CN114335475B - Metal fluoride/porous carbon composite positive electrode material, positive electrode plate comprising same and battery - Google Patents
Metal fluoride/porous carbon composite positive electrode material, positive electrode plate comprising same and battery Download PDFInfo
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- CN114335475B CN114335475B CN202111663662.3A CN202111663662A CN114335475B CN 114335475 B CN114335475 B CN 114335475B CN 202111663662 A CN202111663662 A CN 202111663662A CN 114335475 B CN114335475 B CN 114335475B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 229910001512 metal fluoride Inorganic materials 0.000 title claims abstract description 70
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims description 39
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 11
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000003682 fluorination reaction Methods 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001007 Nylon 4 Polymers 0.000 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- 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
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 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
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000835 fiber Substances 0.000 description 8
- 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
- 239000010406 cathode material Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 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
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification 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
- 102000020897 Formins Human genes 0.000 description 2
- 108091022623 Formins Proteins 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
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 238000012360 testing method Methods 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
- 229910013870 LiPF 6 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
- 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
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001523 electrospinning Methods 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
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 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
- 238000004321 preservation Methods 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
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a metal fluoride/porous carbon composite positive electrode material, a positive electrode plate and a battery comprising the same, wherein the metal fluoride in the metal fluoride/porous carbon composite positive electrode material is obtained by an in-situ generation method and is firmly combined with porous carbon of which the surface is compounded, so that the problem of poor electronic conductivity of the metal fluoride is solved, and the battery prepared from the metal fluoride/porous carbon composite positive electrode material has excellent cycle performance. In addition, the invention also provides a preparation method and application of the positive electrode 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
The lithium ion battery is a typical representation in the secondary battery, has the advantages of high specific capacity, good cycle performance, high power density, environmental friendliness and the like, and is 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 on endurance, safety and the like in the actual scene. There is a need to develop a new battery material system, which significantly improves the performance of the battery.
Compared with the embedding and extracting mechanism of the single electron reaction of the traditional intercalation type positive electrode material, the positive electrode material based on the conversion reaction can carry out multi-electron transfer, thereby realizing higher energy density. The metal fluoride is representative of a conversion type anode material, and has the advantages of high theoretical specific capacity, high voltage platform, good thermal stability, low cost, environmental friendliness and the like.
However, there are some problems in the case of metal fluorides as positive electrode materials for secondary batteries. Because the cathode material contains fluorine ions with strong electronegativity and is combined by metal-fluorine ionic bonds with strong bond energy, the cathode material shows electrical insulation and trace solubility in electrolyte, so that the rate performance of the cathode 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 deteriorated.
In order to improve the problems of metal fluorides, the prior art solutions generally combine them with highly conductive materials, such as metal fluorides into the pores of activated carbon powder, or metal fluorides onto the surface of reduced graphene oxide, etc. However, in the above technical solution, due to the problem of uniformity of dispersion between the metal fluoride and the conductive material, the metal fluoride is very easily pulverized and separated from the positive electrode sheet during long-term circulation of the battery, resulting in performance degradation.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a metal fluoride/porous carbon composite positive electrode material, a positive electrode plate and a battery comprising the metal fluoride/porous carbon composite positive electrode material, wherein the metal fluoride in the metal fluoride/porous carbon composite positive electrode material is obtained through an in-situ generation method and is firmly combined with porous carbon of which the surface is compounded, so that the problem of poor electronic conductivity of the metal fluoride is solved, and the battery prepared from the metal fluoride/porous carbon composite positive electrode material has excellent cycle performance. In addition, the invention also provides a preparation method and application of the positive electrode material.
Specifically, the invention provides the following technical scheme:
the metal fluoride/porous carbon composite positive electrode material comprises metal fluoride and porous carbon, wherein the porous carbon is coated on the surface of the metal fluoride, the porous carbon contains a pore structure, and the porosity P of the porous carbon is more than or equal to 1% and 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 type of polymer and a second type of polymer, wherein the first type of polymer forms a pore structure and the second type of 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 converting the mass ratio.
According to the embodiment of the invention, the porosity P of the porous carbon is 10 percent-60 percent, and the porosity P of the porous carbon is 10 percent, 20 percent-30 percent-40 percent-50 percent-60 percent 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 porous carbon may be coated in a full or partial manner.
According to an embodiment of the present invention, in the composite positive electrode material, metal fluoride and porous carbon are physically bonded.
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 particulate or fibrous form.
