CN117253995A - High-voltage high-entropy metal fluoride positive electrode, preparation method and application thereof - Google Patents
High-voltage high-entropy metal fluoride positive electrode, preparation method and application thereof Download PDFInfo
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- CN117253995A CN117253995A CN202311405101.2A CN202311405101A CN117253995A CN 117253995 A CN117253995 A CN 117253995A CN 202311405101 A CN202311405101 A CN 202311405101A CN 117253995 A CN117253995 A CN 117253995A
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- fluoride
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- 229910001512 metal fluoride Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims abstract description 23
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 20
- 239000000661 sodium alginate Substances 0.000 claims abstract description 20
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims abstract description 4
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims abstract description 4
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims abstract description 4
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229910016509 CuF 2 Inorganic materials 0.000 abstract description 14
- 239000011230 binding agent Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 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 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- RBNHXGOCXJPVEK-UHFFFAOYSA-L [C].[Cu](F)F Chemical compound [C].[Cu](F)F RBNHXGOCXJPVEK-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- -1 copper fluoride-sodium Chemical compound 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 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
- H01M4/13—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
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Abstract
A high-voltage high-entropy metal fluoride positive electrode, a preparation method and application thereof belong to the technical field of lithium ion batteries. Copper fluoride, ferric fluoride, cobalt fluoride, nickel fluoride and manganese fluoride are mixed, sodium alginate is added, and high-entropy metal fluoride material which is evenly fused with the sodium alginate is obtained through ball milling under the protection of argon; then adding the mixture into the reactor under the protection of argonBlack, and ball milling under the same conditions; mixing the powder obtained by ball milling with Mxene aqueous dispersion, coating the mixture on a titanium foil after ball milling, and drying to obtain the high-entropy metal fluoride anode combined with the conductive adhesive. The invention applies the high entropy material and the high conductivity crosslinking binder to the copper fluoride anode, and utilizes the improvement of the conductivity of the high entropy material and the high conductivity crosslinking binder, the protection effect on the copper fluoride and the CuF 2 The crosslinking effect among the three substances SA and MXene improves the conductivity and the cycling stability of the positive electrode, and simultaneously enables the average discharge voltage of the full battery to break through 2.5V, thereby being capable of being used for assembling the full battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage high-entropy metal fluoride positive electrode of a lithium-fluoride battery, a preparation method and application of the positive electrode in the assembly of a full battery.
Background
In recent years, with the development of new energy sources such as solar energy, wind energy and nuclear energy and the construction of infrastructure, the demands of the country for an energy storage and conversion system for solving the time domain and the territory of the new energy sources are increasing correspondingly, so that a novel energy storage battery is paid attention as a key of the energy storage system. Nowadays, due to the need of large-scale energy storage, the development of commercial lithium ion battery anodes faces the problems of low average discharge voltage, low energy density, rising cost and the like, and the most advanced intercalation type anodes already reach the theoretical capability limit of the intercalation type anodes, so that the development of novel battery anodes with high energy density becomes the key point and hot point of current academic research.
At present, the discharge process of the conversion type fluoride positive electrode involves multiple electron transfer, has higher specific capacity, and the ferric fluoride positive electrode has high energy density and low cost, and is a candidate of the positive electrode of a novel large-scale energy storage lithium ion battery system. However, the iron fluoride anode has a low electron conductivity, and the actual average discharge voltage is far lower than the theoretical value, which limits the exertion of the energy density. Whereas copper fluoride positive electrode because of its relative Li/Li + The high theoretical potential of 3.55V and higher energy density are expected to replace the ferric fluoride anode to be a new development direction of a fluoride anode system. However, the copper fluoride anode also has the problems of larger volume expansion, poor conductivity and aggregation of copper nano particles in the charge and discharge process during discharge, and serious shadowThe cycle life of the copper fluoride anode is prolonged; again, the severe dissolution of the active material copper fluoride during battery loading results in irreversible capacity loss, further limiting the development of copper fluoride anodes.
