CN110931735A - Modified composite material, preparation method thereof, and positive electrode material and lithium battery comprising modified composite material - Google Patents
Modified composite material, preparation method thereof, and positive electrode material and lithium battery comprising modified composite material Download PDFInfo
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- CN110931735A CN110931735A CN201911119779.8A CN201911119779A CN110931735A CN 110931735 A CN110931735 A CN 110931735A CN 201911119779 A CN201911119779 A CN 201911119779A CN 110931735 A CN110931735 A CN 110931735A
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910052744 lithium Inorganic materials 0.000 title abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 40
- 239000011149 active material Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000000227 grinding Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- 239000013543 active substance Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 12
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910017665 NH4HF2 Inorganic materials 0.000 claims description 7
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 7
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 6
- 229910003638 H2SiF6 Inorganic materials 0.000 claims description 6
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 claims description 6
- 229910004883 Na2SiF6 Inorganic materials 0.000 claims description 6
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 claims description 6
- 229910004014 SiF4 Inorganic materials 0.000 claims description 6
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 claims description 6
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 6
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 6
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 6
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000010405 anode material Substances 0.000 abstract description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 71
- 239000000463 material Substances 0.000 description 36
- 229910019142 PO4 Inorganic materials 0.000 description 20
- 229910016153 LiMn0.9Fe0.1PO4 Inorganic materials 0.000 description 17
- 239000007772 electrode material Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 12
- -1 ion compound Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000008040 ionic compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/388—Halogens
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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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- Y02E60/10—Energy storage using batteries
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Abstract
The application discloses a modified composite material, a preparation method thereof, and a positive electrode material and a lithium battery comprising the modified composite material. A modified composite comprising an active material and a fluorine source, the active material being selected from at least one of compounds having the formula shown in formula (I) and formula (ii): li1‑xAxMnyM1‑yPO4/C(I)；mLi1‑aAaMnbM1‑bPO4‑nLi1‑cAcFedN1‑dO4C (II). The modified composite material greatly improves the electrochemical performance of the anode material, and particularly improves the battery capacity.
Description
Technical Field
The application relates to a composite electrode material, and belongs to the field of electrode materials.
Background
The lithium ion battery is an electrochemical energy storage device which realizes energy storage and release by utilizing the migration of lithium ions between a positive electrode and a negative electrode in the battery, and the lithium ion battery is widely applied to the fields of electronic products, power batteries, power grid energy storage and the like at present, but the development of the lithium ion battery is limited due to the lower energy density of the lithium ion battery.
Phosphate positive electrode materials have received much attention due to their advantages of low cost, excellent stability, and good safety. However, there is still a continuing need to obtain higher capacity cathode materials.
Disclosure of Invention
According to one aspect of the present application, there is provided a modified composite material comprising an active substance and a fluorine source,
wherein the active substance is at least one selected from compounds having the formula shown in formula (I) and formula (II):
Li1-xAxMnyM1-yPO4/C (I)
wherein,
0 ≦ x ≦ 0.5, e.g., x ≦ 0,
a is at least one selected from Na, K and Mg,
0 ≦ y ≦ 1, e.g., y ≦ 1, and
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti;
mLi1-aAaMnbM1-bPO4-nLi1-cAcFedN1-dPO4/C (Ⅱ)
wherein,
0 < m < 1, for example m 0.9,
0 ≦ a ≦ 0.5, e.g., a ≦ 0,
a is at least one selected from Na, K and Mg,
0 ≦ b ≦ 1, e.g., b ≦ 1,
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti,
0 < n < 1, for example n-0.1,
0 ≦ c ≦ 0.5, e.g., c ≦ 0,
0. ltoreq. d.ltoreq.1, e.g. d 1, and
n is at least one selected from Mg, Co, Ni, V, Al and Ti.
Optionally, a fluorine source coats the active.
In one preferred embodiment of the modified composite material of the present invention, in formula (I), x ═ 0, y ═ 1, and M ═ Fe; and in formula (II), M is 0.9, a is 0, b is 1, M is Fe, n is 0.1, c is 0 and d is 1.
