CN115411236B - Nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, preparation method and application - Google Patents
Nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 120
- 239000001488 sodium phosphate Substances 0.000 title claims abstract description 72
- 229910000162 sodium phosphate Inorganic materials 0.000 title claims abstract description 72
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 title claims abstract description 72
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 title claims abstract description 71
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011572 manganese Substances 0.000 claims abstract description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- RMZMFASTOVOJPY-UHFFFAOYSA-N [Fe].[Mn].[Ni].[Na] Chemical compound [Fe].[Mn].[Ni].[Na] RMZMFASTOVOJPY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 96
- 239000000843 powder Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 36
- 229910001415 sodium ion Inorganic materials 0.000 claims description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000011734 sodium Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 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 23
- 229910052708 sodium Inorganic materials 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 238000010248 power generation Methods 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 238000004146 energy storage Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 238000004891 communication Methods 0.000 claims description 7
- -1 iron ions Chemical class 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000002482 conductive additive Substances 0.000 claims description 2
- 229910017119 AlPO Inorganic materials 0.000 description 14
- 239000002585 base Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, a preparation method and application. The material is a layered oxide material, and the space group isIn the material, aluminum phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material or is distributed on the surface of the sodium nickel iron manganese material and is dispersed in a sodium nickel iron manganese material bulk phase; the sodium phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material; the chemical general formula of the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is as follows: alPO 4@Naa[NibFecMndMee]O2+β; wherein the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence is alpha; +2.ltoreq.α.ltoreq. +4; a. b, c, d, e and beta are mole percentages of corresponding elements respectively; the relationship between them satisfies b+c+d+e=1, and a+2b+3c+4d+αe=2× (2+β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; -0.02.ltoreq.β.ltoreq.0.02.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, a preparation method and application.
Background
Since the industrial revolution, human society has entered a rapidly developing era, behind which is the massive consumption of traditional energy and the resulting environmental pollution. There is a need to tightly control the consumption of fossil fuels and to find new sources of energy. Nuclear energy has been considered as a solution to future energy sources, but since this technology presents safety problems that are difficult to fully solve, many countries have a trend to limit the use of nuclear energy. Future energy viable approaches are the development of renewable energy sources such as hydraulic resources, wind energy and solar energy, with the advantage of no pollution and safety issues. However, one drawback of developing these energy sources is that they are limited by geographic location or time, and they preferably need to be as close as possible to the electricity consumption location. In addition, a significant disadvantage of wind and solar energy is the discontinuity of its power generation, i.e. the large fluctuation of the power generated, and the inability to output at a constant power over a long period of time. The cycle of power generation fluctuation of wind power generation varies from hours, days to weeks, while solar power generation is several minutes or hours. Furthermore, solar cells can only produce power near the nominal value (peak current) at noon of solar irradiation, which is not the most concentrated period of power consumption in the day. This is inconvenient from the grid point of view and cannot be directly incorporated into the grid. The most convenient form of energy is that which people can reach, its stable supply determines the stable and orderly development of society. By the end of 2020, the accumulated installed scale of the energy storage project put into operation in China is 35.6GW, and the same ratio is increased by 9.8%; wherein the maximum proportion of the pumped storage accumulation machine is 89.30%, the secondary electrochemical energy storage is carried out, the accumulation machine scale is 3.28GW, and the proportion is 9.2%; for large scale energy storage, battery parameters that need to be considered include: price, lifetime, and power density. And here, raw materials with wide sources (low price) are required. Under the background, sodium ion batteries are paid more and more attention by researchers in recent years, and the world sodium resources are extremely sufficient, so that the application potential of the sodium ion batteries in the field of large-scale energy storage can be extremely huge.
The main advantages of sodium ion batteries over lithium ion batteries are their low cost, mainly from two points: the abundance of sodium element in crust is much higher than that of lithium element, and the sodium element is distributed at all corners of the earth, unlike the lithium resource which is mainly concentrated in south america and australia; in addition, the current collector of the negative electrode in the sodium ion battery can use aluminum which is a metal with lower cost, and lithium can react with the aluminum to form an alloy and is irreversible. Therefore, the negative electrode in the lithium ion battery can only select copper foil with higher cost as a current collector. In addition to low cost, a further advantage of sodium ion batteries is that they can be rapidly industrialized using the relatively mature production lines of lithium ion batteries, which is more evident than other emerging energy storage technologies, since most of the problems with sodium ion batteries are found in lithium ion batteries.
