CN114335475A - Metal fluoride/porous carbon composite positive electrode material and positive plate and battery comprising same - Google Patents
Metal fluoride/porous carbon composite positive electrode material and positive plate and battery comprising same Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 229910001512 metal fluoride Inorganic materials 0.000 title claims abstract description 61
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 18
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000003682 fluorination reaction Methods 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910020323 ClF3 Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001007 Nylon 4 Polymers 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000835 fiber Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000889 atomisation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- 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
Abstract
The invention provides a metal fluoride/porous carbon composite positive electrode material, a positive plate and a battery comprising the same. In addition, the invention also provides a preparation method and application of the cathode material.
Description
Technical Field
The invention belongs to the field of secondary battery anode materials, and relates to a metal fluoride/porous carbon composite anode material, an anode plate comprising the same and a battery.
Background
Lithium ion batteries are typical representatives of secondary batteries, have the advantages of high specific capacity, good cycle performance, high power density, environmental friendliness and the like, and are widely applied to the fields of consumer electronics, electric automobiles, energy storage and the like. However, the energy density in the existing battery system is close to the theoretical limit, and it is still difficult to meet the increasing demands for endurance, safety and the like in the practical scene. The development of a novel battery material system is urgently needed, so that the related performance of the battery is obviously improved.
Compared with the intercalation and deintercalation mechanism of single electron reaction of the traditional intercalation type anode material, the anode material based on the conversion reaction can carry out multi-electron transfer, thereby realizing higher energy density. The metal fluoride is a representative of conversion type anode materials, and has the advantages of high theoretical specific capacity, high voltage platform, good thermal stability, low cost, environmental friendliness and the like.
However, metal fluorides also have some problems as positive electrode materials for secondary batteries. Because the material contains fluorine ions with strong electronegativity and is combined by metal-fluorine ionic bonds with strong bond energy, the material shows electric insulation and trace solubility in electrolyte, and the rate capability of the anode material is poor. Meanwhile, in the phase conversion reaction process, the metal fluoride can generate larger volume expansion, and the material is pulverized and separated from the pole piece, so that the cycle performance is poor.
In order to improve the problems of the metal fluoride, the prior art generally compounds the metal fluoride with a highly conductive material, such as the metal fluoride is compounded into the pores of the activated carbon powder, or the metal fluoride is compounded on the surface of the reduced graphene oxide, and so on. However, in the above technical solution, due to the problem of dispersion uniformity between the metal fluoride and the conductive material, the metal fluoride is easily pulverized and separated from the positive electrode sheet during long-term cycling of the prepared battery, resulting in performance degradation.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a metal fluoride/porous carbon composite cathode material, and a cathode plate and a battery comprising the same, wherein the metal fluoride in the metal fluoride/porous carbon composite cathode material is obtained by an in-situ generation method, is firmly combined with surface-compounded porous carbon, improves the problem of poor electronic conductivity of the metal fluoride, and shows excellent cycle performance. In addition, the invention also provides a preparation method and application of the cathode material.
Specifically, the invention provides the following technical scheme:
the utility model provides a metal fluoride/porous carbon composite anode material, composite anode material includes metal fluoride and porous carbon, the porous carbon cladding is on the metal fluoride surface, the porous carbon contains the hole structure, the porosity P of porous carbon satisfies that 1% is less than or equal to P and is less than or equal to 60%.
According to an embodiment of the invention, the porous carbon is obtained by high temperature carbonization of a polymer; illustratively, the porous carbon is obtained by high-temperature carbonization of a first polymer and a second polymer, wherein the first polymer forms a pore structure, and the second polymer forms a carbon material.
According to the embodiment of the invention, the porosity P of the porous carbon is the ratio of the pore volume to the volume of the carbon layer, and can be obtained by conversion through a mass ratio.
According to the embodiment of the invention, the porosity P of the porous carbon is more than or equal to 10% and less than or equal to 60%, and the porosity P of the porous carbon is 10%, 20%, 30%, 40%, 50%, 60% or any point value in the range formed by two points.
According to an embodiment of the present invention, the metal element in the metal fluoride is one or more of iron, copper, cobalt, nickel, manganese, aluminum, titanium, and cerium.
