CN116344792B - High-capacity P3-phase sodium ion battery layered oxide positive electrode material, preparation and application thereof - Google Patents
High-capacity P3-phase sodium ion battery layered oxide positive electrode material, preparation and application thereof Download PDFInfo
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- CN116344792B CN116344792B CN202310609369.1A CN202310609369A CN116344792B CN 116344792 B CN116344792 B CN 116344792B CN 202310609369 A CN202310609369 A CN 202310609369A CN 116344792 B CN116344792 B CN 116344792B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 67
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 53
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 82
- 239000012071 phase Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 84
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 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 7
- 238000000498 ball milling Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 claims description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021572 Manganese(IV) fluoride Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 229910001627 beryllium chloride Inorganic materials 0.000 claims description 2
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 claims description 2
- 229910001633 beryllium fluoride Inorganic materials 0.000 claims description 2
- 229910001865 beryllium hydroxide Inorganic materials 0.000 claims description 2
- PPYIVKOTTQCYIV-UHFFFAOYSA-L beryllium;selenate Chemical compound [Be+2].[O-][Se]([O-])(=O)=O PPYIVKOTTQCYIV-UHFFFAOYSA-L 0.000 claims description 2
- BYTPBBQZQOLICY-UHFFFAOYSA-N fluoro hypofluorite manganese Chemical compound [Mn].FOF BYTPBBQZQOLICY-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000005486 organic electrolyte Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- KWKYNMDHPVYLQQ-UHFFFAOYSA-J tetrafluoromanganese Chemical compound F[Mn](F)(F)F KWKYNMDHPVYLQQ-UHFFFAOYSA-J 0.000 claims description 2
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 7
- 238000006467 substitution reaction Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000036961 partial effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 28
- 238000012512 characterization method Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011056 performance test Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 230000002427 irreversible effect Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- BBKXDHBLPBKCFR-FDGPNNRMSA-L beryllium;(z)-4-oxopent-2-en-2-olate Chemical compound [Be+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BBKXDHBLPBKCFR-FDGPNNRMSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 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 2
- 229920000447 polyanionic polymer Chemical class 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a high-capacity P3-phase sodium ion battery layered oxide anode material, and preparation and application thereof, and belongs to the technical field of sodium ion battery electrode materials. The chemical formula of the positive electrode material is abbreviated as P3-Na 0.6 Li 0.2 Be x Mn 0.8‑x/2 O 2 X is the mole percent of Be element, the value range of x is more than or equal to 0.05 and less than or equal to 0.5, and the hexagonal shape is regular. The invention adopts Be 2+ Partial substitution of Na 0.6 Li 0.2 Mn 0.8 O 2 Mn in (b) 4+ The problems of low energy density, poor cycle performance and poor rate performance of the layered oxide of the sodium ion battery are obviously improved. The method for preparing the positive electrode material by utilizing the solid-phase sintering method is simple to operate, and the P3-phase sodium ion battery layered oxide positive electrode material with uniformly distributed elements and regular shape is obtained, so that the positive electrode material shows excellent specific capacity and rate capability when being applied to sodium ion batteries.
Description
Technical Field
The invention relates to a high-capacity P3-phase sodium ion battery layered oxide anode material, and preparation and application thereof, and belongs to the technical field of sodium ion battery electrode materials.
Background
Energy is an important driving force for the development of the current society, and with the massive use of fossil fuels, the increasingly serious energy crisis and environmental pollution problems force people to pay attention to clean and efficient novel renewable energy sources. Considering that the novel renewable energy sources such as solar energy, wind energy and the like have the characteristics of intermittence and randomness, are greatly influenced by geographical factors, if the novel renewable energy sources are directly connected to a power grid, unstable frequency can cause a certain degree of impact on the power grid. Therefore, the development of safe and reliable energy storage systems is a key point in the development and utilization of them. Among the numerous energy storage technologies, electrochemical cell energy storage is widely used in our daily lives due to its excellent portability.