Sodium has a larger relative atomic mass and radius than lithium in lithium ion batteries, and sodium has a higher standard to hydrogen potential than lithium, so that in theory, sodium ion batteries have a lower energy density than lithium ion batteries, and according to the current manufacturing level of sodium ion batteries, the energy density is about half that of lithium ion batteries. But the energy density of sodium ion batteries is much higher than that of lead acid batteries, about three times that of lead acid batteries. The transition metal layered structure oxide is an embedded compound which is researched earlier and has the characteristics of higher energy density and easiness in preparation. The structural general formula is Na xMO2 (M represents one or more transition metal elements). Typically, each transition metal element combines with the surrounding six oxygens to form an MO 6 octahedron and is connected by co-edges, and sodium ions are located between the transition metal layers to form a layered structure in which MO 2 layers and Na layers are alternately arranged. The cost of the nickel-iron-manganese-based layered oxide material is very low, and the prices of the contained elements sodium, nickel, iron and manganese are far lower than those of cobalt, vanadium and other elements, but the cycling stability of the material is poor at present, so that the further development of the material is limited.
Disclosure of Invention
The invention provides a nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, a preparation method and application. The nickel-iron-manganese-based layered oxide material is simple to prepare, and the contained elements sodium, nickel, iron and manganese are nontoxic and safe elements. After the surface of the aluminum phosphate/sodium phosphate is modified, side reactions between the electrode material and electrolyte can be effectively inhibited, and the circulation stability is improved. The improved nickel-iron-manganese-based oxide material prepared by the method has the advantages of capacity retention rate improved by about 20% compared with that before improvement, good rate capability and great practical value. The sodium ion secondary battery based on the nickel-iron-manganese-based layered oxide material with the aluminum phosphate/sodium phosphate modified surface can be used for large-scale energy storage equipment of solar power generation, wind power generation, intelligent power grid peak shaving, distribution power stations, backup power sources or communication base stations.
The first aspect of the invention discloses a nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, wherein the material is a layered oxide material, and the space group isIn the material, aluminum phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material or is distributed on the surface of the sodium nickel iron manganese material and is dispersed in a sodium nickel iron manganese material bulk phase; the sodium phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material;
the chemical general formula of the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is as follows: alPO 4@Naa[NibFecMndMee]O2+β;
Wherein the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence state of Me is alpha; +2.ltoreq.α.ltoreq. +4; a. b, c, d, e and beta are mole percentages of corresponding elements respectively; the relationship between them satisfies b+c+d+e=1, and a+2b+3c+4d+αe=2× (2+β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; -0.02.ltoreq.β.ltoreq.0.02;
Preferably, the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is used for a positive electrode active material of a sodium ion secondary battery, when the positive electrode active material is charged for the first week, nickel ions lose electrons, the valence state is changed from +2 to +3, meanwhile, iron ions lose electrons, and the valence state is changed from +3 to +4; and when the first week of discharge is carried out, nickel ions with higher valence state obtain electrons again to be changed back to +2 valence, and iron ions obtain electrons to be changed back to +3 valence.
Preferably, the surface-modified aluminum phosphate/sodium phosphate of the nickel-iron-manganese based material does not participate in the redox reaction.