To address these challenges, researchers have conducted extensive research. However, only limited progress has been made. At present, the initial performance of the copper fluoride anode can be improved by using a nanoscale copper fluoride carbon composite anode or using an iron doping method, but the cycle cannot exceed 10 circles; the use of copper fluoride-sodium alginate composite anode can make the battery stably circulate, but the average discharge voltage still can not reach 2.5V.
Disclosure of Invention
The invention aims to provide a high-voltage high-entropy metal fluoride positive electrode of a lithium-fluoride battery, a preparation method and application thereof in the assembly of a full battery.
The lithium-fluoride battery of the invention is a high-voltage high-entropy metal fluoride positive electrode (HE-CuF) 2 Firstly, mixing 0.9 to 1.2g of anhydrous copper fluoride, 0.04 to 0.1g of anhydrous ferric fluoride, 0.04 to 0.1g of anhydrous cobalt fluoride, 0.04 to 0.1g of anhydrous nickel fluoride and 0.04 to 0.1g of anhydrous manganese fluoride, adding 0.2 to 0.4g of anhydrous Sodium Alginate (SA), and ball milling for 1 to 3 hours under the condition of argon protection and 400 to 600rpm to obtain a high-entropy metal fluoride material uniformly fused with the sodium alginate; then adding 0.25-0.8 g of ketjen black under the protection of argon, and ball milling for 2-8 hours under the same conditions to uniformly disperse the high-entropy metal fluoride material in the carbon skeleton; mixing the powder obtained by ball milling with 2-10wt% of Mxene aqueous dispersion according to the mass ratio of 1-10: 1, mixing and continuing ball milling for 0.5-1.5 h; finally coating the high-entropy metal fluoride material on a titanium foil, wherein the loading capacity of the high-entropy metal fluoride material is 0.5-1 mg/cm 3 And then drying the mixture for 18 to 36 hours under the vacuum at 70 to 90 ℃ to obtain the high-entropy metal fluoride anode combined with the conductive adhesive.
The invention applies the high-entropy metal fluoride material and the high-conductivity crosslinking binder to the anode of the lithium ion battery by a ball milling method, and utilizes the improvement of the conductivity of the high-entropy metal fluoride material and the high-conductivity crosslinking binder, the protection effect of the high-entropy metal fluoride material on copper fluoride and CuF 2 Interaction among three substances of SA, MXeneThe coupling effect improves the conductivity and the cycling stability of the positive electrode, and simultaneously enables the average discharge voltage of the whole battery to break through 2.5V.
The beneficial effects of the invention are as follows:
1) Develops a brand new high-entropy metal fluoride anode, the method can synthesize the high-entropy metal fluoride by a one-step ball milling method, the flow is simple, and the average discharge voltage of the product is obviously improved.
2) The prepared high-entropy metal fluoride material has obviously improved conductivity and cycling stability due to the 'cocktail' effect of the high-entropy material (a synergistic effect caused by interaction among elements, namely, the special combination of the elements can cause the change of material properties such as conductivity and the like).
3) CuF is prepared by simple liquid phase method 2 And the SA and the MXene are crosslinked, and a layer of polymer film with high conductivity and protection function is formed on the surface of the active substance, so that the conductivity of the anode is greatly improved, and the average discharge voltage of the material is further improved.
Drawings
In order to more clearly illustrate the technical solution of the present invention and the properties of the materials produced therefrom, the following is given in relation to the drawings.
FIG. 1 is a high entropy metal fluoride cathode (HE-CuF) prepared in example 1 2 -X-ray diffraction (XRD) pattern of SA-M). From the XRD pattern, it can be obtained that the high-entropy metal fluoride is successfully prepared, and the main phase is copper fluoride.
FIG. 2 is a HE-CuF prepared from example 1 2 Scanning Electron Microscope (SEM) image of SA-M powder. SEM image shows HE-CuF 2 SA-M is a nanoparticle with a size of 50-200 nm, bonded together by a binder consisting of SA and Mxene.