Lithium ion batteries, which are typical electrochemical batteries, have the advantages of high energy density, long cycle life, and the like, and are widely used in various portable electronic products. With rapid popularization of new energy automobiles driven by lithium ion batteries, the problem of lithium resource shortage is increasingly prominent, and the lithium ion batteries cannot meet the annual growing large-scale energy storage demands. Sodium and lithium have similar physical and chemical properties, sodium reserves are rich (crust abundance is 2.83%, 6 th position) and sodium ion batteries with resource and price advantages are considered as potential substitutes of lithium ion batteries, and have great application prospects in large-scale energy storage.
In sodium ion batteries, the positive electrode material provides an active sodium ion and high potential redox couple, playing a critical role in determining the operating voltage and reversible capacity of the battery. At present, common positive electrode materials of sodium ion batteries mainly comprise layered transition metal oxides, prussian blue analogues, polyanion compounds, tunnel oxides and the like. Compared with materials such as Prussian blue analogues, polyanion compounds, tunnel oxides, and the like, layered transition metal oxides (Na x TMO 2 ) Exhibits higher specific capacity and meets the requirement of high energy density. But at the same time, since the specific capacity of the conventional layered oxide cathode material is mainly dependent on charge compensation of the cationic redox reaction, this results in a very significant difference in specific capacity compared to lithium ion batteries. To break this limitation, anionic redox has been proposed, and the studies that have been published so far have been mainly focused on electrochemical performance of layered oxide cathodes based on anionic redox reactions, which can remarkably widen the voltage and increase the battery capacity. For example, goodenough et al reported a P3-Na 0.6 [Li 0.2 Mn 0.8 ]O 2 Experiments show that O participates in high-potential oxidation-reduction reaction, a pair of reversible oxidation-reduction platforms are arranged between 3.5 and 4.5V, but a series of problems also occur along with the oxidation-reduction of O element, wherein the foremost point is that lattice O is easy to become unstable and forms (O after contributing too many electrons 2 ) n- Dimers even O 2 Molecules, which cause irreversible loss of oxygen and derivative structural rearrangements, seriously affect the stability of the material.
Disclosure of Invention
For the current P3-Na 0.6 [Li 0.2 Mn 0.8 ]O 2 The invention provides a high-capacity P3 phase sodium ion battery layered oxide anode material, preparation and application thereof, which adopts Be 2+ Partial substitution of Na 0.6 Li 0.2 Mn 0.8 O 2 Mn in (b) 4+ ，Be 2+ Is added with improved Na + The transmission dynamics of the material is improved; meanwhile, be enters the transition metal layer to form a covalent bond with O, so that excessive loss of O is effectively inhibited, charge compensation substitution among Mn/O is promoted, and capacity loss caused by irreversible oxygen release in the circulation process is compensated; furthermore Be 2+ The doping of the material can also effectively inhibit the phase change of the material in a high-voltage stage, so that the problems of low energy density, poor cycle performance and poor multiplying power performance of the layered oxide of the sodium ion battery are obviously improved, and the material has good application prospect in the field of sodium ion batteries; the solid-phase sintering method is used for preparing the positive electrode material, the operation is simple, and the P3-phase sodium ion battery layered oxide positive electrode material with uniformly distributed elements and regular shape is obtained, and the positive electrode material which is used as a positive electrode active material and applied to a sodium ion battery shows excellent specific capacity and rate capability.
The aim of the invention is achieved by the following technical scheme.
High-capacity P3-phase sodium ion battery layered oxide positive electrode material, wherein chemical formula of positive electrode material is abbreviated as P3-Na 0.6 Li 0.2 Be x Mn 0.8-x/2 O 2 X is the mole percent of Be element, the value range of x is more than or equal to 0.05 and less than or equal to 0.5, and the hexagonal shape is regular.
Further, x=0.2 to 0.4.
The preparation method of the layered oxide cathode material of the high-capacity P3-phase sodium ion battery specifically comprises the following steps:
mixing a sodium source, a lithium source, a beryllium source and a manganese source according to stoichiometric ratio (namely, stoichiometric ratio of Na, li, be and Mn elements according to 0.6:0.2:x (0.8-x/2)) and adding an organic solvent, and uniformly mixing to obtain slurry; removing the organic solvent in the slurry, and grinding to obtain precursor powder; and (3) placing the precursor powder into a furnace, performing solid-phase sintering in an air atmosphere, sintering at 600-750 ℃ for 12-24 hours, cooling, and grinding the sintered product to obtain the sodium ion battery layered oxide positive electrode material with good powder crystallinity and uniform distribution.