In a second aspect, an embodiment of the present invention provides a method for preparing a nickel-iron-manganese-based material having a surface modified by aluminum phosphate/sodium phosphate, the method comprising:
Dissolving Ni, fe, mn, me nitrate or sulfate in water or absolute ethyl alcohol according to stoichiometric ratio, and mixing them into precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
Dropwise adding the precursor solution into an ammonia water solution with a certain concentration and pH value by using a peristaltic pump to generate a precipitate [ Ni bFecMndMee]O2+β precursor; wherein the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, a, b, c, d, e and beta are the mole percentages of the corresponding elements respectively; the relationship between them satisfies b+c+d+e=1, and a+2b+3c+4d+αe=2× (2+β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; -0.02.ltoreq.β.ltoreq.0.02;
Adding [ Ni bFecMndMee]O2+β precursor, naOH and/or Na 2CO3 with required stoichiometric amount of 100-108 wt%, alNO 3 with the required stoichiometric amount of 0.01-5 mol% and NH 4H2PO4 with the required stoichiometric amount of 0.01-5 mol% and/or (NH 4)2HPO4) into water or absolute ethyl alcohol, heating and stirring until the mixture is evaporated to dryness, and drying the mixture to obtain precursor powder;
Placing the precursor powder into a muffle furnace, and performing heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
And grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
In a third aspect, an embodiment of the present invention provides a method for preparing a nickel-iron-manganese-based material having a surface modified by aluminum phosphate/sodium phosphate, the method comprising:
Mixing sodium carbonate with the required sodium stoichiometry of 100-108 wt% and NiO, fe 2O3 and/or Fe 3O4、Mn2O3 and/or MnO 2、MeOα/2 with the required stoichiometry in proportion to form a precursor; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
Adding absolute ethyl alcohol or water into the precursor, and uniformly stirring to form slurry;
Spray drying the slurry to obtain precursor powder; dispersing the precursor powder and AlNO 3,NH4H2PO4 and/or (NH 4)2HPO4) with required stoichiometric amount in deionized water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain coated precursor powder;
Placing the precursor powder into a muffle furnace, and performing heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
And grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
In a fourth aspect, an embodiment of the present invention provides a method for preparing a nickel-iron-manganese-based material having a surface modified by aluminum phosphate/sodium phosphate, the method comprising:
Mixing any one or more of sodium acetate, sodium nitrate, sodium carbonate and sodium sulfate with the stoichiometric amount of 100-108 wt% of required sodium, and dissolving nitrate or sulfate containing Ni, fe, mn, me in water or absolute ethyl alcohol according to the stoichiometric ratio to form a precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
Placing the precursor gel in a crucible, and presintering for 2 hours in an air atmosphere at 200-500 ℃ to obtain a precursor;
Dispersing the precursor and AlNO 3,NH4H2PO4 and/or (NH 4)2HPO4) with required stoichiometric amount in water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain precursor powder;
And then carrying out heat treatment for 2-24 hours at 600-1000 ℃, and grinding the heat-treated powder to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
In a fifth aspect, an embodiment of the present invention provides a method for preparing a nickel-iron-manganese-based material having a surface modified by aluminum phosphate/sodium phosphate, the method comprising:
Mixing sodium carbonate with the required sodium stoichiometry of 100-108 wt% and NiO, fe 2O3 and/or Fe 3O4、Mn2O3 and/or MnO 2、MeOα/2 with the required stoichiometry in proportion to form a precursor; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
Uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
dispersing the precursor powder and AlNO 3,(NH4)2HPO4 with required stoichiometric amount in absolute ethyl alcohol, heating, stirring and evaporating to dryness;
the product obtained after the evaporation is put into a muffle furnace and is heat treated for 2 to 24 hours in the air atmosphere at 600 to 1000 ℃;
Grinding the product after heat treatment to obtain the nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface.
In a sixth aspect, an embodiment of the present invention provides a positive electrode tab of a sodium ion secondary battery, the positive electrode tab including:
a current collector, a conductive additive and binder coated on the current collector, and a nickel-iron-manganese-based material with a modified surface of aluminum phosphate/sodium phosphate as described in the first aspect above.
In a seventh aspect, an embodiment of the present invention provides a sodium-ion secondary battery including the positive electrode sheet according to the sixth aspect.
Preferably, the sodium ion secondary battery is used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distribution power stations, backup power sources or communication base stations.
The invention provides a nickel-iron-manganese-based layered oxide material with aluminum phosphate/sodium phosphate modified surface, which is simple to prepare, and the contained elements sodium, nickel, iron and manganese are nontoxic and safe elements. The nickel-iron-manganese-based layered oxide material with the aluminum phosphate/sodium phosphate modified surface can effectively improve the cycling stability of the material. The improved nickel-iron-manganese-based oxide material prepared by the method has the advantages of improved capacity retention rate of about 20% in 200 weeks, good cycle stability and great practical value. The sodium ion secondary battery based on the sodium-nickel-iron-manganese-based layered oxide material can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distribution power stations, backup power sources or communication base stations.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a flow chart of a preparation method for preparing a nickel-iron-manganese-based layered oxide material with an aluminum phosphate/sodium phosphate modified surface by a solid phase method provided by the embodiment of the invention;
FIG. 2 is a flow chart of a preparation method of a nickel-iron-manganese-based layered oxide material with aluminum phosphate/sodium phosphate modified surface by a sol-gel method according to an embodiment of the present invention;
FIG. 3 is a flow chart of a preparation method of a nickel-iron-manganese-based layered oxide material with aluminum phosphate/sodium phosphate modified surface by a spray drying method according to an embodiment of the present invention;
FIG. 4 is a flow chart of a preparation method of nickel-iron-manganese-based layered oxide material with aluminum phosphate/sodium phosphate modified surface by a coprecipitation method according to an embodiment of the present invention;
FIG. 5 is an X-ray diffraction (XRD) pattern of nickel-iron-manganese-based layered oxide materials modified by varying mole percentages of aluminum phosphate content provided by the examples of this invention;
FIG. 6 is a graph showing the charge and discharge of a sodium ion battery according to example 1 of the present invention at 2-4V;
FIG. 7 is a 200-cycle chart of the sodium ion battery provided in example 1 of the present invention at 2-4V;
fig. 8 is a graph of charge and discharge of the sodium ion battery according to example 1 of the present invention at 2-4.2V.
