific steps are：
（1）According to the ratio that mass volume ratio g ︰ mL are 5 ︰ 100, it is 68% that 3g carbon nanotubes are dispersed in 40mL mass fractions
In the mixed acid that nitric acid and the sulfuric acid that 20mL mass fractions are 98% mix, magnetic agitation 6h, obtains mixed liquor at room temperature
A；
（2）It is 30% hydrofluoric acid to measure with the isometric mass fraction of mixed liquor A, is slowly added into mixed liquor A, stirring is extremely
It is fully dispersed, obtain mixed liquid B；
（3）Acetylacetone,2,4-pentanedione is weighed according to the ratio that the mass volume ratio g ︰ mL of ferric acetyl acetonade and ethanol water are 20 ︰ 100
72g ferric acetyl acetonades and 4.32g surfactants alkyl phenol polyoxyethylene ether (APEO) are added to the ethanol water of 360mL by iron
In solution, ethanol water is mixed to get in equal volume for second alcohol and water, is configured to mixed liquor C；
（4）By step（2）In mixed liquid B obtained as bottom liquid, while magnetic agitation, according to mixed liquid B and mixed liquor C
Volume ratio is 1 ︰ 3, and mixed liquor C is added drop-wise to dropwise in mixed liquid B with peristaltic pump and is reacted, drop rate 3mL/min, drop
Stirring is further continued for after the completion of adding for 24 hours；
（5）By step（4）Gained reaction product filters, and is washed respectively 8 times with deionized water and ethyl alcohol, then in 50 DEG C of vacuum drying
Drying for 24 hours, roasts 3h, up to FeF after cooling under the conditions of being then 300 DEG C in argon inert atmosphere, temperature in case3/ CNTs is just
Pole material.
Electrochemical property test：The FeF that the present embodiment is prepared3/ CNTs powder assembles in the way of embodiment 1
Into CR2025 button cells；Standing tests its charge-discharge performance afterwards for 24 hours；The FeF that the present embodiment is synthesized with liquid phase method3/ CNTs systems
Standby obtained FeF3/ CNTs lithium ion battery maximums specific discharge capacity is 326.257mA hg-1。
Embodiment 4
A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, the specific steps are：
（1）According to the ratio that mass volume ratio g ︰ mL are 3 ︰ 100, it is 68% that 3g carbon nanotubes are dispersed in 75mL mass fractions
In the mixed acid that nitric acid and the sulfuric acid that 25mL mass fractions are 98% mix, magnetic agitation 5h, obtains mixed liquor at room temperature
A；
（2）It is 30% hydrofluoric acid to measure with the isometric mass fraction of mixed liquor A, is slowly added into mixed liquor A, stirring is extremely
It is fully dispersed, obtain mixed liquid B；
（3）Acetylacetone,2,4-pentanedione is weighed according to the ratio that the mass volume ratio g ︰ mL of ferric acetyl acetonade and ethanol water are 25 ︰ 100
50g ferric acetyl acetonades and 4g surfactants high-carbon fatty alcohol polyoxyethylene ether (AEO) are added to the ethanol water of 200mL by iron
In solution, ethanol water is mixed to get in equal volume for second alcohol and water, is configured to mixed liquor C；
（4）By step（2）In mixed liquid B obtained as bottom liquid, while magnetic agitation, according to mixed liquid B and mixed liquor C
Volume ratio is 1 ︰ 1, and mixed liquor C is added drop-wise to dropwise in mixed liquid B with peristaltic pump and is reacted, drop rate 4mL/min, drop
Stirring 20h is further continued for after the completion of adding；
（5）By step（4）Gained reaction product filters, and is washed respectively 5 times with deionized water and ethyl alcohol, then in 70 DEG C of vacuum drying
Dry 16h in case roasts 1.5h, up to FeF after cooling under the conditions of being then 450 DEG C in nitrogen inert atmosphere, temperature3/CNTs
Positive electrode.