Further, the sodium source is at least one selected from sodium carbonate, sodium bicarbonate, sodium nitrate and sodium fluoride; the lithium source is at least one selected from lithium carbonate, lithium hydroxide, lithium hexafluorophosphate, lithium perchlorate, lithium nitrate and organic electrolyte lithium salt; the beryllium source is at least one selected from beryllium oxide, beryllium hydroxide, beryllium fluoride, beryllium chloride and organic electrolytic beryllium salt; the manganese source is selected from one of manganese dioxide, manganese tetrafluoride and manganese oxyfluoride.
Further, the organic solvent is acetone, methanol, ethyl acetate, N-dimethylformamide or dimethyl sulfoxide.
Further, a ball milling method is adopted for mixing, ball milling is carried out for 8-12 hours at the rotating speed of 400-800 r/min, and the evenly mixed slurry is obtained.
Further, placing the slurry in a forced air drying oven, drying at 80-120 ℃ for 3-5 hours, and then grinding to obtain precursor powder.
Further, heating to 600-750 ℃ at a heating rate of 1-5 ℃/min, and cooling at a cooling rate of 1-5 ℃/min after sintering.
The application of the high-capacity P3-phase sodium ion battery layered oxide positive electrode material is that the positive electrode material is used as an active substance to be applied to a positive electrode of a sodium ion battery, and the positive electrode is a current collector (such as common aluminum foil) coated with conductive paste, wherein the conductive paste is prepared from the active substance, a conductive agent (such as common conductive carbon black, acetylene black, graphene, carbon nano tube or chopped carbon fiber and the like) and an adhesive (such as common polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber or sodium alginate and the like).
The beneficial effects are that:
(1) Compared with the currently disclosed O3 phase and P2 phase layered oxides, the P3 phase sodium ion battery layered oxide containing Be has more stable structure and higher sodium ion mobility. The lithium element can effectively activate the oxidation reduction of oxygen element under high voltage, and the capacity of the layered oxide is obviously improved. The invention innovatively selects Be element to replace part of Mn element, and has the following main benefits:
① Be 2+ the addition of the positive electrode material can enlarge the c-axis distance, provide a better transmission channel for sodium ions, increase the kinetics of ion transmission, improve the electrochemical activity of the positive electrode material and further improve the capacity;
(2) be atoms can form a strong covalent bond with O after entering the transition metal layer, and the excessive oxidation reduction of O element is limited in the battery cycle process, the average valence state of Mn element is indirectly promoted to Be reduced due to charge balance, and the dominant Mn is represented by Mn at the moment 4+ Becomes Mn 3+ And more Mn 3+ Can replace O to generate oxidation-reduction reaction in the subsequent circulation process, and can be used for Na + The intercalation and deintercalation of the Mn/O complex is subjected to charge compensation, so that the Be element effectively excites charge compensation substitution among Mn/O, and the capacity loss caused by irreversible oxygen release in the circulation process is compensated;
③ Be 2+ the doping of the material can effectively inhibit the transition of the material from P3 phase to X phase to Y phase in the high voltage phase, thereby improving the circulation stability of the material.
(2) The invention explores P3-Na 0.6 Li 0.2 Be x Mn 0.8-x/2 O 2 Influence of Be doping amount x in series materials on electrochemical performance of materials, and sodium-ion battery capacity assembled by using the materials as positive electrodes is compared with that of P3-Na without being doped with Be 0.6 Li 0.2 Mn 0.8 O 2 The (abbreviated as NLMO) material has a remarkable improvement, and the capacity tends to be increased and then reduced with the increase of the doping proportion.
(3) The invention can synthesize the layered oxide positive electrode material of the P3-phase sodium ion battery with good crystallinity by adopting a solid-phase sintering method in one step, does not need additional annealing treatment, has simple preparation method operation and is easy to realize large-scale production.
Drawings
Fig. 1 is a comparative graph of X-ray diffraction patterns (XRD) of the positive electrode materials prepared in example 1, example 2, example 4, example 7 and comparative example 1.