Detailed Description
The present invention will be described in further detail with reference to examples, but is not intended to limit the scope of the present invention.
The invention provides a nickel-iron-manganese-based layered oxide material with an aluminum phosphate/sodium phosphate modified surface formed in situ, a preparation method and application.
The material is a layered oxide material, and the space group isIn the nickel-iron-manganese-based layered oxide material with the surface modified by aluminum phosphate/sodium phosphate, aluminum phosphate formed in situ is distributed on the surface of the sodium-nickel-iron-manganese material or is distributed on the surface of the sodium-nickel-iron-manganese material and is dispersed in a sodium-nickel-iron-manganese material bulk phase; the sodium phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material. The aluminum phosphate/sodium phosphate formed in situ is interspersed on the surface of the material, so that the progress of side reaction can be reduced; sodium phosphate formed by reaction with residual alkali on the surface is used as a fast ion conductor of sodium, a channel is provided for sodium intercalation and deintercalation, the rate capability can be effectively improved, and the air stability of the material is improved to a certain extent.
The chemical general formula of the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is as follows: alPO 4@Naa[NibFecMndMee]O2+β; wherein, the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4; a. b, c, d, e and beta are mole percentages of corresponding elements respectively; the relationship between them satisfies b+c+d+e=1, and a+2b+3c+4d+αe=2× (2+β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; -0.02.ltoreq.β.ltoreq.0.02.
The nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is used for the positive electrode active material of a sodium ion secondary battery, when the positive electrode active material is charged for the first week, nickel ions lose electrons, the valence state is changed from +2 to +3, and meanwhile, iron ions lose electrons, and the valence state is changed from +3 to +4; and when the first week of discharge is carried out, nickel ions with higher valence state obtain electrons again to be changed back to +2 valence, and iron ions obtain electrons to be changed back to +3 valence.
The aluminum phosphate/sodium phosphate modified on the surface of the nickel-iron-manganese base material does not participate in the oxidation-reduction reaction. The existence of the electrolyte reduces the erosion of the electrolyte to the material and protects the matrix structure of the electrode material.
The nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface can be used for the positive electrode plate of a sodium ion secondary battery. The sodium ion secondary battery using the sodium ion secondary battery as the positive electrode plate can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power sources or communication base stations.
The nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface can be prepared by various methods.
FIG. 1 is a flow chart of a preparation method for preparing a nickel-iron-manganese-based layered oxide material with an aluminum phosphate/sodium phosphate modified surface by a solid phase method according to an embodiment of the invention. As shown in fig. 1, the main steps of the method include:
Step 110, mixing sodium carbonate with the required sodium stoichiometry of 100-108 wt% and NiO, fe 2O3 and/or Fe 3O4、Mn2O3 and/or MnO 2、MeOα/2 with the required stoichiometry according to a proportion to form a precursor;
Wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
step 120, uniformly mixing the precursor by adopting a ball milling method to obtain precursor powder;
Step 130, dispersing the precursor powder and AlNO 3,(NH4)2HPO4 with required stoichiometric amount in absolute ethyl alcohol, heating, stirring and evaporating to dryness;
Preferably, the AlNO 3,(NH4)2HPO4 is used in an amount of 0.01% -5% by mole of the total amount of the nickel-iron-manganese-based layered oxide, respectively.