According to an embodiment of the present invention, the coating mode of the porous carbon may be full coating or partial coating.
According to the embodiment of the invention, in the composite cathode material, the metal fluoride and the porous carbon are physically combined.
According to an embodiment of the invention, the molar ratio of the metal fluoride to the porous carbon is (30-80: 1), for example 30:1, 40:1, 50:1, 60:1, 70:1 or 80: 1.
According to an embodiment of the invention, the metal fluoride is in the form of particles or fibers.
According to the embodiment of the invention, the morphology structure of the metal fluoride/porous carbon composite cathode material is a granular structure (such as a spherical granular structure, as shown in fig. 2 in particular) or a fibrous structure (as shown in fig. 1).
According to the embodiment of the present invention, the particle diameter D50 of the metal fluoride/porous carbon composite positive electrode material having a particulate structure is 3 μm to 15 μm.
According to the embodiment of the present invention, the average diameter of the metal fluoride/porous carbon composite positive electrode material having a fibrous structure is 0.1 μm to 5 μm.
The invention also provides a preparation method of the metal fluoride/porous carbon composite cathode material, which comprises the following steps:
(1) mixing an organic solvent, a first polymer, a second polymer and soluble metal salt to prepare a prefabricated solution;
(2) processing the prefabricated solution obtained in the step (1) by using electrostatic spinning to obtain a fibrous structure, drying, and placing under high-purity argon gas at T1Carbonizing at the temperature to prepare a fibrous porous carbon-coated metal oxide;
or, atomizing and granulating the prefabricated solution obtained in the step (1) to obtain a granular structure, drying, and placing under high-purity argon gas at T2Carbonizing at the temperature to prepare a granular porous carbon-coated metal oxide;
(3) the porous carbon-coated metal oxide obtained in the step (2) is put in T3And sequentially carrying out reduction and fluorination treatment at the temperature to prepare the metal fluoride/porous carbon composite cathode material.
According to the embodiment of the invention, in the step (1), specifically, the following steps are performed: sequentially adding the first polymer and the second polymer into an organic solvent, then adding soluble metal salt, and uniformly mixing to obtain a prefabricated solution.
According to an embodiment of the present invention, in the step (1), the organic solvent is at least one selected from the group consisting of dimethylformamide, dimethylacetamide, and acetone.
According to an embodiment of the invention, in step (1), the decomposition temperature of the first polymer type is much lower than the decomposition temperature of the second polymer type. Illustratively, the first type of polymer has a decomposition temperature 100 ℃ to 250 ℃ lower than the decomposition temperature of the second type of polymer.
According to an embodiment of the present invention, in the step (1), the mass ratio of the first polymer to the second polymer is (0.01 to 0.6):1, preferably (0.1 to 0.6):1, more preferably (0.2 to 0.5):1, for example, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1 or 0.6: 1.
According to an embodiment of the present invention, in step (1), the first polymer is selected from one of polymethyl methacrylate, polyvinyl chloride and polyvinylidene chloride, and the second polymer is selected from one of polyacrylonitrile and polypyrrolidone.
According to an embodiment of the present invention, in the step (1), the soluble metal salt is selected from one or more of soluble iron salt, soluble copper salt, soluble cobalt salt, soluble nickel salt, soluble manganese salt, soluble aluminum salt, soluble titanium salt and soluble cerium salt.
According to an embodiment of the present invention, in step (1), the molar ratio of the soluble metal salt to the second polymer is (30-80: 1), for example 30:1, 40:1, 50:1, 60:1, 70:1 or 80: 1.
According to an embodiment of the present invention, in the step (2), the voltage of the electrospinning process is 10kV to 20kV, and the solution advancing speed is 2mL/h to 10 mL/h.
According to an embodiment of the present invention, in the step (2), the diameter of the fibrous structure is 0.1 to 5 μm.
According to an embodiment of the present invention, in step (2), the parameters of the atomization granulation are set as follows: the solution flow is 2mL/min to 12mL/min, the air flow is 4L/min to 8L/min, the air inlet temperature is 155 ℃ to 185 ℃, and the air pressure is 0.1MPa to 0.7 MPa.
According to an embodiment of the present invention, in the step (2), the particle size of the granular structure is 1 μm to 30 μm.
