CN113764669B - Layered oxide positive electrode material of high-voltage sodium ion battery - Google Patents
Layered oxide positive electrode material of high-voltage sodium ion battery Download PDFInfo
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- CN113764669B CN113764669B CN202110969800.4A CN202110969800A CN113764669B CN 113764669 B CN113764669 B CN 113764669B CN 202110969800 A CN202110969800 A CN 202110969800A CN 113764669 B CN113764669 B CN 113764669B
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- sodium
- positive electrode
- lithium
- fluoride
- oxide
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 137
- 239000011734 sodium Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 150000001450 anions Chemical class 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 36
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 24
- 239000012071 phase Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 20
- 102000020897 Formins Human genes 0.000 description 14
- 108091022623 Formins Proteins 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy 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
- H01M4/36—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
High-voltage sodium ion battery layered oxide positive electrode material with general formula Na x Li a N b M c O 2‑y F y Wherein 0.4<x≤1；a+b+c＝1；0<y<0.2. The invention is characterized in that Li is introduced into a metal layer of a layered oxide + At the same time introducing F into the oxygen layer of the layered oxide ‑ ，Li + And F ‑ The co-introduction of the material can not only improve the structural stability of the material, promote the sodium ion transmission rate and improve the multiplying power performance of the material, but also excite the reversible oxidation reduction of the anion oxygen of the material in the high-voltage charge-discharge process, thereby effectively improving the energy density and the power density of the material.
Description
Technical Field
The invention relates to a positive electrode material of a sodium ion battery and a preparation method thereof.
Background
With the continuous development of society and economy, the demand for energy by human beings is gradually increasing. Traditional fossil energy belongs to non-renewable energy, and excessive development leads to exhaustion of fossil energy on one hand and serious environmental pollution on the other hand. Therefore, developing clean, efficient, convenient, and abundant energy storage means to relieve energy and environmental stress is an important approach to achieve sustainable development for humans. In recent years, sodium ion batteries are popular among various domestic and foreign enterprises and researchers as an efficient and environment-friendly energy storage mode. And the sodium resource is widely distributed, the crust content is rich, the price is low, and the method is very suitable for large-scale energy storage application.
Similar to the composition of lithium ion batteries, sodium ion batteries also consist of a positive electrode material, a negative electrode material, a separator, and an electrolyte. The electrode material is an important component of the battery and plays a decisive role in the performance of the sodium ion battery. The positive electrode material of the sodium ion battery mainly comprises layered transition metal oxide, polyanion material, prussian blue analogues and an organic positive electrode. The layered transition metal oxide positive electrode material has wide sources and reversible ion extraction and intercalation capability, is widely used for researching the secondary battery positive electrode material, and is the most hot research object. However, the layered oxide cathode material has various problems such as low capacity, poor structural stability, poor cycle performance, and the like. The energy density and the power density of the battery can be effectively improved by improving the charge cut-off voltage of the battery. However, increasing the charge cutoff voltage of the battery can lead to irreversible phase changes and structural collapse of the material, which in turn can lead to a significant reduction in the cycle life of the battery. The usual P2 phase structure will be transformed into an O2 phase structure and the O3 phase structure will be transformed into a P3 phase structure. In addition, the layered positive electrode material can generate irreversible oxygen oxidation and reduction during high-voltage charge and discharge, and the surface releases gas, so that the crystal structure is deteriorated, and the potential safety hazard problem is brought.
Disclosure of Invention
The invention aims to provide a high-voltage sodium ion electric layered anode material which at least can solve the problems of low energy density, poor cycle performance and the like of the existing sodium ion battery anode material.
According to a first aspect of the present invention, there is provided a layered oxide cathode material for sodium ion batteries having a general structural formula of Na x Li a N b M c O 2-y F y Wherein 0.4<x≤1；a+b+c＝1；0<y<0.2; wherein M is a variable valence metal selected from at least one of Ni, mn, fe, co, cu, V and Cr; n is an unchangeable metal selected from Ti, mg, zn, K, al, ca, ru, nb, ir, mo, andat least one of Zr. The general formula overall satisfies the neutrality or assumes a zero valence state.