In the present invention, the active material is preferably selected from LiMn0.9Fe0.1PO4、0.9LiMnPO4-0.1LiFePO4At least one of (1).
In the present invention, the fluorine source is selected from at least one of fluoride ion-containing compounds.
In a preferred embodiment of the modified composite material of the present invention, said fluorine source is selected from the group consisting of LiF, NaF, NaHF2、KF、KHF2、NH4HF2、NH4F、CaF2、MgF2、AlF3、ZnF2、CoF3、NiF2、MnF2、FeF2、BaF2、Na2SiF6、H2SiF6、SiF4At least one of (1).
In a preferred embodiment of the modified composite material of the present invention, the mass ratio of the fluorine source to the active material is 0.1:100 to 50: 100.
Optionally, the upper limit of the mass ratio of the fluorine source to the active substance in the raw material containing the fluorine source and the active substance is selected from 50:100, 40:100, 30:100, 20:100, 10:100, 8:100, 5:100, 3:100 or 1: 100; the lower limit is selected from 1:100, 0.8:100, 0.5:100 or 0.1: 100.
Optionally, the material is generated in situ by a fluorine source and an active species.
Optionally, the fluorine source is selected from LiF, NaF, NaHF2、KF、KHF2、NH4HF2、NH4F、CaF2、MgF2、AlF3、ZnF2、CoF3、NiF2、MnF2、FeF2、BaF2、Na2SiF6、H2SiF6、SiF4At least one of (1).
Optionally, the fluorine-containing compound is LiF.
Therefore, in the present invention, preferably, the modified composite material is a LiF coated active material.
Optionally, the active material is a phosphate positive electrode material.
Optionally, A in the formula I or the formula II is selected from at least one of Mg, K and Na.
In the invention, the modified composite material is prepared by adopting a surface doping method, so that the capacity is effectively improved. The method adopts ionic compounds to modify the surface of the phosphate anode material, and generates the fluorine-containing compounds such as LiF-coated phosphate anode material in situ. Fluorine-containing compounds such as LiF have high chemical/electrochemical stability, and can greatly improve the electrochemical performance of the phosphate anode material. Moreover, after the surface of the positive electrode material is coated with the inert substance, the direct contact between the electrolyte and the active material can be reduced, so that the side reaction with the electrolyte is reduced, and the electrochemical activity of the positive electrode material is improved.
According to a second aspect of the present application, there is provided a method for preparing a modified composite material, the method comprising at least the steps of:
mixing raw materials containing a fluorine source and an active substance, heating to 80-800 ℃, preserving heat for 0.5-20 h to obtain a modified composite material,
wherein the active substance is at least one selected from compounds having the formula shown in formula (I) and formula (II):
Li1-xAxMnyM1-yPO4/C (I)
wherein,
0 ≦ x ≦ 0.5, e.g., x ≦ 0,
a is at least one selected from Na, K and Mg,
0 ≦ y ≦ 1, e.g., y ≦ 1, and
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti;
mLi1-aAaMnbM1-bPO4-nLi1-cAcFedN1-dPO4/C (Ⅱ)
wherein,
0 < m < 1, for example m 0.9,
0 ≦ a ≦ 0.5, e.g., a ≦ 0,
a is at least one selected from Na, K and Mg,
0 ≦ b ≦ 1, e.g., b ≦ 1,
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti,
0 < n < 1, for example n-0.1,
0 ≦ c ≦ 0.5, e.g., c ≦ 0,
0. ltoreq. d.ltoreq.1, e.g. d 1, and
n is at least one selected from Mg, Co, Ni, V, Al and Ti.
In a preferred embodiment of the process of the invention, in formula I, x ═ 0, y ═ 1 and M ═ Fe; and formula II wherein M is 0.9, a is 0, b is 1, M is Fe, n is 0.1, c is 0 and d is 1.
In a preferred embodiment of the process according to the invention, the fluorine source is selected from LiF, NaF, NaHF2、KF、KHF2、NH4HF2、NH4F、CaF2、MgF2、AlF3、ZnF2、CoF3、NiF2、MnF2、FeF2、BaF2、Na2SiF6、H2SiF6、SiF4At least one of (1).