According to an embodiment of the present invention, in the step (2), the temperature of the drying is 60 ℃ to 100 ℃; the drying time is 12-36 h.
According to an embodiment of the present invention, in step (2), said at T1The temperature rise rate of carbonization at the temperature is 2 ℃ min-1～5℃·min-1(ii) a The T is1The temperature is 300-600 ℃; said at T1The carbonization time at the temperature is 2 to 12 hours. Illustratively, at 3 ℃ min-1The temperature is raised to 300-400 ℃ at the speed rate, and the temperature is kept for 1-2 h; then at 5 ℃ for min-1The temperature is raised to 550-600 ℃ at the rate, and the temperature is kept for 3-5 h.
According to an embodiment of the present invention, in step (2), said at T2The temperature rise rate of carbonization at the temperature is 2 ℃ min-1～5℃·min-1(ii) a The T is2The temperature is 300-600 ℃; said at T2The carbonization time at the temperature is 2 to 12 hours. Illustratively, at 3 ℃ min-1The temperature is raised to 300-400 ℃ at the speed rate, and the temperature is kept for 1-2 h; then at 5 ℃ for min-1The temperature is raised to 550-600 ℃ at the rate, and the temperature is kept for 3-5 h.
According to an embodiment of the present invention, in step (3), the T3The temperature is 350-550 ℃.
According to an embodiment of the present invention, in the step (3), the reduction time is 1 to 5 hours.
According to an embodiment of the present invention, in the step (3), the reduction is performed under a hydrogen atmosphere, for example, under a mixed gas atmosphere of hydrogen and an inert gas (e.g., argon), wherein the volume ratio of the inert gas is 90 to 96 vol%, and the volume ratio of the hydrogen is 4 to 10 vol%.
According to an embodiment of the present invention, in the step (3), the fluorination is performed in a fluorine-containing gas atmosphere, for example, in a mixed gas atmosphere of a fluorine-containing gas and an inert gas (e.g., argon), wherein the volume ratio of the inert gas is 90 to 96 vol%, and the volume ratio of the fluorine-containing gas is 4 to 10 vol%.
According to an embodiment of the present invention, in the step (3), the fluorine-containing gas is selected from NF3、ClF3At least one of (1).
According to an embodiment of the present invention, in the step (3), the fluorination time is 1 to 5 hours.
The invention also provides the metal fluoride/porous carbon composite cathode material prepared by the method.
The invention also provides application of the metal fluoride/porous carbon composite cathode material in a battery.
The invention also provides a positive plate which comprises the metal fluoride/porous carbon composite positive electrode material.
The invention also provides a battery, which comprises the metal fluoride/porous carbon composite positive electrode material or comprises the positive electrode sheet.
According to an embodiment of the present invention, the battery is, for example, a secondary battery.
The invention has the beneficial effects that:
the invention provides a metal fluoride/porous carbon composite positive electrode material, and further provides a preparation method and application thereof.
In the present invention, a porous carbon/metal fluoride composite having a specific porosity is prepared by using two polymers having different decomposition temperatures (i.e., a first type polymer and a second type polymer) as a carbon source. Specifically, in the temperature rise process of the metal fluoride/porous carbon composite positive electrode material, the first polymer is preferentially decomposed and leaves small holes on fibers or particles, soluble metal salt nucleates inside the fibers or particles to form metal oxide, the second polymer is finally carbonized to obtain a porous carbon layer, and the composite material is prepared through a hydrogen reduction and fluorine-containing gas fluorination method.
Further, the porosity of the porous carbon can be controlled by controlling the ratio of the first polymer to the second polymer, and the ratio of the metal fluoride to the porous carbon in the composite material can be controlled by controlling the ratio of the second polymer to the soluble metal salt.
Drawings
Fig. 1 is a schematic structural view of a composite material prepared by an electrospinning technique.
Fig. 2 is a schematic structural view of a composite material prepared by the atomization granulation technique.
Fig. 3 is a battery capacity retention rate curve of the composite cathode materials prepared in example 1 and comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first", "second", etc. are used for descriptive purposes only and do not indicate or imply relative importance.