The invention introduces negative and positive ions Li into the layered positive electrode material + And F - The method solves the problems existing in the high-voltage charge and discharge process of the layered anode material of the sodium ion battery. Wherein Li is introduced into the metal layer of the layered oxide + The oxidation-reduction reaction of anionic oxygen is excited by the non-bonding state effect between Li-O to improve the energy density and power density of the layered positive electrode material, and F is introduced into the oxygen layer of the layered oxide - ，F - The electron density of the oxygen layer can be concentrated, and the oxygen redox reversibility at high voltage can be improved. Li (Li) + And F - The mutual introduction of the composite material can regulate and control the layer-to-layer spacing of the transition metal layer and the sodium layer, so that the layer-to-layer spacing of the transition metal layer of the obtained layered oxide anode material is reduced, and the layer-to-layer spacing of the sodium layer is increased. The structural stability of the material is improved, the sodium ion transmission rate is promoted, and the rate capability of the material is improved.
The positive electrode material according to the present invention, wherein M preferably contains at least one of Ni, fe, and Mn.
The positive electrode material according to the present invention is preferably 0.6< x <0.9 and 0.05< y <0.15.
The positive electrode material according to the present invention is preferably 0.05< a <0.15,0.05< b <0.15.
The positive electrode material according to the present invention is basically a sheet-like particle having a particle diameter of 1 to 5. Mu.m. The positive electrode material of the present invention has a stable layered structure. By utilizing anions and cations Li + And F - The doping means stabilizes the reversible oxidation reduction of the material by anionic oxygen in a high voltage region, and obviously improves the energy density and the power density of the material.
According to a second aspect of the present invention, there is provided a method for producing the above-described positive electrode material, comprising:
providing a sodium source material selected from at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium nitrate, sodium oxide, sodium peroxide, and sodium fluoride;
providing an M source material selected from at least one of an oxide, carbonate, hydroxide, fluoride, nitrate and hydrated compounds thereof, and acetate and hydrated compounds thereof of M;
providing an N source material selected from at least one of an oxide, carbonate, hydroxide, fluoride, nitrate and hydrated compounds thereof, and acetate and hydrated compounds thereof of N;
providing a lithium source material selected from at least one of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium nitrate, lithium oxide, lithium peroxide, and lithium fluoride;
providing a fluorine source material selected from at least one of lithium fluoride, sodium fluoride, M fluoride, N fluoride;
ball-milling and uniformly mixing the source materials according to the stoichiometric ratio determined by the structural general formula to form a mixture; and
calcining the mixture and cooling to room temperature to form a positive electrode material, wherein the calcining temperature is 400-1200 ℃, the heat preservation time is 2-24 h, and the heating rate is 1-10 ℃/min; the cooling rate is 1-10 ℃/min during cooling.
According to the invention, the actual proportion of the sodium source material is preferably higher than the stoichiometric proportion thereof during ball-milling mixing, so as to compensate volatilization of the sodium source material at high temperature. The ratio of the actual proportion of the sodium source material to the stoichiometric ratio is preferably (1-1.1): 1.
according to the present invention, the ball-milling mixing time is preferably 1 to 30 hours, more preferably 1 to 3 hours, and the rotational speed of the ball mill is 200 to 1000rpm, more preferably 300 to 600rpm.
According to the invention, the calcination temperature is preferably 900-1000 ℃; the calcination time is 10-16h. The calcination atmosphere is preferably air.
According to still another aspect of the present invention, there is also provided a positive electrode for a sodium ion battery, comprising a current collector and a positive electrode coating material coated on the current collector, wherein the positive electrode coating material has a coating thickness of 50 to 400 μm and a composition of:
the positive electrode material: 60 to 90 wt%;
conductive carbon black: 5 to 20 wt%; and
and (2) a binder: 5 to 20 weight percent.
The binder may be, for example, polyvinylidene fluoride.
According to the invention, the positive electrode can be assembled into a full-cell or half-cell sodium ion cell. For testing the electrical properties of the battery electrode material, half-cells may be used for testing. The half-cell can be assembled in a glove box filled with argon, and comprises a counter electrode, a diaphragm and an electrolyte, wherein the counter electrode is made of metal sodium sheet, the diaphragm has the function of avoiding the short circuit of the cell caused by direct contact between the anode and the cathode, for example, gelgard 2400 glass fiber can be adopted, and the electrolyte can be electrolyte commonly used in the field, for example, naPF 6 Or NaClO 4 Propylene carbonate solution of (a). The electrode of the sodium ion battery assembled according to the invention has higher specific charge-discharge capacity and capacity retention rate, and can realize rapid charge-discharge under high current density.
In summary, the present invention has the following advantages.