Electrochemical property test：The FeF that the present embodiment is prepared3/ CNTs powder assembles in the way of embodiment 1
Into CR2025 button cells；Standing tests its charge-discharge performance afterwards for 24 hours；The FeF that the present embodiment is synthesized with liquid phase method3/ CNTs systems
Standby obtained FeF3/ CNTs lithium ion battery maximums specific discharge capacity is 264.136mA hg-1。
Embodiment 5
A kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, the specific steps are：
（1）According to the ratio that mass volume ratio g ︰ mL are 5 ︰ 100, it is 68% that 3.75g carbon nanotubes are dispersed in 50mL mass fractions
Nitric acid and the mixed acid that mixes of sulfuric acid that 25mL mass fractions are 98% in, magnetic agitation 3h, is mixed at room temperature
Liquid A；
（2）It is 30% hydrofluoric acid to measure with the isometric mass fraction of mixed liquor A, is slowly added into mixed liquor A, stirring is extremely
It is fully dispersed, obtain mixed liquid B；
（3）Acetylacetone,2,4-pentanedione is weighed according to the ratio that the mass volume ratio g ︰ mL of ferric acetyl acetonade and ethanol water are 15 ︰ 100
Iron, the ethyl alcohol that 45g ferric acetyl acetonades and 3.15g surfactant fatty acids polyoxyethylene ester (AE) are added to 300mL are water-soluble
In liquid, ethanol water is mixed to get in equal volume for second alcohol and water, is configured to mixed liquor C；
（4）By step（2）In mixed liquid B obtained as bottom liquid, while magnetic agitation, according to mixed liquid B and mixed liquor C
Volume ratio is 1 ︰ 2, and mixed liquor C is added drop-wise to dropwise in mixed liquid B with peristaltic pump and is reacted, drop rate 5mL/min, drop
Stirring 22h is further continued for after the completion of adding；
（5）By step（4）Gained reaction product filters, and is washed respectively 6 times with deionized water and ethyl alcohol, then in 50 DEG C of vacuum drying
Dry 20h in case roasts 2.5h, up to FeF after cooling under the conditions of being then 350 DEG C in nitrogen inert atmosphere, temperature3/CNTs
Positive electrode.
Electrochemical property test：The FeF that the present embodiment is prepared3/ CNTs powder assembles in the way of embodiment 1
Into CR2025 button cells；Standing tests its charge-discharge performance afterwards for 24 hours；The FeF that the present embodiment is synthesized with liquid phase method3/ CNTs systems
Standby obtained FeF3/ CNTs lithium ion battery maximums specific discharge capacity is 273.541mA hg-1。
Claims (6)
1. a kind of liquid phase method synthesizes FeF3The method of/CNTs positive electrodes, which is characterized in that the specific steps are：
（1）According to the ratio that mass volume ratio g ︰ mL are 3~5 ︰ 100, carbon nanotube is dispersed in mixed acid, mixed acid is matter
It according to volume ratio is that 1~3 ︰ 1 is mixed that the nitric acid and mass fraction that amount score is 68%, which are 98%, at room temperature magnetic agitation 3
~6h, obtains mixed liquor A；
（2）It takes and step（1）The isometric mass fraction of middle mixed liquor A is 30% hydrofluoric acid, is added in mixed liquor A, is stirred
It is extremely fully dispersed, obtain mixed liquid B；
（3）According to the ratio that the mass volume ratio g ︰ mL of ferric acetyl acetonade and ethanol water are 10~30 ︰ 100, by levulinic
Ketone iron and surfactant are added in ethanol water, and the amount of surfactant is the 5~8% of acetylacetone,2,4-pentanedione weight of iron, is matched
Mixed liquor C is made；
（4）By step（2）In mixed liquid B obtained as bottom liquid, while magnetic agitation, according to mixed liquid B and mixed liquor C
Volume ratio is the ratio of 1 ︰, 1~1 ︰ 3, and mixed liquor C is added drop-wise to dropwise in mixed liquid B and is reacted, is further continued for after being added dropwise to complete
Stirring 15~for 24 hours；
（5）By step（4）Gained reaction product filters, and is washed with deionized water and ethyl alcohol, then in 50~80 DEG C of vacuum drying chambers
Middle drying 12~for 24 hours, 1~3h is roasted under the conditions of being then 300~500 DEG C in inert atmosphere, temperature, up to FeF after cooling3/
CNTs positive electrodes.
2. liquid phase method synthesis FeF according to claim 13The method of/CNTs positive electrodes, which is characterized in that step（3）Institute
Surfactant is stated as polyethylene glycol, alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether or aliphatic acid polyethenoxy
Ester.
3. liquid phase method synthesis FeF according to claim 13The method of/CNTs positive electrodes, which is characterized in that step（3）Institute
Ethanol water is stated to be mixed to get in equal volume for second alcohol and water.
4. liquid phase method synthesis FeF according to claim 13The method of/CNTs positive electrodes, which is characterized in that step（4）Institute
The drop rate for stating mixed liquid B is 2~5mL/min.
5. liquid phase method synthesis FeF according to claim 13The method of/CNTs positive electrodes, which is characterized in that step（4）Institute
It states and is added dropwise using peristaltic pump.
6. liquid phase method synthesis FeF according to claim 13The method of/CNTs positive electrodes, which is characterized in that step（5）Institute
It can be nitrogen atmosphere or argon gas atmosphere to state inert atmosphere.
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| CN114361449A (en) * | 2022-01-24 | 2022-04-15 | 中南大学 | Carbon nanotube coated FeF3Method of synthesis of |
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| CN114361449A (en) * | 2022-01-24 | 2022-04-15 | 中南大学 | Carbon nanotube coated FeF3Method of synthesis of |
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