Fig. 2 is a comparative view of Scanning Electron Microscope (SEM) images of the positive electrode materials prepared in example 1, example 2, example 4, and example 7; wherein (a) is Na prepared in example 2 0.6 (Li 0.2 Be 0.05 Mn 0.775 )O 2 (b) is Na prepared in example 4 0.6 (Li 0.2 Be 0.15 Mn 0.725 )O 2 (c) is Na prepared in example 1 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 (d) is Na prepared in example 7 0.6 (Li 0.2 Be 0.35 Mn 0.625 )O 2 SEM images of (a).
Fig. 3 is a graph showing the comparison of the rate performance of batteries assembled by using the positive electrode materials prepared in examples 1 to 8 and comparative example 1, respectively.
Fig. 4 is a scanning electron microscope image of the positive electrode material prepared in comparative example 1.
Detailed Description
The present invention will be further described with reference to the following detailed description, wherein the processes are conventional, and wherein the starting materials are commercially available from the open market, unless otherwise specified.
In the following examples, the specific steps of battery assembly are as follows: the positive electrode material prepared in the example or the comparative example, conductive carbon black (SuperP) and polyvinylidene fluoride (PVDF) are weighed according to the mass ratio of 7:2:1, N-methyl pyrrolidone (NMP) is taken as a solvent, the mixture is fully ground into uniform slurry in a mortar, a scraper is used for uniformly smearing the slurry on an aluminum foil, the aluminum foil is dried at 80 ℃ for 12h under a vacuum environment, and a cutting machine is used for cutting into slices, so that the slices are taken as positive electrodes; in addition, metal sodium sheet is used as negative electrode, glass fiber (Whatman GF/C) is used as diaphragm, CR2032 type stainless steel battery shell is selected, 1mol/L sodium perchlorate (NaClO) is selected as electrolyte 4 ) Dissolve in Polycarbonate (PC) and add 5vol% fluoroethylene carbonate (FEC); and (3) assembling the battery in a glove box filled with argon and with water and oxygen values lower than 0.1ppm, and performing electrochemical test by taking the mass of the positive electrode material as the mass of the active substance, wherein the test temperature is 25 ℃, the test electrochemical window is 2.0-4.5V, and 1C= 185.78 mAh/g.
Example 1
High-capacity P3-phase sodium ion battery layered oxide positive electrode material Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 The specific preparation steps of (a) are as follows:
(1) Mixing sodium carbonate, lithium hydroxide, beryllium acetylacetonate and manganese dioxide according to the molar ratio of Na to Li to Be of Mn=0.6 to 0.2 to 0.25 to 0.675, adding 7 mL acetone, transferring into a planetary ball mill, and ball-milling at a rotating speed of 500r/min for 12h to obtain mixed slurry;
(2) Putting the mixed slurry obtained in the step (1) into a blast drying oven, drying at 80 ℃ for 5 h, and grinding to obtain precursor powder;
(3) Transferring the precursor powder obtained in the step (2) into a crucible, putting into a muffle furnace, heating to 700 ℃ at a heating rate of 4 ℃/min, sintering at the temperature of 700 ℃ under an air atmosphere for 24h, and cooling to room temperature at a cooling rate of 4 ℃/min to obtain the anode material Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 The phase characterization was performed and the test results are shown in fig. 1.
For the prepared Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 The topography was characterized and the test results are shown in fig. 2 (c).
The prepared Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Example 2
Based on the example 1, except that the molar ratio of Na to Li to Be to Mn is modified from 0.6:0.2:0.25:0.675 to 0.6:0.2:0.05:0.775, other steps and preparation conditions are the same as in the example 1, and accordingly, the high-capacity P3-phase sodium-ion battery layered oxide cathode material Na is obtained 0.6 (Li 0.2 Be 0.05 Mn 0.775 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.05 Mn 0.775 )O 2 The phase characterization was performed and the test results are shown in fig. 1.