Firstly, the invention provides a layered oxide positive electrode material of a sodium ion battery, which is prepared by introducing positive and negative ions Li + And F - The interlayer distance of the transition metal is reduced, the crystal structure is stabilized, and the precipitation of the transition metal is relieved; the interlayer spacing of the sodium layer is increased, the rapid transmission of sodium ions is facilitated, and the rate capability of the battery is improved.
In addition, the layered oxide positive electrode material has the stability of reversible charge and discharge under higher voltage, and the anion oxygen redox provides additional capacity under high voltage, so that the working voltage, the energy density and the power density of the battery are effectively increased.
Finally, the preparation method provided by the invention is simple to operate, strong in repeatability, wide in raw material sources, mild in reaction conditions, low in cost and capable of realizing large-scale industrial production.
Drawings
FIG. 1 is an X-ray powder diffraction test chart of example 1 of the present invention;
FIG. 2 is a scanning electron microscope test chart of the powder prepared in example 1 of the present invention;
FIG. 3 is an X-ray powder diffraction test chart of example 2 of the present invention;
FIG. 4 is a graph showing a transmission electron microscope test of the powder prepared in example 2 of the present invention; and
FIG. 5 is a scanning electron microscope test chart of the powder prepared in example 2 of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Example 1
(1) Preparation of O3-NaLi 0.1 Fe 0.4 Mn 0.5 O 1.9 F 0.1 Layered positive electrode material: mixing 2.1mmol of sodium carbonate, 0.2mmol of lithium fluoride, 1.6mol of ferrous oxide and 2mol of manganese oxide, placing the mixture in a ball milling tank, and filling Ar gas shielding gas in the ball milling tank, wherein the ball material ratio is 40:1, the rotating speed of the ball mill is 600rpm, the running time is 120min, and four materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace, calcining at a temperature rising speed of 5 deg.C for min -1 The temperature is 900 ℃, the heat preservation time is 16 hours, and the mixture is cooled to the room temperature; the calcined material is ground into a powder.
XRD testing of the powder material produced, as shown in FIG. 1, can find that the material exhibits a pure O3 phase, the space group is R-3m (166), and the microscopic morphology of the material is micron-sized particles, as shown in FIG. 2. The prepared positive electrode material, binder and conductive agent are prepared according to the following ratio of 7:2:1, coating the mixture on an aluminum foil with a coating thickness of 200 mu m, and drying the cut pieces.
The battery is assembled in a glove box filled with argon atmosphere, the cut pole piece is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, and 1M NaClO is used as a diaphragm 4 The PC solution is dissolved as electrolyte. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 171mAh g -1 。
Comparative example 1
(1) Preparation of O3-NaFe 0.5 Mn 0.5 O 2 Layered positive electrode material: mixing 2.1mmol of sodium carbonate, 2mol of ferrous oxide and 2mol of manganese oxide, placing the mixture in a ball milling tank, filling Ar gas shielding gas in the ball milling tank, and the ball material ratio is 40:1, the rotating speed of the ball mill is 600rpm, the running time is 120min, and three materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 5 deg.C for min -1 The temperature is 900 ℃, the heat preservation time is 16 hours, and the mixture is cooled to the room temperature; the calcined material is ground into a powder.
XRD testing was performed on the prepared powder material, the synthesized material showed a pure-phase O3 phase, the space group was R-3m (166), and the microscopic morphology of the material was micron-sized amorphous particles. A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 1. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 86mAh g -1 。
Example 2
(1) Preparation of P2-Na 0.8 Li 0.12 Ni 0.22 Mn 0.66 O 1.92 F 0.08 Layered positive electrode material: mixing 0.42mmol of sodium carbonate, 0.08mmol of lithium fluoride, 0.08mmol of lithium carbonate, 0.22mol of nickel oxide and 0.66mol of manganese oxide, and placing in a ball milling tank, wherein the ball-material ratio is 60:1, the rotating speed of the ball mill is 450rpm, the running time is 60min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 5 deg.C for min -1 The temperature is 950 ℃, the heat preservation time is 12 hours, the cooling speed is 1 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcined material is ground into a powder.