In a preferred embodiment of the process of the present invention, the mass ratio of the fluorine source to the active material is 0.1:100 to 50: 100.
Optionally, the upper limit of the mass ratio of the fluorine source to the active substance in the raw material containing the fluorine source and the active substance is selected from 50:100, 40:100, 30:100, 20:100, 10:100, 8:100, 5:100, 3:100 or 1: 100; the lower limit is selected from 1:100, 0.8:100, 0.5:100 or 0.1: 100.
The preparation method of the composite material is characterized by comprising the following steps:
mixing raw materials containing a fluorine source and an active substance, heating to 80-800 ℃, and preserving heat for 0.5-20 hours to obtain the composite material.
Optionally, the upper limit of the temperature of the heating is selected from 800 ℃, 700 ℃, 600 ℃, 500 ℃, 400 ℃ or 300 ℃; the lower limit is selected from 300 deg.C, 200 deg.C, 100 deg.C or 80 deg.C.
In the present invention, the fluorine source is at least one selected from fluorine ion-containing compounds.
Optionally, the fluorine source is selected from LiF, NaF, NaHF2、KF、KHF2、NH4HF2、NH4F、CaF2、MgF2、AlF3、ZnF2、CoF3、NiF2、MnF2、FeF2、BaF2、Na2SiF6、H2SiF6、SiF4At least one of (1).
Optionally, the fluorine source is LiF.
Optionally, the fluorine source is NH4F。
Optionally, the heating temperature is 100-600 ℃; the heating rate is 1-10 ℃/min.
Optionally, the heating temperature is 200-400 ℃.
Optionally, the heating ramp rate is 5 deg.C/min.
Optionally, in the method of the present invention, the raw materials containing the fluorine source and the active material are mixed, ground and then heated, wherein the grinding time is 10 to 120 minutes.
Optionally, the method comprises the steps of:
mixing raw materials containing a fluorine source and an active substance, and grinding to obtain a mixture I; and heating the mixture I to 100-600 ℃ at the heating rate of 5 ℃/min, and cooling to room temperature to obtain the composite material.
As an embodiment, the method of the invention comprises the steps of:
mixing a phosphate anode material and a fluorine-containing ion compound according to a certain proportion, and grinding to obtain a mixture I; and (3) putting the mixture I into a muffle furnace, heating to 100-600 ℃ at a speed of 5 ℃/min, and cooling to room temperature to obtain the modified composite electrode material.
As a specific embodiment, the present invention provides a method for in-situ generation of a LiF-coated lithium ion battery phosphate positive electrode material, comprising the steps of:
mixing a phosphate anode material (LiAMnMP/C) and an ionic compound according to a certain proportion, and grinding; and (3) putting the sample into a muffle furnace, heating to 100-600 ℃ at a speed of 5 ℃/min, and cooling to room temperature. Obtaining the LiAMnMP/C-LiF sample.
Wherein the molecule of the phosphate anode material is Li1-xAxMnyM1-yPO4The formula is represented by the general formula I, wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1, M is selected from at least one of Mg, Fe, Co, Ni, V, Al or Ti, and A is selected from at least one of Na, K and Mg; the ionic compound is selected from LiF and KHF2，NH4HF2，NH4F，NaHF2One or more of (a).
According to a third aspect of the present invention, there is provided a positive electrode material comprising the modified composite material of the present invention or the modified composite material prepared according to the method of the present invention.
In the present application, it is preferred that,treating the surface of a phosphate anode sample by adopting a fluorine-containing ion compound, uniformly mixing the fluorine-containing ion compound and a phosphate anode material, and then adding protective gas (N)2Ar, different proportions H2Inert gases such as/Ar mixed gas) and then subjected to low-temperature treatment to generate a phosphate anode material coated by a fluorine-containing ion compound in situ; the ionic compound is fluoride selected from LiF, NaF and NaHF2、KF、KHF2、NH4HF2、NH4F、CaF2、MgF2、AlF3、ZnF2、CoF3、NiF2、MnF2、FeF2、BaF2、Na2SiF6、H2SiF6、SiF4One or more of (a).