According to an embodiment of the present invention, the morphology structure of the metal fluoride/porous carbon composite positive electrode material is a granular structure (such as a spherical granular structure, particularly shown in fig. 2), or a fibrous structure (such as shown in fig. 1).
According to an embodiment of the present invention, the particle diameter D50 of the metal fluoride/porous carbon composite positive electrode material having a granular structure is 3 μm to 15 μm.
According to an 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 anode material, which comprises the following steps:
(1) Mixing an organic solvent, a first polymer, a second polymer and a soluble metal salt to prepare a prefabricated solution;
(2) Treating the prefabricated solution obtained in the step (1) by using electrostatic spinning to obtain a fibrous structure, drying and then placing under high-purity argon under T 1 Carbonizing at the temperature to prepare 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 then placing under high-purity argon under T 2 Carbonizing at the temperature to obtain granular porous carbon-coated metal oxide;
(3) Subjecting the porous carbon-coated metal oxide obtained in step (2) to T 3 And sequentially carrying out reduction and fluorination treatment at the temperature to prepare the metal fluoride/porous carbon composite anode material.
According to an embodiment of the present invention, in step (1), specifically: sequentially adding a first polymer and a 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 step (1), the organic solvent is selected from at least one of dimethylformamide, dimethylacetamide and acetone.
According to an embodiment of the invention, in step (1), the decomposition temperature of the first type of polymer is substantially lower than the decomposition temperature of the second type of polymer. Illustratively, the first class of polymers has a decomposition temperature that is 100 ℃ to 250 ℃ lower than the decomposition temperature of the second class of polymers.
According to an embodiment of the invention, in step (1), the mass ratio of the first type of polymer to the second type of polymer is (0.01-0.6): 1, preferably (0.1-0.6): 1, and more preferably (0.2-0.5): 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 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.
According to an embodiment of the present invention, in 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 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 the embodiment of the invention, in the step (2), the voltage of the electrostatic spinning treatment is 10 kV-20 kV, and the solution advancing speed is 2 mL/h-10 mL/h.
According to an embodiment of the present invention, in step (2), the fibrous structure has a diameter of 0.1 μm to 5 μm.
According to an embodiment of the present invention, in step (2), parameters of the atomized granulation are set as follows: the flow rate of the solution is 2-12 mL/min, the air flow rate is 4-8L/min, the temperature of the air inlet is 155-185 ℃, and the air pressure is 0.1-0.7 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 drying temperature is 60 ℃ to 100 ℃; the drying time is 12-36 h.
According to an embodiment of the present invention, in step (2), the step (c) is performed by 1 The heating rate of carbonization at the temperature is 2 ℃ min -1 ～5℃·min -1 The method comprises the steps of carrying out a first treatment on the surface of the The T is 1 The temperature is 300-600 ℃; said at T 1 The carbonization time is 2-12 h at the temperature. Illustratively at 3 ℃ min -1 Raising the temperature to 300-400 ℃ and preserving the temperature for 1-2 h; then at 5 ℃ min -1 The temperature is raised to 550-600 ℃ and the temperature is kept for 3-5 h.
According to an embodiment of the present invention, in step (2), the step (c) is performed by 2 The heating rate of carbonization at the temperature is 2 ℃ min -1 ～5℃·min -1 The method comprises the steps of carrying out a first treatment on the surface of the The T is 2 The temperature is 300-600 ℃; said at T 2 The carbonization time is 2-12 h at the temperature. Illustratively at 3 ℃ min -1 Raising the temperature to 300-400 ℃ and preserving the temperature for 1-2 h; then at 5 ℃ min -1 The temperature is raised to 550-600 ℃ and the temperature is kept for 3-5 h.
According to an embodiment of the present invention, in step (3), the T 3 The temperature is 350-550 ℃.
According to an embodiment of the present invention, in the step (3), the time for the reduction is 1 to 5 hours.
According to an embodiment of the present invention, in step (3), the reduction is performed under a hydrogen atmosphere, and illustratively, under a mixed gas atmosphere of hydrogen and an inert gas (e.g., argon), wherein the inert gas is 90 to 96vol% in volume and the hydrogen is 4 to 10vol% in volume.
According to an embodiment of the present invention, in the step (3), the fluorination is performed under a fluorine-containing gas atmosphere, and illustratively, under a mixed gas atmosphere of a fluorine-containing gas and an inert gas (e.g., argon gas), wherein the inert gas accounts for 90 to 96vol% and the fluorine-containing gas accounts for 4 to 10vol%.