XRD testing of the powder material produced, as shown in FIG. 3, can find that the material exhibits a pure phase P2 phase, and the space group is P 63 And/mmc, the material can be seen to be a layered single crystal structure by transmission electron microscopy, as shown in FIG. 4. SEM test characterization found that the material had a microscopic morphology of micron-sized particles, as shown in figure 5. The prepared positive electrode material, binder and conductive agent are mixed according to the following proportion of 8:1: ratio of 1Mixing, coating on aluminum foil with thickness of 250 μm, and oven drying.
The battery is assembled in a glove box filled with argon atmosphere, the cut pole piece is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, and 1M NaClO is used as a diaphragm 4 The PC solution is dissolved as electrolyte. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.3V, and the reversible capacity of the material after 20 weeks of circulation is 122mAh g -1 。
Comparative example 2
(1) Preparation of P2-Na 0.8 Ni 0.34 Mn 0.66 O 2 Layered positive electrode material: mixing 0.42mmol of sodium carbonate, 0.34mol of nickel oxide and 0.66mol of manganese oxide, and placing the mixture in a ball milling tank, wherein the ball material ratio is 60:1, the rotating speed of the ball mill is 450rpm, the running time is 60min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 5 deg.C for min -1 The temperature is 950 ℃, the heat preservation time is 12 hours, the cooling speed is 1 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcined material is ground into a powder.
XRD testing of the prepared powder material can find that the material presents a pure phase P2 phase, and the space group is P 63 And/mmc, wherein the microstructure of the material is micron-sized particles. A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 2. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.3V, and the reversible capacity of the material after 20 weeks of circulation is 73mAh g -1 。
Example 3
(1) Preparation of P2-Na 0.8 Li 0.3 Ni 0.2 Mn 0.5 O 1.7 F 0.3 Layered positive electrode material: mixing 0.42mmol of sodium carbonate, 0.3mmol of lithium fluoride, 0.2mol of nickel oxide and 0.5mol of manganese oxide, placing the mixture in a ball milling tank, filling Ar gas shielding gas in the ball milling tank, and the ball material ratio is 50:1, the rotating speed of the ball mill is 450rpm, the running time is 60min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 5 deg.C for min -1 The temperature is 950 ℃, the heat preservation time is 12 hours, the cooling speed is 1 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcined material is ground into a powder.
The material is P2 phase with pure phase, and the space group is P 63 And/mmc, wherein the microstructure of the material is micron-sized particles. A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 1. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.3V, and the reversible capacity of the material after 20 weeks of circulation is 105mAh g -1 。
Example 4
(1) Preparation of P2-Na 0.8 Li 0.08 Al 0.06 Ni 0.26 Fe 0.3 Mn 0.3 O 1.86 F 0.14 Layered positive electrode material: mixing 0.42mmol of sodium carbonate, 0.08mmol of lithium fluoride, 0.02mmol of aluminum fluoride, 0.26mol of nickel oxide, 0.3mol of ferrous oxide and 0.3mol of manganese oxide, and placing the mixture in a ball milling tank, wherein the ball material ratio is 60:1, the rotating speed of the ball mill is 650rpm, the running time is 200min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 5 deg.C for min -1 The temperature is 1000 ℃, the heat preservation time is 16 hours, the cooling speed is 5 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcined material is ground into a powder.
The material is P2 phase with pure phase, and the space group is P 63 And/mmc, wherein the microstructure of the material is micron-sized particles. A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 2. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 162mAh g -1 。
Example 5
(1) Preparation of O3-NaLi 0.2 Mn 0.8 O 1.88 F 0.12 Layered positive electrode material: taking 0.55mmol of sodium carbonate and 0.12mmol of lithium fluorideMixing 0.04mmol of lithium carbonate and 0.8mol of manganese oxide, placing the mixture in a ball milling tank, filling Ar gas shielding gas in the ball milling tank, and the ball material ratio is 60:1, the rotating speed of the ball mill is 300rpm, the running time is 300min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 5 deg.C for min -1 The temperature is 950 ℃, the heat preservation time is 20 hours, and the mixture is cooled to room temperature; the calcined material is ground into a powder.
The prepared material shows a pure-phase O3 phase, the space group is R-3m (166), and the microstructure of the material is micron-sized particles. A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 1. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 168mAh g -1 。
Example 6
(1) Preparation of O3-NaLi 0.1 Co 0.3 Ni 0.2 Mn 0.4 O 1.9 F 0.1 Layered positive electrode material: mixing 0.55mmol of sodium carbonate, 0.1mmol of lithium fluoride, 0.1mmol of cobaltosic oxide, 0.2mmol of nickel oxide and 0.5mol of manganese oxide, and placing the mixture in a ball milling tank, wherein the ball material ratio is 50:1, the rotating speed of the ball mill is 800rpm, the running time is 100min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 2deg.C for min -1 The temperature is 900 ℃, the heat preservation time is 16 hours, and the mixture is cooled to the room temperature; the calcined material is ground into a powder.