Example 1
(1) Dissolving polymethyl methacrylate and polyacrylonitrile in dimethylformamide, adding ferric acetylacetonate after full dissolution, and stirring for 12 hours to obtain a prefabricated solution, wherein the mass ratio of the polymethyl methacrylate to the polyacrylonitrile is 1:2, and the molar ratio of the polyacrylonitrile to the ferric acetylacetonate is 1: 40.
(2) And (2) processing the prefabricated solution obtained in the step (1) by using an electrostatic spinning technology to obtain a fiber membrane (after electrostatic spinning, a fiber structure is obtained, and during receiving, fibers are continuously generated and are randomly stacked to form a fiber membrane structure, wherein the fiber membrane structure is in a film state on the macro scale and is composed of a plurality of fibers on the micro scale). Wherein the electrostatic spinning potential is 15kV, the distance between the needle point and the receiving membrane is 20cm, and the solution advancing speed is 1 mL/min.
(3) Drying the fiber membrane obtained in the step (2) at 80 ℃ for 24 hours, and then transferring the fiber membrane to a high-temperature sintering furnace filled with Ar for carbonization treatment, wherein the specific operation condition is 3 ℃ per minute-1Heating to 300 ℃ at the speed of (1), and keeping the temperature for 1 h; then at 5 ℃ for min-1The temperature is raised to 550 ℃ at the rate of (1), and the temperature is kept for 4 hours. Polymethyl methacrylate is preferentially decomposed due to its low decomposition temperature, and polyacrylonitrile is then carbonized, thereby obtaining Fe2O3A composite material with porous carbon.
(4) Fe obtained in the step (3)2O3The composite with porous carbon was transferred to a high temperature furnace at 3 ℃ min-1The temperature is raised to 450 ℃ at a speed of, H is introduced2Keeping the temperature for 2 hours by using the/Ar mixed gas to ensure that Fe in the composite material is2O3Reducing the iron into Fe. Subsequently introducing NF into the furnace3Keeping the temperature for 2 hours by using/Ar mixed gas, and adding Fe2O3After fluorination, FeF can be obtained3A composite material with porous carbon.
Finally, the porous carbon/iron fluoride composite cathode material with the porosity P of 50% can be obtained, and the molar ratio of the iron fluoride to the porous carbon is 40: 1.
Example 2
The other operations are the same as example 1, except that: the mass ratio of polymethyl methacrylate to polyacrylonitrile in example 2 was 0.25: 1.
Finally, the porous carbon/iron fluoride composite cathode material with the porosity P of 25% is obtained, and the molar ratio of the iron fluoride to the porous carbon is 40: 1.
Example 3
The other operations are the same as example 1, except that: the soluble metal salt in example 3 is an equimolar portion of cobalt acetylacetonate.
Finally, the porous carbon/cobalt fluoride composite cathode material with the porosity P of 50% can be obtained, and the molar ratio of the cobalt fluoride to the porous carbon is 40: 1.
Example 4
The other operations are the same as example 1, except that: the molar ratio of polyacrylonitrile to iron acetylacetonate in example 4 was 1: 60.
Finally, the porous carbon/iron fluoride composite cathode material with the porosity P of 50% can be obtained, and the molar ratio of the iron fluoride to the porous carbon is 60: 1.
Example 5
The other operations are the same as example 1, except that:
and (3) processing the prefabricated solution obtained in the step (1) by using atomization and granulation to obtain granules. Wherein the solution flow rate is controlled to be 3mL/min, the air flow rate is 5L/min, the air inlet temperature is 175 ℃, and the air pressure is 0.4MPa in the atomization granulation process.
Finally, the porous carbon/iron fluoride composite cathode material with the porosity P of 50% can be obtained, and the molar ratio of the iron fluoride to the porous carbon is 40: 1.
Comparative example 1
Selecting 0.5 molar part of conductive graphite and 20 molar parts of ferric fluoride, uniformly mixing, carrying out planetary ball milling for 12 hours by taking isopropanol as a ball milling medium, taking out and drying to obtain FeF3The composite material of the conductive graphite and the iron fluoride is only the physical mixture of the carbon material and the iron fluoride, a specific microstructure is not obtained, and the iron fluoride is distributed in the graphite sheet layer.