Step 140, placing the product obtained after the evaporation to dryness in a muffle furnace, and performing heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
and 150, grinding the heat-treated product to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
Fig. 2 is a flow chart of a preparation method of a nickel-iron-manganese-based layered oxide material with a modified surface of aluminum phosphate/sodium phosphate by a sol-gel method according to an embodiment of the invention. As shown in fig. 2, the main steps of the method include:
Step 210, mixing any one or more of sodium acetate, sodium nitrate, sodium carbonate and sodium sulfate with the stoichiometric amount of 100-108 wt% of required sodium into precursor solution by dissolving nitrate or sulfate containing Ni, fe, mn, me in water or absolute ethanol according to the stoichiometric ratio;
Wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
step 220, stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
Specifically, the chelating agent may specifically preferably be used: ethylene glycol: citric acid=4:1; the addition amount is citric acid: transition metal (Ni, fe, mn, me) molar ratio = 1:1, a step of;
230, placing the precursor gel in a crucible, and presintering for 2 hours in an air atmosphere at 200-500 ℃ to obtain a precursor;
Step 240, dispersing the precursor and AlNO 3,NH4H2PO4 and/or (NH 4)2HPO4) with required stoichiometric amount in water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain precursor powder;
Wherein, evaporating temperature is: 40-200 ℃, and the stirring rate is as follows: 100-1000r/min;
Preferably, the AlNO 3,(NH4)2HPO4 is used in an amount of 0.01% -5% by mole of the total amount of the nickel-iron-manganese-based layered oxide, respectively.
And 250, performing heat treatment at 600-1000 ℃ for 2-24 hours, and grinding the heat-treated powder to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
FIG. 3 is a flow chart of a method for preparing a nickel-iron-manganese-based layered oxide material with a modified surface of aluminum phosphate/sodium phosphate by a spray drying method according to an embodiment of the invention. As shown in fig. 3, the main steps of the method include:
Step 310, mixing sodium carbonate with the required sodium stoichiometry of 100-108 wt% and NiO, fe 2O3 and/or Fe 3O4、Mn2O3 and/or MnO 2、MeOα/2 with the required stoichiometry according to a proportion to form a precursor;
Wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
step 320, adding absolute ethyl alcohol or water into the precursor, and uniformly stirring to form slurry;
Step 330, spray drying the slurry to obtain precursor powder; dispersing the precursor powder and stoichiometric AlNO 3,NH4H2PO4 and/or (NH 4)2HPO4) in deionized water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain coated precursor powder;
Wherein, evaporating temperature is: stirring at 80-120 deg.c and 20-400r/min;
Preferably, the AlNO 3,(NH4)2HPO4 is used in an amount of 0.01% -5% by mole of the total amount of the nickel-iron-manganese-based layered oxide, respectively.
340, Placing the precursor powder in a muffle furnace, and performing heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
And 350, grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
FIG. 4 is a flow chart of a preparation method of a nickel-iron-manganese-based layered oxide material with a modified surface by an aluminum phosphate/sodium phosphate method by a coprecipitation method according to an embodiment of the present invention. As shown in fig. 4, the main steps of the method include:
step 410, dissolving Ni, fe, mn, me nitrate or sulfate in water or absolute ethanol according to stoichiometric ratio, and mixing to form a precursor solution;
Wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
step 420, dropwise adding the precursor solution into an ammonia water solution with a certain concentration and pH value by using a peristaltic pump to generate a precipitate [ Ni bFecMndMee]O2+β precursor;
wherein, the concentration range of the ammonia water solution is as follows: 10% -28%; the pH value is in the range of 10.0-12.0;
The valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, a, b, c, d, e and beta are mole percentages of corresponding elements respectively; the relationship between them satisfies b+c+d+e=1, and a+2b+3c+4d+αe=2× (2+β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; -0.02.ltoreq.β.ltoreq.0.02;
Step 430, adding [ Ni bFecMndMee]O2+β precursor, naOH and/or Na 2CO3 with required stoichiometric amount of 100-108 wt%, alNO 3 with required stoichiometric amount of 0.01-5 mol% and NH 4H2PO4 with required stoichiometric amount of 0.01-5 mol% and/or (NH 4)2HPO4) into water or absolute ethyl alcohol, heating and stirring until the mixture is evaporated to dryness, and drying to obtain precursor powder;
wherein, the heating temperature is: 40-60 ℃, and the stirring rate is as follows: 400-1000 r/min;
Step 440, placing the precursor powder in a muffle furnace, and performing heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
And 450, grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
The preparation methods provided above can be used to prepare the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface of the above embodiment. The method provided by the embodiment is simple and easy to implement, has low cost, contains elements of phosphorus, aluminum, sodium, nickel, iron and manganese which are nontoxic and safe elements, and is suitable for large-scale manufacturing application. Characteristic peaks of aluminum phosphate and sodium phosphate formed in situ on the surface of the material can be measured by XRD test, and the generation of the material is proved. Aluminum phosphate and sodium phosphate can effectively inhibit side reactions with the electrolyte. The improved nickel-iron-manganese-based layered oxide material has a good cycle life and a high practical value. The sodium ion secondary battery based on the sodium-nickel-iron-manganese-based layered oxide material can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distribution power stations, backup power sources or communication base stations.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the sodium-nickel-iron-manganese-based layered oxide material by using the methods provided by the embodiments of the invention, and the method and the battery characteristics for applying the same to a sodium ion battery are respectively described in a plurality of specific examples.