Optionally, the positive electrode with the composite coating layer, wherein the internal active material is a lithium manganese phosphate positive electrode material having a formula of formula (I) or formula (II):
Li1-xAxMnyM1-yPO4/C (I)
wherein,
0 ≦ x ≦ 0.5, e.g., x ≦ 0,
a is at least one selected from Na, K and Mg,
0 ≦ y ≦ 1, e.g., y ≦ 1, and
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti;
mLi1-aAaMnbM1-bPO4-nLi1-cAcFedN1-dPO4/C (Ⅱ)
wherein,
0 < m < 1, for example m 0.9,
0 ≦ a ≦ 0.5, e.g., a ≦ 0,
a is at least one selected from Na, K and Mg,
0 ≦ b ≦ 1, e.g., b ≦ 1,
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti,
0 < n < 1, for example n-0.1,
0 ≦ c ≦ 0.5, e.g., c ≦ 0,
0. ltoreq. d.ltoreq.1, e.g. d 1, and
n is at least one selected from Mg, Co, Ni, V, Al and Ti.
In the invention, the ratio of the fluorine-containing ion compound to the phosphate positive electrode material is 0.1: 100-10: 100, preferably 1:100 to 5: 100.
In the invention, the sintering temperature is 80-800 ℃, preferably 100-600 ℃ and most preferably 200-400 ℃.
In the invention, optionally, the pH value of the cathode material is reduced by 0.2-0.5;
in the invention, optionally, the in-situ generated fluorine-containing ion compound coated positive electrode material can be used as a positive electrode material in a lithium ion battery taking an organic solvent or an aqueous solution as an electrolyte, and can also be used as a positive electrode material in a lithium ion battery adopting a solid electrolyte.
According to a fourth aspect of the present application, there is provided a lithium ion battery characterized by comprising the positive electrode material of the present invention.
Optionally, the lithium ion battery comprises at least one of an organic solvent electrolyte, an aqueous electrolyte, and a solid electrolyte.
According to an embodiment of the present invention, there is provided a composite electrode material including an electrode material and a clad layer; the coating comprises at least one of the fluoride ion-containing compounds of the present invention.
In one embodiment, the coating layer is LiF.
In one embodiment, the pH value of the composite electrode material in water is 11.5-11.8.
According to an embodiment of the present application, there is provided a method of preparing a composite electrode material, including the steps of:
uniformly mixing raw materials containing a fluorine source and an electrode material, grinding, heating to 80-800 ℃, preserving heat for 0.5-20 h, and cooling to room temperature to obtain the composite electrode material.
The invention has the following beneficial effects:
1) according to the composite electrode material provided by the invention, the fluorine source can convert the surface by-product into the fluorine source coating layer in situ, and the structure of the material is not damaged;
2) according to the composite electrode material provided by the application, the fluorine source (such as LiF) is used, so that the electrochemical performance of the cathode material is greatly improved;
3) according to the composite electrode material provided by the application, after the surface of the anode material is coated with the inert substance, the direct contact between the electrolyte and the active material can be reduced, so that the side reaction with the electrolyte is reduced;
4) the preparation method of the composite electrode material provided by the application has the advantages of dry low-temperature treatment, simple process and environmental friendliness.
Drawings
Fig. 1 is a topographical view of a sample prepared in comparative example 1.
FIG. 2 is a topographical view of a sample prepared in example 1 of the present invention.
Fig. 3 is a graph of cycle performance for samples prepared in comparative example 1 and example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and equipment in the examples of the present application were purchased commercially.
Unless otherwise specified, the reaction in the present invention is carried out at normal temperature and pressure.
Main instrument
SEM morphology analysis was performed using an FEI field emission scanning electron microscope thermal field Quanta 250.
XPS spectroscopy was performed using the X-ray photoelectron spectrometer Axis Ultra DLD from Kratos, UK.
In the following examples, the heating rate was 5 ℃/min.
Comparative example 1
Untreated LiMn0.9Fe0.1PO4And C, material.