A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 1. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 177mAh g -1 。
Example 7
(1) Preparation of P2-Na 0.6 Li 0.05 Mg 0.05 Ni 0.2 Fe 0.2 Mn 0.5 O 1.85 F 0.15 Layered positive electrode material: mixing 0.31mmol of sodium carbonate, 0.05mmol of lithium fluoride, 0.05mmol of magnesium fluoride, 0.2mol of nickel oxide, 0.2mol of ferrous oxide and 0.5mol of manganese oxide, and placing the mixture in a ball milling tank, wherein the ball material ratio is 30:1, the rotation speed of a ball mill is 350rpm, the running time is 150min, and a plurality of materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 2deg.C for min -1 The temperature is 900 ℃, the heat preservation time is 22 hours, the cooling speed is 2 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcined material is ground into a powder.
A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 2. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 1.5-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 192mAh g -1 。
Example 8
(1) Preparation of O3-NaLi 0.25 Fe 0.25 Mn 0.5 O 1.7 F 0.3 Layered positive electrode material: 1.mmol of sodium carbonate, 0.25mmol of lithium fluoride, 0.05mmol of sodium fluoride, 0.25mol of ferrous oxide and 0.5mol of manganese oxide are taken, mixed and placed in a ball milling tank, and the ball-material ratio is 20:1, the rotating speed of the ball mill is 200rpm, the running time is 400min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 1 deg.C for min -1 The temperature is 950 ℃, the heat preservation time is 18 hours, the cooling speed is 1 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcined material is ground into a powder.
A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 1. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 1.5-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 187mAh g -1 。
Example 9
(1) Preparation of O3-NaLi 0.2 Mn 0.8 O 1.88 F 0.12 Layered positive electrode material: 0.55mmol of sodium carbonate,Mixing 0.12mmol of lithium fluoride, 0.04mmol of lithium carbonate and 0.8mol of manganese oxide, placing the mixture in a ball milling tank, filling Ar gas shielding gas in the ball milling tank, and the ball material ratio is 60:1, the rotating speed of the ball mill is 300rpm, the running time is 300min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 1 deg.C for min -1 The temperature is 950 ℃, the heat preservation time is 20h, and the temperature is reduced by 1 ℃ for min -1 Cooling to room temperature; the calcined material is ground into a powder.
The prepared material shows a pure-phase O3 phase, the space group is R-3m (166), and the microstructure of the material is micron-sized particles. A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 1. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 179mAh g -1 。
Example 10
(1) Preparation of O3-NaLi 0.2 Mn 0.8 O 1.88 F 0.12 Layered positive electrode material: mixing 0.55mmol of sodium carbonate, 0.12mmol of lithium fluoride, 0.04mmol of lithium carbonate and 0.8mol of manganese oxide, and placing the mixture in a ball milling tank, wherein the ball material ratio is 40:1, the rotating speed of the ball mill is 200rpm, the running time is 30min, and several materials are fully mixed;
(2) Placing the above mixed materials in a muffle furnace for calcination, and heating at 1 deg.C for min -1 The temperature is 950 ℃, the heat preservation time is 20h, and the temperature is reduced by 1 ℃ for min -1 Cooling to room temperature; the calcined material is ground into a powder.
A sodium ion battery pole piece and assembled sodium ion half-cell were prepared according to the protocol in example 2. The assembled battery is subjected to constant current charge and discharge test in a blue electric test system, and the current density is 50mA g -1 The voltage interval is 2-4.5V, and the reversible capacity of the material after 20 weeks of circulation is 114mAh g -1 。
Table 1 shows the electrochemical performance comparison of examples 1 to 5 and comparative examples 1 to 2
TABLE 1
As shown in Table 1, comparing example 1 and comparative example 1 with example 2 and comparative example 2, it can be found that an anion and a cation Li are introduced into the metal layer of the layered oxide + And F - The anion oxygen oxidation-reduction reaction of the material in a high voltage region is effectively excited, the additional reversible specific capacity is provided, and the energy density and the power density of the material are improved. At the same time Li + And F - The introduction of the material can relieve the irreversible phase structure transformation of the material in a high voltage range, inhibit the dissolution and precipitation of transition metal, stabilize the crystal structure, and further improve the cycling stability of the material while realizing high energy density. After the material is assembled into a sodium ion battery, the material is at 50mA g -1 Is cycled for 20 weeks at a current density of (C) and contains Li + And F - The achievable reversible specific capacity of the material is obviously improved.