FIG. 3 is a HE-CuF prepared in example 1 2 -Transmission Electron Microscopy (TEM) image (a) and corresponding High Resolution Transmission Electron Microscopy (HRTEM) image (b) of SA-M powder. TEM images show HE-CuF 2 The SA-M powder is of a size on the nanometer scale and is connected together by a binder consisting of SA and Mxene, corresponding to the morphology in the SEM image; in the graph (b) the lattice fringes corresponding to copper fluoride can be seen, sayThe main body of the bright material is copper fluoride.
FIG. 4 is a HE-CuF prepared in example 1 2 -a Transmission Electron Microscope (TEM) image of the SA-M powder corresponding to an X-ray spectroscopy (EDS) image. The uniform distribution of Na and Ti elements and the distributed distribution of Cu and F elements show that the binding agent composed of SA and Mxene successfully binds the high-entropy fluoride particles together to form a polymer conductive network; and the elements of manganese, cobalt, nickel and iron can be detected, which shows that the main body of the material is copper fluoride, and the high-entropy component of the fluoride of manganese, cobalt, nickel and iron is successfully introduced.
FIG. 5 is a HE-CuF prepared in example 1 2 -discharge profile of SA-M material positive assembled full cell. As can be seen from the figure, the initial capacity of the material is higher, but the discharge voltage is lower, the discharge voltage is obviously improved after 10 cycles, and an obvious discharge platform appears at the high voltage of about 2.7V, which indicates that ion diffusion and charge transfer are gradually enhanced, and the ion diffusion and charge transfer are related to the formation of conductive CEI/SEI and high-entropy material "cocktail" effect along with charge-discharge reaction on the electrode.
FIG. 6 is a HE-CuF prepared in example 1 2 Cycling performance profile of SA-M material assembled full cell at 0.05C. The graph consists of two curves, curve 1 is the discharge specific capacity curve of the positive electrode, and contains HE-CuF 2 The full battery of the SA-M positive electrode can stably circulate for more than 40 weeks, and the residual capacity still has 298.2mAh g -1 Indicating to contain HE-CuF 2 The full cell of the SA-M positive electrode has excellent average discharge voltage and stable cycle performance; curve 2 is the average discharge voltage curve of the positive electrode, and it can be seen from the graph that HE-CuF is activated briefly 2 SA-M can reach more than 2.5V.
FIG. 7 is a CuF prepared in example 2 2 Scanning Electron Microscope (SEM) image of SA-M powder. SEM image shows CuF 2 SA-M powder is of a size on the order of nanometers and is held together by a binder consisting of SA and Mxene, but is heavily aggregated compared to high entropy materials.
FIG. 8 is a CuF prepared in example 2 2 -discharge profile of SA-M material positive assembled full cell. As can be seen, with HE-CuF 2 CuF compared with SA-M 2 The full cell voltage platform assembled by the SA-M material anode is greatly shortened, and the high entropy fluoride promotes the reaction kinetics of the anode, so that the reaction of the copper fluoride at a higher potential is easier to occur.
FIG. 9 is a CuF prepared in example 2 2 Cycling performance profile of SA-M material positive assembled full cell at 0.05C. Curve 1 is the average discharge voltage curve of the positive electrode, and curve 2 is the discharge specific capacity curve of the positive electrode. As can be seen from the figure, it contains CuF 2 The full cell of the SA-M positive electrode has the same structure as HE-CuF 2 The similar discharge specific capacity of the SA-M positive electrode, but the average discharge voltage can only reach about 2.1V at most, which indicates that the cocktail effect of the high-entropy component can optimize the reaction kinetics of the copper fluoride positive electrode and effectively improve the average discharge voltage of the fluoride positive electrode.
FIG. 10 is a CuF prepared in example 3 2 Charge-discharge curve of the M positive assembled full cell, curve 1 being the discharge curve and curve 2 being the charge curve. As can be seen, with HE-CuF 2 SA-M and CuF 2 Compared with the SA-M positive electrode, the battery assembled by the pure copper fluoride positive electrode without sodium alginate cannot be charged to 4.4V after discharging, which proves that the sodium alginate has a protective effect on the copper fluoride positive electrode.