Example 1
In this embodiment, the preparation of the sodium nickel iron manganese-based layered oxide material by the solid phase method includes:
Mixing Na 2CO3 (analytically pure), niO (analytically pure), fe 2O3 (analytically pure), mnO 2 (analytically pure) according to the required stoichiometric ratio; the precursor powder was obtained by grinding for half an hour in an agate mortar.
Dividing the precursor powder into 5 groups, respectively mixing with 1%,2%,3%,4% and 5% stoichiometric AlNO 3 and (NH 4)2HPO4 dispersed in absolute ethanol, heating, stirring, evaporating to dryness, tabletting, transferring into Al 2O3 crucible, processing at 900 deg.C for 15 hr in muffle furnace, grinding to obtain layered oxide material AlPO 4@NaNi0.4Fe0.2Mn0.4O2 of 5 groups of black powder,
For ease of recording NaNi 0.4Fe0.2Mn0.4O2 is denoted NFM. The XRD patterns of the materials of each group are shown in fig. 5. From the XRD pattern, the crystal structure of AlPO 4@NaNi0.4Fe0.2Mn0.4O2 is oxide with an O3 phase lamellar structure.
As limited by XRD measurement accuracy, diffraction peaks for sodium phosphate can be seen at 21℃to 22℃and around 34℃on the test result of 5% AlPO 4 @ NFM, indicating that sodium phosphate is formed by residual base reaction at the surface.
The active substance of the 1% AlPO 4 @NFM material prepared by the method is used for preparing a sodium ion battery, and the specific steps are as follows: mixing the prepared 1% AlPO 4@NaNi0.4Fe0.2Mn0.4O2 powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to the mass ratio of 80:10:10, adding a proper amount of N-methyl pyrrolidone (NMP) solution, grinding in an environment of normal temperature drying to form slurry, uniformly coating the slurry on a current collector aluminum foil, drying under an infrared lamp, and cutting into a pole piece with the thickness of (8 multiplied by 8) mm 2. The pole piece is dried for 10 hours at 110 ℃ under the vacuum condition, and then is transferred to a glove box for standby.
The assembly of the simulated cell was performed in a glove box with Ar atmosphere, with metallic sodium as the counter electrode, and NaClO 4/Propylene Carbonate (PC) and Ethylene Carbonate (EC) (EC: pc=1:1) solutions as the electrolyte, to assemble a CR2032 coin cell. And using a constant current charge and discharge mode, and performing charge and discharge test under the current density of C/10. The test results are shown in fig. 6 under the condition that the discharge cut-off voltage is 2V and the charge cut-off voltage is 4V.
Meanwhile, naNi 0.4Fe0.2Mn0.4O2 materials are directly used as active substances of battery anode materials for preparing sodium ion batteries, and the specific steps are the same as above for comparison.
In fig. 6, the charge-discharge cycle curves of NaNi 0.4Fe0.2Mn0.4O2 (denoted NFM in the figure) and 1% AlPO 4@NaNi0.4Fe0.2Mn0.4O2 (denoted AlPO 4 @ NFM in the figure) are compared, and it can be seen that the specific capacity of the first week discharge can reach 147mAh/g with the 1% AlPO 4@NaNi0.4Fe0.2Mn0.4O2 according to the present invention, with almost no capacity loss.