Comparative example 2
The other operations are the same as example 1, except that the preparation of the preliminary solution is as follows:
and dissolving 1 molar part of polyacrylonitrile in dimethylformamide, adding 40 molar parts of ferric acetylacetonate after the polyacrylonitrile is fully dissolved, and stirring for 12 hours to obtain a prefabricated solution.
Finally, the carbon/ferric fluoride composite cathode material without the pore structure is obtained, and the molar ratio of the ferric fluoride to the carbon material is 40: 1.
Comparative example 3
The other operations are the same as example 1, except that the preparation of the preliminary solution is as follows:
dissolving polymethyl methacrylate and polyacrylonitrile in dimethylformamide, adding ferric acetylacetonate after full dissolution, and stirring for 12 hours to obtain a prefabricated solution, wherein the mass ratio of the polymethyl methacrylate to the polyacrylonitrile is 0.7:1, and the molar ratio of the polyacrylonitrile to the ferric acetylacetonate is 1: 40.
Finally, the porous carbon/iron fluoride composite cathode material with the porosity of 70% is obtained, and the molar ratio of the iron fluoride to the porous carbon is 40: 1.
Comparative example 4
The other operations are the same as example 1, except that the preparation of the preliminary solution is as follows:
dissolving polymethyl methacrylate and polyacrylonitrile in dimethylformamide, adding ferric acetylacetonate after full dissolution, and stirring for 12h to obtain a prefabricated solution, wherein the mass ratio of the polymethyl methacrylate to the polyacrylonitrile is 0.7:1, and the molar ratio of the polyacrylonitrile to the ferric acetylacetonate is 1: 60.
Finally, the porous carbon/iron fluoride composite cathode material with the porosity of 70% is obtained, and the molar ratio of the iron fluoride to the porous carbon is 60: 1.
Test example 1
According to the mass ratio of 8:1:1, sequentially selecting 8 parts by mass of the prepared composite material, 1 part by mass of conductive carbon black and 1 part by mass of binder PVDF, fully grinding, dissolving in methyl pyrrolidone, stirring for 8-12h, uniformly coating the slurry on carbon-coated aluminum foil, baking in an oven at 80 ℃ for 8h, taking out, and cutting into circular pole pieces with the diameter of 12 mm. The pole piece is used as a positive electrode, the metal lithium is used as a negative electrode, and the electrolyte is 1M LiPF6And EC (DEC) is 1:1V/V, 10% FEC is adopted, the button cell is assembled, and the charge and discharge test is carried out within the range of 2-4.5V, and the test charge and discharge multiplying power is 0.33C.
Fig. 3 is a curve of capacity retention rates of example 1 and comparative example 1, the capacity retention rate of the fluoride/porous carbon composite positive electrode material prepared by the technology of the present invention after 500 cycles is 66.6%, and the capacity retention rate of the composite positive electrode material prepared by the traditional ball milling method (comparative example 1) is only 16.8%. The composite anode material prepared by the technology has excellent cycle performance.
As can be seen from examples 1 to 5 and comparative example 1, compared with the composite positive electrode prepared by the conventional ball milling method, the capacity retention rate of the composite positive electrode provided by the invention after 500 cycles is much higher than that of the composite positive electrode prepared by the conventional ball milling method. The composite cathode material provided by the invention has the advantages that the porous carbon and the metal fluoride are tightly combined, the electronic conductivity of the metal fluoride is increased, and the volume change of the metal fluoride in the charge and discharge process can be limited.
As can be seen from examples 1 to 5 and comparative examples 2 to 4, the capacity retention rate of the composite positive electrodes in examples 1 to 5 after 500 cycles is also higher than that of the composite positive electrodes in comparative examples 2 to 4. This is because when the carbon material on the surface of the metal fluoride in the composite positive electrode material does not have a pore structure, contact of the metal fluoride with the electrolyte is affected, resulting in degradation of battery performance; when the porosity of the carbon material on the surface of the metal fluoride is too high, the structure of the porous carbon collapses in the volume change process of the metal fluoride in the charging and discharging process, so that the problems of porous carbon failure and reduced electronic conductivity of the composite positive electrode are caused. Therefore, the composite cathode material with specific porosity provided by the invention can have excellent capacity retention rate and cycling stability.