As can be seen by comparing example 2 with example 3, li in the material is further improved + And F - The reversible specific capacity of the material decays significantly after 20 weeks of cycling. Since Li is an electrochemically inert element, li replaces sites of active elements in the material, such as Ni, fe, and Co, reducing the content of active variable metals. Excessive Li substitution reduces the capacity provided by transition metal valence, and thus the reversible capacity of the material is reduced. Meanwhile, since Li only contains s orbitals, the bonding energy with oxygen is low, and excessive Li can influence the stability of the crystal structure of the material, so that the cycle performance of the material is reduced.
As can be seen from comparative examples 1-2 and examples 4-8, li + And F - The introduction of the material can not only improve the working voltage of the material, but also have stable crystal structure under higher working voltage, and meanwhile, the material has the following characteristics in a lower voltage range<2V) also have good structural stability.
Comparative examples 5 and 9 have found that the control of the calcination temperature, and the rate of temperature rise and the incubation time of the synthetically prepared process material can reduce the production of impurities into a layered structure of the pure phase. Meanwhile, the generation of oxygen vacancies in the material can be reduced by slow cooling, and a metastable state structure caused by the oxygen vacancies is avoided, so that the cycle performance is improved.
Comparative example 9 and example 10 show that the rotational speed and the working time of the solid phase ball milling method have a great influence on the electrochemical properties of the materials. The lower rotation speed of the ball mill is difficult to achieve the uniformity of the initial powder material, and meanwhile, the protective gas can avoid oxidation reaction of the metal oxide material during high-energy ball milling. Non-uniform mixed materials can hinder the formation of uniform layered structures, seriously compromising the stability of the material's crystal structure.
Claims (2)
1. Preparation method of layered oxide positive electrode material of sodium ion battery, wherein the positive electrode material has a structural general formula of Na x Li a N b M c O y2- F y Wherein 0.6<x<0.9；a+b+c=1，0.05<a<0.15, 0.05<b<0.15；0.05<y<0.15, M is a variable valence metal selected from at least one of Ni, mn, fe, co, cu, V and Cr, and N is an non-variable valence metal Mg, the method comprising:
providing a sodium source material selected from at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium nitrate, sodium oxide, sodium peroxide, and sodium fluoride;
providing an M source material selected from at least one of an oxide, carbonate, hydroxide, fluoride, nitrate and hydrated compounds thereof, and acetate and hydrated compounds thereof of M;
providing an N source material selected from at least one of an oxide, carbonate, hydroxide, fluoride, nitrate and hydrated compounds thereof, and acetate and hydrated compounds thereof of N;
providing a lithium source material selected from at least one of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium nitrate, lithium oxide, lithium peroxide, and lithium fluoride;
providing a fluorine source material selected from at least one of lithium fluoride, sodium fluoride, M fluoride, N fluoride;
ball-milling and uniformly mixing the source materials according to the stoichiometric ratio determined by the structural general formula to form a mixture, wherein the ball-milling and mixing time is 1-3h, and the rotating speed of the ball mill is 300-600 rpm;
calcining the mixture and cooling to room temperature to form a positive electrode material, wherein the calcining temperature is 900-1000 ℃, the heat preservation time is 10-16h, the heating rate is 1-10 ℃/min, and the calcining atmosphere is air; the cooling rate during cooling is 1-10 ℃/min; and
grinding the formed positive electrode material into lamellar particles with the particle size of 1-5 mu m,
wherein the actual ratio of the sodium source material is higher than the stoichiometric ratio and the ratio of the sodium source material to the stoichiometric ratio is not higher than 1.1 when ball-milling and mixing are performed.
2. The positive electrode for the sodium ion battery comprises a current collector and a positive electrode coating material coated on the current collector, wherein the coating thickness of the positive electrode coating material is 50-400 microns, and the composition is as follows:
a positive electrode material prepared according to the method of claim 1: 60-90 wt%;
conductive carbon black: 5-20 wt%; and
and (2) a binder: 5-20 wt%.
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