According to an embodiment of the present invention, in step (3), the fluorine-containing gas is selected from NF 3 、ClF 3 At least one of them.
According to an embodiment of the present invention, in the step (3), the time of the fluorination is 1 to 5 hours.
The invention also provides the metal fluoride/porous carbon composite anode material prepared by the method.
The invention also provides application of the metal fluoride/porous carbon composite positive electrode 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 plate.
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 anode material, and further provides a preparation method and application thereof.
In the present invention, a porous carbon/metal fluoride composite material having a specific porosity is prepared by using two polymers having different decomposition temperatures (i.e., a first type of polymer and a second type of polymer) as a carbon source. Specifically, in the heating process of the metal fluoride/porous carbon composite positive electrode material, the first type of polymer is decomposed preferentially and small holes are left on the fibers or particles, soluble metal salt can nucleate in the fibers or particles to form metal oxides, the second type of polymer is carbonized finally to obtain a porous carbon layer, the composite material is prepared by a hydrogen reduction and fluorine-containing gas fluorination method, the metal fluoride in the composite material is obtained by an in-situ generation method and is firmly combined with the porous carbon compounded on the surface, the problem of poor electronic conductivity of the metal fluoride is solved, and meanwhile, excellent cycle performance is presented.
Further, the invention can control the porosity of the porous carbon by controlling the ratio of the first type polymer to the second type polymer, and can control the ratio of the metal fluoride to the porous carbon in the composite material by controlling the ratio of the second type polymer to the soluble metal salt.
Drawings
Fig. 1 is a schematic structural diagram of a composite material prepared by electrospinning technique.
Fig. 2 is a schematic structural diagram of a composite material prepared by an atomization granulation technique.
Fig. 3 is a battery capacity retention 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 illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first," "second," and the like are used for descriptive purposes only and are not indicative or implying relative importance.
Example 1
(1) And 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 polymethyl methacrylate to polyacrylonitrile is 1:2, and the molar ratio of polyacrylonitrile to ferric acetylacetonate is 1:40.
(2) And (3) treating the prefabricated solution obtained in the step (1) by using an electrostatic spinning technology to obtain a fiber membrane (a fiber structure is obtained after electrostatic spinning, fibers are continuously generated in the receiving process and are randomly piled to form the fiber membrane structure, and the fiber membrane structure is in a macroscopic film state and is formed by a plurality of fibers in a microscopic state). Wherein the potential of the electrostatic spinning is 15kV, the distance between the needle tip and the receiving film is 20cm, and the advancing speed of the solution is 1mL/min.
(3) Drying the fibrous membrane obtained in the step (2) at 80 ℃ for 24 hours, and then transferring the fibrous membrane into a high-temperature sintering furnace filled with Ar for carbonization treatment, wherein the specific operation conditions are that the temperature is 3 ℃ for min -1 Raising the temperature to 300 ℃ at the rate of (2) and preserving the heat for 1h; then at 5 ℃ min -1 The temperature is raised to 550 ℃ and the temperature is kept for 4 hours. Polymethyl methacrylate is decomposed preferentially due to its low decomposition temperature, and polyacrylonitrile is carbonized to obtain Fe 2 O 3 Composite with porous carbon.
(4) Fe obtained in the step (3) 2 O 3 Transferring the composite material with porous carbon into a high temperature furnace at 3 ℃ for min -1 Is heated to 450 ℃ and is filled with H 2 Heat preservation is carried out for 2h on the mixed gas of Ar and Fe in the composite material 2 O 3 Reducing into Fe. Subsequently, NF was introduced into the furnace 3 Heat-insulating for 2h by mixing Ar and/or Fe 2 O 3 After fluorination, feF can be obtained 3 Composite with porous carbon.
Finally, the porous carbon/ferric fluoride composite positive electrode material with the porosity P of 50% can be obtained, and the molar ratio of ferric fluoride to porous carbon is 40:1.
Example 2
Other operations are the same as in example 1, except that: the mass ratio of polymethyl methacrylate to polyacrylonitrile in example 2 was 0.25:1.
Finally, the porous carbon/ferric fluoride composite positive electrode material with the porosity P of 25% is obtained, and the molar ratio of ferric fluoride to porous carbon is 40:1.
Example 3
Other operations are the same as in example 1, except that: the soluble metal salt in example 3 was an equimolar portion of cobalt acetylacetonate.
Finally, the porous carbon/cobalt fluoride composite positive electrode material with the porosity P of 50% can be obtained, and the molar ratio of cobalt fluoride to porous carbon is 40:1.