Comparative example 2
Untreated 0.9LiMnPO4-0.1LiFePO4C material
Example 1
Weighing 10g LiMn0.9Fe0.1PO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material/C into a muffle furnace, heating to 100 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 2
Weighing 10g LiMn0.9Fe0.1PO4Adding 2g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 100 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 3
Weighing 10g of LiMn0.9Fe0.1PO4Adding 5g of lithium fluoride into the material/C, grinding for 30min, putting the material/C into a muffle furnace, heating to 100 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 4
Weighing 10g LiMn0.9Fe0.1PO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 200 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 5
Weighing 10g of LiMn0.9Fe0.1PO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 300 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 6
Weighing 10g LiMn0.9Fe0.1PO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 400 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 7
Weighing 10g LiMn0.9Fe0.1PO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 500 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 8
Weighing 10g LiMn0.9Fe0.1PO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 600 ℃, and preserving heat for 0.5-8h to obtain LiMn0.9Fe0.1PO4the/C-LiF sample.
Example 9
Weighing 10g of 0.9LiMnPO4-0.1LiFePO4Adding 0.01g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 600 ℃, and preserving heat for 0.5-8h to obtain 0.9LiMnPO4-0.1LiFePO4the/C-LiF sample.
Example 10
Weighing 10g of 0.9LiMnPO4-0.1LiFePO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 500 ℃, and preserving heat for 0.5-8h to obtain 0.9LiMnPO4-0.1LiFePO4the/C-LiF sample.
Example 11
Weighing 10g of 0.9LiMnPO4-0.1LiFePO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 600 ℃, and preserving heat for 0.5-8h to obtain 0.9LiMnPO4-0.1LiFePO4the/C-LiF sample.
Example 12
Weighing 10g of 0.9LiMnPO4-0.1LiFePO4Adding 1g of lithium fluoride into the material/C, grinding for 30min, putting the material into a muffle furnace, heating to 700 ℃, and preserving heat for 0.5-8h to obtain 0.9LiMnPO4-0.1LiFePO4the/C-LiF sample.
Example 13 topography characterization
The materials prepared in comparative example 2 and example 9 were subjected to SEM test. Typical SEM pictures are shown in FIGS. 1 and 2, in which FIG. 1 is 0.9LiMnPO prepared in comparative example 24-0.1LiFePO4SEM picture of/C sample, FIG. 2 is 0.9LiMnPO prepared in example 94-0.1LiFePO4SEM image of/C-LiF sample. As can be seen from fig. 1 and 2, 0.9LiMnPO after LiF modification4-0.1LiFePO4The particle morphology of the/C sample is not substantially changed.
In the same manner, SEM tests were conducted on the materials prepared in examples 1 to 8 and 10 to 12. The SEM images obtained for each are similar to the results of FIG. 2 obtained for the material prepared in example 9.
Example 14 electrochemical Performance characterization
The materials obtained in comparative example 2 and example 9 of the invention are used as a positive electrode material, and are uniformly mixed with acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in a N-methyl pyrrolidone (NMP) solvent, the mass ratio of the positive electrode material to the conductive agent to the binder is 85:10:5, the uniformly mixed slurry is coated on an aluminum foil, and the aluminum foil is dried in vacuum at 120 ℃ for 12 hours to prepare the lithium ion battery positive electrode sheet.
The CR2032 type button lithium ion battery is assembled by using the battery positive plate as a positive electrode, using metal lithium as a negative electrode, adopting a solution of ethylene carbonate and dimethyl carbonate of 1mol/L lithium hexafluorophosphate as an electrolyte and adopting a polyethylene and polypropylene composite material with the thickness of 20 microns as a diaphragm.
Performing cycle performance test on the battery, wherein the charge-discharge voltage is 2.2-4.4V, the charge-discharge activation is performed for five weeks at 0.1C, and then the 1C charge and 1C discharge are performed for cycle;
and (3) carrying out rate performance test on the battery, wherein the charging and discharging voltage is 2.2-4.4V, and the charging and discharging cycles are respectively carried out by using 0.1C, 0.5C, 1C, 2C and 5C.