Detailed Description
Example 1:
firstly, mixing 1g of anhydrous copper fluoride, 0.05g of anhydrous ferric fluoride, 0.05g of anhydrous cobalt fluoride, 0.05g of anhydrous nickel fluoride and 0.05g of anhydrous manganese fluoride, adding 0.3g of anhydrous sodium alginate, and ball-milling for 2 hours under the conditions of argon protection and 450rpm to obtain a high-entropy metal fluoride material uniformly fused with the sodium alginate; then adding 0.6g of Keqin black under the protection of argon, and ball-milling for 4 hours under the same conditions to uniformly disperse the high-entropy metal fluoride material in the carbon skeleton; mixing the powder obtained by ball milling with 5wt% of Mxene aqueous dispersion liquid according to the mass ratio of 3:1, mixing and continuing ball milling for 1h; finally, coating the high-entropy metal fluoride material on a titanium foil with the thickness of 3cm multiplied by 3cm, wherein the loading amount of the high-entropy metal fluoride material is 0.8mg/cm 3 Drying in a vacuum oven at 80 ℃ for 24 hours to obtain the high-entropy metal fluoride anode (HE-CuF) combined with the conductive adhesive 2 -SA-M)。
When the full cell was assembled, the high entropy metal fluoride positive electrode combined with the conductive adhesive was used as the positive electrode, the metal lithium was used as the negative electrode, whatman 1822-090 was used as the separator, and 60. Mu.L of 4M LiClO was dissolved in each of both sides of the separator 4 The volume ratio is 1:1 (multi-reagent).
Example 2:
example 2 differs from example 1 in that only one fluoride of copper fluoride and anhydrous sodium alginate are used in the first ball milling step to prepare CuF 2 -SA-M positive electrode. The electrochemical performance test was similar to that in example 1.
Example 3:
example 3 differs from example 2 in that anhydrous sodium alginate was not used in the first ball milling, copper fluoride was used directly with ketjen black ball milling, and the material was mixed with polyvinylidene fluoride (PVDF) at 9:1, and coating on 3cm×3cm titanium foil to obtain CuF 2 -an M positive electrode. The electrochemical performance test was similar to that in example 1.
Claims (5)
1. A preparation method of a high-voltage high-entropy metal fluoride positive electrode is characterized by comprising the following steps of: firstly, mixing 0.9 to 1.2g of anhydrous copper fluoride, 0.04 to 0.1g of anhydrous ferric fluoride, 0.04 to 0.1g of anhydrous cobalt fluoride, 0.04 to 0.1g of anhydrous nickel fluoride and 0.04 to 0.1g of anhydrous manganese fluoride, adding 0.2 to 0.4g of anhydrous sodium alginate, and ball milling for 1 to 3 hours under the conditions of argon protection and 400 to 600rpm to obtain a high-entropy metal fluoride material uniformly fused with the sodium alginate; then adding 0.25-0.8 g of ketjen black under the protection of argon, and ball milling for 2-8 hours under the same conditions to uniformly disperse the high-entropy metal fluoride material in the carbon skeleton; mixing the powder obtained by ball milling with 2-10wt% of Mxene aqueous dispersion according to the mass ratio of 1-10: 1, mixing and continuing ball milling for 0.5-1.5 h; finally coating the high entropy metal fluoride anode combined with the conductive adhesive on a titanium foil, and drying the high entropy metal fluoride anode under vacuum.
2. The method for preparing the high-voltage high-entropy metal fluoride positive electrode according to claim 1, wherein the method comprises the following steps: high entropy goldThe loading of the fluoride material is 0.5-1 mg/cm 3 。
3. The method for preparing the high-voltage high-entropy metal fluoride positive electrode according to claim 1, wherein the method comprises the following steps: is dried for 18 to 36 hours under the vacuum at 70 to 90 ℃.
4. A high voltage high entropy metal fluoride positive electrode, characterized in that: is prepared by the method of claim 1, 2 or 3.
5. Use of a high voltage high entropy metal fluoride cathode as claimed in claim 4 in assembling a full cell.
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| CN117638006B (en) * | 2024-01-23 | 2024-03-29 | 江苏华富储能新技术股份有限公司 | Lithium metal fluoride high-entropy SEI layer, preparation method and application thereof |
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