Example 4
Other operations are the same as in example 1, except that: the molar ratio of polyacrylonitrile to iron acetylacetonate in example 4 was 1:60.
Finally, the porous carbon/ferric fluoride composite positive electrode material with the porosity P of 50% can be obtained, and the molar ratio of ferric fluoride to porous carbon is 60:1.
Example 5
Other operations are the same as in example 1, except that:
and (3) carrying out atomization granulation on the prefabricated solution obtained in the step (1) to obtain particles. Wherein the flow rate of the solution is controlled to be 3mL/min, the air flow rate is 5L/min, the temperature of the air inlet is 175 ℃, and the air pressure is 0.4MPa in the atomization granulation process.
Finally, the porous carbon/ferric fluoride composite positive electrode material with the porosity P of 50% can be obtained, and the molar ratio of ferric fluoride to porous carbon is 40:1.
Comparative example 1
Selecting 0.5 mole part of conductive graphite and 20 mole parts of ferric fluoride, uniformly mixing, performing planetary ball milling for 12 hours by taking isopropanol as a ball milling medium, taking out and drying to obtain FeF 3 And the molar ratio of the ferric fluoride to the graphite is 40:1, and the composite positive electrode material is only the physical mixture of the carbon material and the ferric fluoride, does not obtain a specific microstructure, and the ferric fluoride is distributed in the graphite sheet.
Comparative example 2
The other operations were identical to example 1, except that the preparation of the pre-prepared solution was as follows:
1 molar part of polyacrylonitrile is dissolved in dimethylformamide, 40 molar parts of ferric acetylacetonate is added after the polyacrylonitrile is fully dissolved, and the prefabricated solution is obtained after stirring for 12 hours.
Finally, the carbon/ferric fluoride composite anode material without a hole structure is obtained, and the molar ratio of ferric fluoride to carbon material is 40:1.
Comparative example 3
The other operations were identical to example 1, except that the preparation of the pre-prepared solution was as follows:
and 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 polymethyl methacrylate to polyacrylonitrile is 0.7:1, and the molar ratio of polyacrylonitrile to ferric acetylacetonate is 1:40.
Finally, the porous carbon/ferric fluoride composite positive electrode material with the porosity of 70% is obtained, and the molar ratio of ferric fluoride to porous carbon is 40:1.
Comparative example 4
The other operations were identical to example 1, except that the preparation of the pre-prepared solution was as follows:
and 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 polymethyl methacrylate to polyacrylonitrile is 0.7:1, and the molar ratio of polyacrylonitrile to ferric acetylacetonate is 1:60.
Finally, the porous carbon/ferric fluoride composite positive electrode material with the porosity of 70% is obtained, and the molar ratio of ferric fluoride to porous carbon is 60:1.
Test example 1
According to the mass ratio of 8:1:1, 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 are sequentially selected, the mixture is fully ground and then dissolved in methyl pyrrolidone, the mixture is stirred for 8-12 hours, the slurry is uniformly coated on a carbon-coated aluminum foil, and the mixture is baked in an oven at 80 ℃ for 8 hours, taken out and cut into round pole pieces with the diameter of 12 mm. The pole piece is taken as an anode, the metal lithium is taken as a cathode, and the electrolyte is 1M LiPF 6 EC: dec=1:1V/V, 10% fec, assembled into a coin cell, and charge and discharge tests were performed in the range of 2 to 4.5V, with the charge and discharge rates of 0.33C.
Fig. 3 is a graph showing the capacity retention rate of example 1 and comparative example 1 according to the present invention, wherein the capacity retention rate of the fluoride/porous carbon composite cathode material prepared by the inventive technique after 500 cycles is 66.6%, and the composite cathode material prepared by the conventional ball milling method (comparative example 1) is only 16.8%. The composite positive electrode material prepared by the technology has excellent cycle performance.
As can be seen from examples 1 to 5 and comparative example 1, the capacity retention rate of the composite positive electrode provided by the present invention after 500 cycles is much higher than that of the composite positive electrode prepared by the conventional ball milling method, compared with the composite positive electrode prepared by the conventional ball milling method. This is because in the composite positive electrode material provided by the invention, the porous carbon is tightly combined with the metal fluoride, the electron conductivity of the metal fluoride is increased, and the volume change of the metal fluoride in the charge-discharge process can be limited.