Typical cycle performance is shown in fig. 3, corresponding to comparative example 2 and inventive example 9. As can be seen from fig. 3, the cycle retention of the lithium fluoride-coated positive electrode material was significantly improved.
As can be seen from FIG. 3, the specific capacity of the material (0.9 LMP-0.1LFP/C-LiF in FIG. 3) prepared in example 9 of the present invention is 165mAh/g
According to the same manner, the electrochemical properties of the materials obtained in the embodiments 1-8 and 10-12 are characterized, and the measured electrical properties of the materials obtained in the embodiments 1-8 and 10-12 are similar to the electrochemical properties shown in the embodiment 9 in FIG. 3, and the specific capacity of the material is not less than 160 mAh/g.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A modified composite material is characterized by comprising an active substance and a fluorine source,
wherein the active substance is at least one selected from compounds having the formula shown in formula (I) and formula (II):
Li1-xAxMnyM1-yPO4/C (I)
wherein,
0≤x≤0.5，
a is at least one selected from Na, K and Mg,
y is not less than 0 and not more than 1, and
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti;
mLi1-aAaMnbM1-bPO4-nLi1-cAcFedN1-dO4/C (Ⅱ)
wherein,
0＜m＜1，
0≤a≤0.5，
a is at least one selected from Na, K and Mg,
0≤b≤1，
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti,
0＜n＜1，
0≤c≤0.5，
d is more than or equal to 0 and less than or equal to 1, and
n is at least one selected from Mg, Co, Ni, V, Al and Ti.
2. The modified composite material according to claim 1,
formula (I) wherein x is 0, y is 1 and M is Fe; and is
In formula (II), M is 0.9, a is 0, b is 1, M is Fe, n is 0.1, c is 0, and d is 1.
3. The modified composite of claim 1, wherein the fluorine source is selected from the group consisting of LiF, NaF, NaHF2、KF、KHF2、NH4HF2、NH4F、CaF2、MgF2、AlF3、ZnF2、CoF3、NiF2、MnF2、FeF2、BaF2、Na2SiF6、H2SiF6、SiF4At least one of (1).
4. The modified composite material according to claim 1, wherein the mass ratio of the fluorine source to the active material is 0.1:100 to 50: 100.
5. Process for the preparation of the modified composite according to any one of claims 1 to 4, characterized in that it comprises at least the following steps:
mixing raw materials containing a fluorine source and an active substance, heating to 80-800 ℃, preserving heat for 0.5-20 h to obtain a modified composite material,
wherein the active substance is at least one selected from compounds having the formula shown in formula (I) and formula (II):
Li1-xAxMnyM1-yPO4/C (I)
wherein,
0≤x≤0.5，
a is at least one selected from Na, K and Mg,
y is not less than 0 and not more than 1, and
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti;
mLi1-aAaMnbM1-bPO4-nLi1-cAcFedN1-dPO4/C (Ⅱ)
wherein,
0＜m＜1，
0≤a≤0.5，
a is at least one selected from Na, K and Mg,
0≤b≤1，
m is at least one selected from Mg, Fe, Co, Ni, V, Al and Ti,
0＜n＜1，
0≤c≤0.5，
d is more than or equal to 0 and less than or equal to 1, and
n is at least one selected from Mg, Co, Ni, V, Al and Ti.
6. The method of claim 5,
formula (I) wherein x is 0, y is 1 and M is Fe; and is
In formula (II), M is 0.9, a is 0, b is 1, M is Fe, n is 0.1, c is 0, and d is 1.
7. The method according to claim 5, wherein the heating rate is 1-10 ℃/min;
preferably, the heating ramp rate is 5 deg.C/min.
8. The method of claim 5,
grinding raw materials containing a fluorine source and an active substance, and heating;
the grinding time is 10-120 minutes.
9. A positive electrode material comprising the modified composite material according to any one of claims 1 to 4 or the modified composite material produced by the method according to any one of claims 5 to 8.
10. A lithium ion battery comprising the positive electrode material according to claim 8.
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