Fig. 7 is a 200-cycle chart of the sodium ion battery provided in example 1 of the present invention at 2-4V. The capacity retention rate of the NFM material without surface modification is about 60% at 200 weeks, while the capacity retention rate of the material of 1% alpo 4 @ NFM reaches about 80% at 200 weeks. The cycle stability is obviously improved.
And using a constant current charge and discharge mode, and performing charge and discharge test under the current density of C/10. The test results are shown in fig. 8 under the condition that the discharge cut-off voltage is 2V and the charge cut-off voltage is 4.2V.
In FIG. 8, the charge-discharge cycle curves of NaNi 0.4Fe0.2Mn0.4O2 (shown as NFM) and 1mol% AlPO 4@NaNi0.4Fe0.2Mn0.4O2 (shown as AlPO 4 @ NFM) are compared, and it can be seen that the 1mol% AlPO 4@NaNi0.4Fe0.2Mn0.4O2 of the present invention can achieve a specific capacity of 181mAh/g at the first week with little capacity loss.
Example 2
In this embodiment, the preparation of the sodium nickel iron manganese-based layered oxide material by the aforementioned coprecipitation method includes:
dissolving nitrate of Ni, nitrate of Fe, sulfate of Mn and sulfate of Mg in absolute ethyl alcohol according to stoichiometric ratio, and mixing to obtain precursor solution;
dropwise adding the precursor solution, ammonia water with the concentration of 18% and sodium hydroxide solution into a reaction kettle by a peristaltic pump, and maintaining the pH value in the reaction kettle to be 11 (precision at 25 ℃), so as to generate a precipitate [ Ni 0.39Mg0.01Fe0.2Mn0.4]O2 precursor;
Adding [ Ni 0.39Mg0.01Fe0.2Mn0.4]O2 precursor, required stoichiometric amount 105wt% of Na 2CO3, 3% of AlNO 3 and 3% of NH 4H2PO4 into water, heating and stirring until the precursor is evaporated to dryness, and drying to obtain precursor powder;
Placing the precursor powder in a muffle furnace, and performing heat treatment for 10 hours in an air atmosphere at 800 ℃;
And grinding the precursor powder after the heat treatment to obtain the aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese base material 3mol% AlPO 4@[Ni0.39Mg0.01Fe0.2Mn0.4]O2.
Example 3
In this embodiment, the preparation of the sodiumcaroferrite-manganese-based layered oxide material by the spray drying method described above includes:
Mixing 104wt% of sodium carbonate, niO and Fe 2O3、MnO2、TiO2 with required stoichiometric amounts in proportion to form a precursor;
adding absolute ethyl alcohol into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder;
Dispersing the precursor powder, 3mol% of AlNO 3 and 3mol% of (NH 4)2HPO4 in deionized water, stirring and evaporating to dryness to obtain coated precursor powder;
placing the precursor powder in a muffle furnace, and performing heat treatment for 12 hours in an air atmosphere at 1000 ℃;
And grinding the precursor powder after the heat treatment to obtain the aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese base material 3mol% AlPO 4@[Ni0.4Fe0.2Mn0.39Ti0.01]O2.
Example 4
In this embodiment, the preparation of the sodium nickel iron manganese-based layered oxide material by the sol-gel method includes:
Dissolving sodium acetate and sodium sulfate with the required sodium stoichiometry of 108wt%, nitrate of Ni, nitrate of Fe, sulfate of Mn and sulfate of Al in absolute ethanol to form a precursor solution;
stirred at 50 ℃ and an appropriate amount of chelating agent ethylene glycol was added: citric acid=4:1, evaporated to dryness to form a precursor gel;
placing the precursor gel in a crucible, and presintering for 2 hours in an air atmosphere at 500 ℃ to obtain a precursor;
Dispersing the precursor, 3mol% of AlNO 3 and 3mol% of (NH 4)2HPO4 in absolute ethyl alcohol, stirring and evaporating to dryness to obtain precursor powder;
And then carrying out heat treatment at 600 ℃ for 24 hours, and grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material 3mol% AlPO 4@Ni0.4Fe0.19Al0.01Mn0.4O2 with the aluminum phosphate/sodium phosphate modified surface.