For the prepared Na 0.6 (Li 0.2 Be 0.05 Mn 0.775 )O 2 Characterization of the morphology was performed, and the test results are shown in FIG. 2 (a)
The prepared Na 0.6 (Li 0.2 Be 0.05 Mn 0.775 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Example 3
Based on the example 1, except that the molar ratio of Na to Li to Be to Mn is modified from 0.6:0.2:0.25:0.675 to 0.6:0.2:0.1:0.75, other steps and preparation conditions are the same as those of the example 1, and accordingly the high-capacity P3-phase sodium-ion battery layered oxide positive electrode material Na is obtained 0.6 (Li 0.2 Be 0.1 Mn 0.75 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.1 Mn 0.75 )O 2 According to the test result, the prepared positive electrode material has good crystallinity, corresponds to PDF card #54-0839, and is in tetragonal symmetry index with the R3m space group, and other impurity phases are not detected.
For the prepared Na 0.6 (Li 0.2 Be 0.1 Mn 0.75 )O 2 And carrying out morphology characterization, wherein the prepared positive electrode material has regular hexagonal morphology, contains fewer impurities, and the regular morphology is beneficial to enhancing the structural integrity in the electrode circulation process.
The prepared Na 0.6 (Li 0.2 Be 0.1 Mn 0.75 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Example 4
Based on the example 1, except that the molar ratio of Na to Li to Be to Mn is modified from 0.6:0.2:0.25:0.675 to 0.6:0.2:0.15:0.725, other steps and preparation conditions are the same as those of the example 1, and accordingly the high-capacity P3-phase sodium-ion battery layered oxide positive electrode material Na is obtained 0.6 (Li 0.2 Be 0.15 Mn 0.725 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.15 Mn 0.725 )O 2 The phase characterization was performed and the test results are shown in fig. 1.
For the prepared Na 0.6 (Li 0.2 Be 0.15 Mn 0.725 )O 2 The topography was characterized and the test results are shown in fig. 2 (b).
The prepared Na 0.6 (Li 0.2 Be 0.15 Mn 0.725 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Example 5
Based on the example 1, except that the molar ratio of Na to Li to Be to Mn is modified from 0.6:0.2:0.25:0.675 to 0.6:0.2:0.2:0.7, other steps and preparation conditions are the same as those of the example 1, and accordingly the high-capacity P3-phase sodium-ion battery layered oxide positive electrode material Na is obtained 0.6 (Li 0.2 Be 0.2 Mn 0.7 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.2 Mn 0.7 )O 2 According to the test result, the prepared positive electrode material has good crystallinity, corresponds to PDF card #54-0839, and is in tetragonal symmetry index with the R3m space group, and other impurity phases are not detected.
For the prepared Na 0.6 (Li 0.2 Be 0.2 Mn 0.7 )O 2 Performing morphology characterization, and obtaining the prepared product according to the characterization resultThe positive electrode material has a regular hexagonal morphology with fewer impurities, and the regular morphology helps to enhance structural integrity during cycling of the electrode.
The prepared Na 0.6 (Li 0.2 Be 0.2 Mn 0.7 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Example 6
Based on the example 1, except that the molar ratio of Na to Li to Be to Mn is modified from 0.6:0.2:0.25:0.675 to 0.6:0.2:0.3:0.65, other steps and preparation conditions are the same as those of the example 1, and accordingly the high-capacity P3-phase sodium-ion battery layered oxide positive electrode material Na is obtained 0.6 (Li 0.2 Be 0.3 Mn 0.65 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.3 Mn 0.65 )O 2 According to the test result, the prepared positive electrode material has good crystallinity, corresponds to PDF card #54-0839, and is in tetragonal symmetry index with the R3m space group, and other impurity phases are not detected.
For the prepared Na 0.6 (Li 0.2 Be 0.3 Mn 0.65 )O 2 And carrying out morphology characterization, wherein the prepared positive electrode material has regular hexagonal morphology, contains fewer impurities, and the regular morphology is beneficial to enhancing the structural integrity in the electrode circulation process.
The prepared Na 0.6 (Li 0.2 Be 0.3 Mn 0.65 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Example 7
Based on the example 1, except that the molar ratio of Na to Li to Be to Mn is modified from 0.6:0.2:0.25:0.675 to 0.6:0.2:0.35:0.625, other steps and preparation conditions are the same as in the example 1, and accordingly a high-capacity P3-phase sodium-ion battery layered oxide positive electrode material Na is obtained 0.6 (Li 0.2 Be 0.35 Mn 0.625 )O 2 。
To the preparedPrepared Na 0.6 (Li 0.2 Be 0.35 Mn 0.625 )O 2 The phase characterization was performed and the test results are shown in fig. 1.