As can be seen from examples 1 to 5 and comparative examples 2 to 4, the capacity retention rates of the composite anodes in examples 1 to 5 after 500 cycles were also higher than those of the composite anodes provided 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 between the metal fluoride and 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 metal fluoride can generate volume change in the charging and discharging process, so that the structure of the porous carbon is collapsed, and the problems of failure of the porous carbon and reduction of the electronic conductivity of the composite positive electrode are caused. Therefore, the composite positive electrode material with specific porosity provided by the invention can have excellent capacity retention rate and cycle stability.
The foregoing has outlined rather broadly the more detailed description of the invention in order that the detailed description of the invention and the embodiments herein may be implemented using specific embodiments that are merely provided to facilitate the understanding of the principles and core concepts of the invention and to enable any person skilled in the art to practice the invention. It should be noted that it will be apparent to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the principle of the invention, and these improvements and modifications fall within the scope of the claims of the invention. The scope of the invention is defined by the claims and may include other embodiments and methods that will 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, improvement, etc. 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 metal fluoride/porous carbon composite positive electrode material is characterized by comprising metal fluoride and porous carbon, wherein the porous carbon is coated on the surface of the metal fluoride, the porous carbon contains a pore structure, and the porosity P of the porous carbon is more than or equal to 1% and less than or equal to 60%;
the metal fluoride/porous carbon composite positive electrode material is prepared by the following method:
(1) Mixing an organic solvent, a first polymer, a second polymer and a soluble metal salt to prepare a prefabricated solution;
(2) Treating the prefabricated solution obtained in the step (1) by using electrostatic spinning to obtain a fibrous structure, drying and then placing under high-purity argon under T 1 Carbonizing at the temperature to prepare 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 then placing under high-purity argon under T 2 Carbonizing at the temperature to obtain granular porous carbon-coated metal oxide;
(3) Subjecting the porous carbon-coated metal oxide obtained in step (2) to T 3 Sequentially carrying out reduction and fluorination treatment at the temperature to prepare the metal fluoride/porous carbon composite anode material;
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; the mass ratio of the first polymer to the second polymer is (0.01-0.6): 1;
in step (2), the T 1 The temperature is 300-600 ℃; the T is 2 The temperature is 300-600 ℃;
in step (3), the T 3 The temperature is 350-550 ℃.
2. The metal fluoride/porous carbon composite positive electrode material according to claim 1, wherein the porous carbon has a porosity P satisfying 10% p.ltoreq.60%.
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 to 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 granular structure is 3 μm 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. A method for preparing the metal fluoride/porous carbon composite positive electrode material of any one of claims 1 to 6, comprising the steps of:
(1) Mixing an organic solvent, a first polymer, a second polymer and a soluble metal salt to prepare a prefabricated solution;
(2) Treating the prefabricated solution obtained in the step (1) by using electrostatic spinning to obtain a fibrous structure, drying and then placing under high-purity argon under T 1 Carbonizing at temperature to obtain fibrous porous carbon coatingMetal oxide of (2);
or, atomizing and granulating the prefabricated solution obtained in the step (1) to obtain a granular structure, drying and then placing under high-purity argon under T 2 Carbonizing at the temperature to obtain granular porous carbon-coated metal oxide;
(3) Subjecting the porous carbon-coated metal oxide obtained in step (2) to T 3 Sequentially carrying out reduction and fluorination treatment at the temperature to prepare the metal fluoride/porous carbon composite anode material;
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; the mass ratio of the first polymer to the second polymer is (0.01-0.6): 1;
in step (2), the T 1 The temperature is 300-600 ℃; the T is 2 The temperature is 300-600 ℃;
in step (3), the T 3 The temperature is 350-550 ℃.
8. The method according to claim 7, wherein 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), said at T 1 The heating rate of carbonization at the temperature is 2 ℃ min -1 ~5℃·min -1 The method comprises the steps of carrying out a first treatment on the surface of the Said at T 1 Carbonizing at the temperature for 2-12 hours;
and/or, in step (2), said at T 2 The heating rate of carbonization at the temperature is 2 ℃ min -1 ~5℃·min -1 The method comprises the steps of carrying out a first treatment on the surface of the Said at T 2 Carbonizing at the temperature for 2-12 hours;
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 performed under a hydrogen atmosphere;
and/or, in step (3), the fluorination is carried out under an atmosphere of a fluorine-containing gas selected from NF 3 、ClF 3 At least one of them.
9. A positive electrode sheet comprising the metal fluoride/porous carbon composite positive electrode material of any one of claims 1 to 6.
10. A battery comprising the metal fluoride/porous carbon composite positive electrode material of any one of claims 1 to 6, or the positive electrode sheet of claim 9.
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