The present invention has been described in detail above, and the present invention principles and embodiments have been described herein using specific examples, which are provided only to help understand the method and core concept of the present invention, so that anyone skilled in the art can practice the present invention. It should be noted that, for those skilled in the art, it is possible to make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments and methods that occur to those skilled in the art.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a metal fluoride/porous carbon composite anode material which characterized in that, composite anode material includes metal fluoride and porous carbon, the porous carbon cladding is on the metal fluoride surface, the porous carbon contains the hole structure, the porosity P of porous carbon satisfies that P is more than or equal to 1% and is less than or equal to 60%.
2. The metal fluoride/porous carbon composite positive electrode material according to claim 1, wherein a porosity P of the porous carbon satisfies 10% or more and P or less and 60% or less.
3. The metal fluoride/porous carbon composite positive electrode material according to claim 1, wherein the metal element in the metal fluoride is one or more of iron, copper, cobalt, nickel, manganese, aluminum, titanium, and cerium.
4. The metal fluoride/porous carbon composite positive electrode material according to claim 1, wherein the molar ratio of the metal fluoride to the porous carbon is (30-80): 1.
5. The metal fluoride/porous carbon composite positive electrode material according to claim 1, wherein the morphology structure of the metal fluoride/porous carbon composite positive electrode material is a granular structure or a fibrous structure.
6. The metal fluoride/porous carbon composite positive electrode material according to claim 5, wherein the particle diameter D50 of the metal fluoride/porous carbon composite positive electrode material having a particulate structure is 3 to 15 μm;
and/or the average diameter of the metal fluoride/porous carbon composite positive electrode material with the fibrous structure is 0.1-5 mu m.
7. The method for preparing a metal fluoride/porous carbon composite positive electrode material as claimed in any one of claims 1 to 6, which comprises the steps of:
(1) mixing an organic solvent, a first polymer, a second polymer and soluble metal salt to prepare a prefabricated solution;
(2) processing the prefabricated solution obtained in the step (1) by using electrostatic spinning to obtain a fibrous structure, drying, and placing under high-purity argon gas at T1Carbonizing at the temperature to prepare a fibrous porous carbon-coated metal oxide;
or, atomizing and granulating the prefabricated solution obtained in the step (1) to obtain a granular structure, drying, and placing under high-purity argon gas at T2Carbonizing at the temperature to prepare a granular porous carbon-coated metal oxide;
(3) the porous carbon-coated metal oxide obtained in the step (2) is put in T3And sequentially carrying out reduction and fluorination treatment at the temperature to prepare the metal fluoride/porous carbon composite cathode material.
8. The method according to claim 7, wherein in the step (1), the mass ratio of the first polymer to the second polymer is (0.01-0.6): 1;
and/or, in the step (1), the first polymer is selected from one of polymethyl methacrylate, polyvinyl chloride and polyvinylidene chloride, and the second polymer is selected from one of polyacrylonitrile and polypyrrolidone;
and/or in the step (1), the molar ratio of the soluble metal salt to the second polymer is (30-80): 1;
and/or, in step (2), the said is at T1The temperature rise rate of carbonization at the temperature is 2 ℃ min-1～5℃·min-1(ii) a The T is1The temperature is 300-600 ℃; said at T1The carbonization time at the temperature is 2 to 12 hours;
and/or, in step (2), the said is at T2The temperature rise rate of carbonization at the temperature is 2 ℃ min-1～5℃·min-1(ii) a The T is2The temperature is 300-600 ℃; said at T2The carbonization time at the temperature is 2 to 12 hours;
and/or, in step (3), said T3The temperature is 350-550 ℃;
and/or in the step (3), the reduction time is 1-5 h;
and/or, in the step (3), the fluorination time is 1-5 h;
and/or, in step (3), the reduction is carried out under a hydrogen atmosphere;
and/or, in the step (3), the fluorination is carried out in the atmosphere of fluorine-containing gas selected from NF3、ClF3At least one of (1).
9. A positive electrode sheet comprising the metal fluoride/porous carbon composite positive electrode material according to any one of claims 1 to 6.
10. A battery comprising the metal fluoride/porous carbon composite positive electrode material according to any one of claims 1 to 6, or the battery comprising the positive electrode sheet according to claim 9.
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