For the prepared Na 0.6 (Li 0.2 Be 0.35 Mn 0.625 )O 2 The topography was characterized and the test results are shown in fig. 2 (d).
The prepared Na 0.6 (Li 0.2 Be 0.35 Mn 0.625 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Example 8
Based on the example 1, except that the molar ratio of Na to Li to Be to Mn is modified from 0.6:0.2:0.25:0.675 to 0.6:0.2:0.4:0.6, other steps and preparation conditions are the same as those of the example 1, and accordingly the high-capacity P3-phase sodium-ion battery layered oxide positive electrode material Na is obtained 0.6 (Li 0.2 Be 0.4 Mn 0.6 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.4 Mn 0.6 )O 2 According to the test result, the prepared positive electrode material has good crystallinity, corresponds to PDF card #54-0839, and is in tetragonal symmetry index with the R3m space group, and other impurity phases are not detected.
For the prepared Na 0.6 (Li 0.2 Be 0.4 Mn 0.6 )O 2 And carrying out morphology characterization, wherein the prepared positive electrode material has regular hexagonal morphology, contains fewer impurities, and the regular morphology is beneficial to enhancing the structural integrity in the electrode circulation process.
The prepared Na 0.6 (Li 0.2 Be 0.4 Mn 0.6 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Comparative example 1
P3-phase sodium ion battery layered oxide positive electrode material Na 0.6 (Li 0.2 Mn 0.8 )O 2 The specific preparation steps of (a) are as follows:
(1) Mixing sodium carbonate, lithium hydroxide and manganese dioxide according to the molar ratio of Na to Li to Mn=0.6 to 0.2 to 0.8, adding 7 mL acetone, transferring into a planetary ball mill, and ball-milling for 12h at the rotating speed of 500r/min to obtain mixed slurry;
(2) Placing the mixed slurry obtained in the step (1) into a forced air drying oven, drying at 80 ℃ for 5 h, and then manually grinding and agglomerating to obtain powder;
(3) Transferring the powder obtained in the step (2) into a crucible, putting the crucible into a muffle furnace, heating to 700 ℃ at a heating rate of 4 ℃/min, sintering 24h in an air atmosphere at 700 ℃, and cooling to room temperature at a cooling rate of 4 ℃/min to obtain the anode material Na 0.6 (Li 0.2 Mn 0.8 )O 2 。
For the prepared Na 0.6 (Li 0.2 Mn 0.8 )O 2 The phase characterization was performed and the test results are shown in fig. 1.
For the prepared Na 0.6 (Li 0.2 Mn 0.8 )O 2 By carrying out morphology characterization, according to the characterization result of fig. 4, the prepared cathode material does not have regular morphology, mainly comprises micron-sized particles with relatively uniform distribution, has a certain agglomeration phenomenon, and simultaneously has certain impurity particles.
The prepared Na 0.6 (Li 0.2 Mn 0.8 )O 2 After the battery is assembled, the rate performance test is carried out, and the test result is shown in fig. 3.
Comparative example 2
Sodium ion battery layered oxide positive electrode material Na 0.6 (Li 0.2 Be 0.6 Mn 0.5 )O 2 The specific preparation steps of (a) are as follows:
(1) Mixing sodium carbonate, lithium hydroxide, beryllium acetylacetonate and manganese dioxide according to the molar ratio of Na to Li to Be of Mn=0.6 to 0.2 to 0.6 to 0.5, adding 7 mL acetone, transferring into a planetary ball mill, and ball-milling at a rotating speed of 500r/min for 12h to obtain mixed slurry;
(2) Placing the mixed slurry obtained in the step (1) into a forced air drying oven, drying at 80 ℃ for 5 h, and then manually grinding and agglomerating to obtain powder;
(3) Transferring the powder obtained in the step (2) into a crucible, putting the crucible into a muffle furnace, heating to 700 ℃ at a heating rate of 4 ℃/min, sintering for 24 hours in an air atmosphere at 700 ℃, and cooling to room temperature at a cooling rate of 4 ℃/min to obtain the anode material Na 0.6 (Li 0.2 Be 0.6 Mn 0.5 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.6 Mn 0.5 )O 2 According to the test result, the prepared positive electrode material has certain crystallinity, and part corresponds to PDF card #54-0839, but obvious hetero-phase peaks appear near 25 DEG, 55 DEG and 60 DEG at the moment, and a large amount of BeO and MnO of an unsintered phase possibly exist at the moment 2 Such impurities, the material does not fully conform to the P3 phase characteristics.
For the prepared Na 0.6 (Li 0.2 Be 0.6 Mn 0.5 )O 2 And carrying out morphology characterization, wherein according to a characterization result, the prepared positive electrode material does not have a regular morphology, the particle size is obviously increased, a certain agglomeration phenomenon exists, and a large number of impurity particles exist.
The prepared Na 0.6 (Li 0.2 Be 0.6 Mn 0.5 )O 2 After the positive electrode material is assembled into a battery, the rate performance test is carried out, and according to the test result, the corresponding specific discharge capacities of the positive electrode material at 0.1C, 0.2C, 0.5C, 1C and 2C are 122.51 mAh/g, 118.47 mAh/g, 104.60 mAh/g, 96.37 mAh/g and 82.7 mAh/g respectively, so that the specific capacity and the rate performance of the battery are obviously reduced compared with those of the battery in the example 1 and the comparative example 1.
Comparative example 3
Based on example 1, except that the sintering temperature in step (2) was modified to 800 ℃, other steps and preparation conditions were the same as in example 1, and a sodium ion battery layered oxide cathode material Na was obtained accordingly 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 。
For the prepared Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 According to the phase characterization, the prepared positive electrode material has certain crystallinity, and part of the positive electrode material corresponds to PDF card #54-0839, but obvious hetero-phase peaks appear near 40 degrees and 60 degrees at the moment, and the coexistence of P2 phase and P3 phase is possible, so that the influence of changing the sintering temperature on the phase formation of the material is obvious.
For the prepared Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 And carrying out morphology characterization, wherein the prepared positive electrode material does not have regular morphology, is irregular particles with micron level, has a certain agglomeration phenomenon and contains more impurities according to the characterization result.
The prepared Na 0.6 (Li 0.2 Be 0.25 Mn 0.675 )O 2 After the positive electrode material is assembled into a battery, the rate performance test is carried out, and according to the test result, the specific discharge capacities of the positive electrode material at 0.1C, 0.2C, 0.5C, 1C and 2C are 124.51 mAh/g, 108.78 mAh/g, 101.49 mAh/g, 90.57 mAh/g and 74.77 mAh/g respectively, and compared with the example 1, the specific capacity and the rate performance of the positive electrode material are obviously reduced.
Analysis of performance characterization results:
as can be seen from the XRD patterns of fig. 1, the positive electrode materials prepared in example 1, example 2, example 4, example 7 and comparative example 1 have no significant difference in diffraction peak-to-peak positions, and can correspond to PDF cards #54-0839, and are square symmetrical indexes in R3m space group, and no other impurity phases are detected. The XRD test result shows that the invention can successfully synthesize the P3-phase sodium ion battery layered oxide positive electrode material with good crystallinity and no impurity by adopting a solid phase sintering method, and the crystal structure is not changed obviously along with the increase of the Be doping proportion.
As can Be seen from the SEM images of fig. 2, the positive electrode materials prepared in example 1, example 2, example 4 and example 7 have regular hexagonal morphology, and the regular morphology helps to enhance structural integrity during electrode cycling, and meanwhile, it can Be found that the doping of the Be element effectively improves crystallinity of the materials. The crystallinity of the positive electrode material obtained in example 1 was the best if the doping ratio was 25%, and a hexagonal micron-sized block was obtained.
As can Be seen from the rate performance test results of fig. 3, at current densities of 0.1C, 0.2C, 0.5C, 1C, and 2C, the electrochemical performance of the positive electrode material doped with Be element in all the examples is improved to a certain extent, compared with the positive electrode material undoped with Be in comparative example 1, and the discharge specific capacity of the positive electrode material shows a trend of increasing and decreasing with increasing of Be doping ratio. When the Be doping ratio is 25% (corresponding to example 1), the positive electrode material shows the most excellent rate performance, at this time, the corresponding specific discharge capacities at 0.1C, 0.2C, 0.5C, 1C and 2C can respectively reach 200.3 mAh/g, 178 mAh/g, 156.4 mAh/g, 139 mAh/g and 119.7 mAh/g, and when the current density returns to 0.1C, the specific discharge capacity still reaches 192.4 mAh/g, which is equivalent to 97.9% of the initial discharge capacity. The batteries assembled in comparative example 1 had specific discharge capacities of 141.1 mAh/g, 128.5 mAh/g, 116.8 mAh/g, 101.4 mAh/g and 81.2 mAh/g at 0.1C, 0.2C, 0.5C, 1C and 2C, respectively, and 160.39 mAh/g when returned to the current density of 0.1C. This result shows that the P3 phase sodium ion battery layered oxide anode material Na prepared by the solid phase sintering method of the invention 0.6 Li 0.2 Be x Mn 0.8-x/2 O 2 The material has excellent battery capacity and rate capability, and is a potential application material of a high-performance sodium ion battery.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A high-capacity P3-phase sodium ion battery layered oxide positive electrode material is characterized in that: the chemical formula of the positive electrode material is abbreviated as P3-Na 0.6 Li 0.2 Be x Mn 0.8-x/2 O 2 X isThe mol percent of Be element, and the value range of x is more than or equal to 0.05 and less than or equal to 0.5, and has regular hexagonal morphology.
2. The high capacity P3 phase sodium ion battery layered oxide positive electrode material of claim 1, wherein: x=0.2 to 0.4.
3. A method for preparing the high-capacity P3-phase sodium ion battery layered oxide cathode material according to claim 1 or 2, wherein the method comprises the following steps: the method specifically comprises the following steps:
mixing a sodium source, a lithium source, a beryllium source and a manganese source according to stoichiometric ratio, adding an organic solvent, and uniformly mixing to obtain slurry; removing the organic solvent in the slurry, and grinding to obtain precursor powder; and (3) placing the precursor powder into a furnace, performing solid-phase sintering in an air atmosphere, sintering at 600-750 ℃ for 12-24 hours, cooling, and grinding the sintered product to obtain the high-capacity P3-phase sodium ion battery layered oxide positive electrode material.
4. The method for preparing the layered oxide cathode material of the high-capacity P3-phase sodium ion battery according to claim 3, wherein the method comprises the following steps: the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium nitrate and sodium fluoride; the lithium source is at least one selected from lithium carbonate, lithium hydroxide, lithium hexafluorophosphate, lithium perchlorate, lithium nitrate and organic electrolyte lithium salt; the beryllium source is at least one selected from beryllium oxide, beryllium hydroxide, beryllium fluoride, beryllium chloride and organic electrolytic beryllium salt; the manganese source is selected from one of manganese dioxide, manganese tetrafluoride and manganese oxyfluoride.
5. The method for preparing the layered oxide cathode material of the high-capacity P3-phase sodium ion battery according to claim 3, wherein the method comprises the following steps: the organic solvent is acetone, methanol, ethyl acetate, N-dimethylformamide or dimethyl sulfoxide.
6. The method for preparing the layered oxide cathode material of the high-capacity P3-phase sodium ion battery according to claim 3, wherein the method comprises the following steps: mixing by adopting a ball milling method, and ball milling for 8-12 hours at a rotating speed of 400-800 r/min to obtain uniformly mixed slurry.
7. The method for preparing the layered oxide cathode material of the high-capacity P3-phase sodium ion battery according to claim 3, wherein the method comprises the following steps: and (3) placing the slurry in a forced air drying oven, drying at 80-120 ℃ for 3-5 hours, and then grinding to obtain precursor powder.
8. The method for preparing the layered oxide cathode material of the high-capacity P3-phase sodium ion battery according to claim 3, wherein the method comprises the following steps: heating to 600-750 ℃ at a heating rate of 1-5 ℃/min, and cooling at a cooling rate of 1-5 ℃/min after sintering.
9. Use of the high capacity P3 phase sodium ion battery layered oxide positive electrode material according to claim 1 or 2, characterized in that: the positive electrode material is used as an active substance and applied to a positive electrode of a sodium ion battery.
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