The nickel-iron-manganese-based layered oxide material with the aluminum phosphate/sodium phosphate modified surface provided by the invention is simple to prepare, and the contained elements sodium, nickel, iron and manganese are nontoxic and safe elements. The nickel-iron-manganese-based layered oxide material with the aluminum phosphate/sodium phosphate modified surface can effectively improve the cycling stability of the material. The improved nickel-iron-manganese-based oxide material prepared by the method has the advantages of improved capacity retention rate of about 20% in 200 weeks, good cycle stability and great practical value. The sodium ion secondary battery based on the sodium-nickel-iron-manganese-based layered oxide material can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distribution power stations, backup power sources or communication base stations.
Claims (10)
1. The nickel-iron-manganese-based material with the surface modified by aluminum phosphate/sodium phosphate is characterized in that the material is a layered oxide material, and the space group isIn the material, aluminum phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material or is distributed on the surface of the sodium nickel iron manganese material and is dispersed in a sodium nickel iron manganese material bulk phase; the sodium phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material;
the chemical general formula of the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is as follows: alPO 4@Naa[NibFecMndMee]O2+β;
Wherein the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence state of Me is alpha; +2.ltoreq.α.ltoreq. +4; a. b, c, d, e and beta are mole percentages of corresponding elements respectively; the relationship between them satisfies b+c+d+e=1, and a+2b+3c+4d+αe=2× (2+β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; -0.02.ltoreq.β.ltoreq.0.02.
2. The aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese based material according to claim 1, wherein the aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese based material is used for a positive electrode active material of a sodium ion secondary battery, and when charged for the first week, nickel ions lose electrons, valence state is changed from +2 to +3, and simultaneously iron ions lose electrons, valence state is changed from +3 to +4; and when the first week of discharge is carried out, nickel ions with higher valence state obtain electrons again to be changed back to +2 valence, and iron ions obtain electrons to be changed back to +3 valence.
3. The material of claim 1, wherein the surface modified aluminum phosphate/sodium phosphate of the nickel iron manganese based material does not participate in the redox reaction.
4. A method for preparing the aluminum phosphate/sodium phosphate modified surface nickel iron manganese base material according to any one of claims 1-3, comprising the steps of:
Dissolving Ni, fe, mn, me nitrate or sulfate in water or absolute ethyl alcohol according to stoichiometric ratio, and mixing them into precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
Dropwise adding the precursor solution into an ammonia water solution with a certain concentration and pH value by using a peristaltic pump to generate a precipitate [ Ni bFecMndMee]O2+β precursor; wherein the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, a, b, c, d, e and beta are the mole percentages of the corresponding elements respectively; the relationship between them satisfies b+c+d+e=1, and a+2b+3c+4d+αe=2× (2+β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; -0.02.ltoreq.β.ltoreq.0.02;
Adding [ Ni bFecMndMee]O2+β precursor, naOH and/or Na 2CO3 with required stoichiometric amount of 100-108 wt%, alNO 3 with the required stoichiometric amount of 0.01-5 mol% and NH 4H2PO4 with the required stoichiometric amount of 0.01-5 mol% and/or (NH 4)2HPO4) into water or absolute ethyl alcohol, heating and stirring until the mixture is evaporated to dryness, and drying the mixture to obtain precursor powder;
Placing the precursor powder into a muffle furnace, and performing heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
And grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
5. A method for preparing the aluminum phosphate/sodium phosphate modified surface nickel iron manganese base material according to any one of claims 1-3, comprising the steps of:
Mixing sodium carbonate with the required sodium stoichiometry of 100-108 wt% and NiO, fe 2O3 and/or Fe 3O4、Mn2O3 and/or MnO 2、MeOα/2 with the required stoichiometry in proportion to form a precursor; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
Adding absolute ethyl alcohol or water into the precursor, and uniformly stirring to form slurry;
Spray drying the slurry to obtain precursor powder; dispersing the precursor powder and AlNO 3,NH4H2PO4 and/or (NH 4)2HPO4) with required stoichiometric amount in deionized water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain coated precursor powder;
Placing the precursor powder into a muffle furnace, and performing heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
And grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
6. A method for preparing the aluminum phosphate/sodium phosphate modified surface nickel iron manganese base material according to any one of claims 1-3, comprising the steps of:
Mixing any one or more of sodium acetate, sodium nitrate, sodium carbonate and sodium sulfate with the stoichiometric amount of 100-108 wt% of required sodium, and dissolving nitrate or sulfate containing Ni, fe, mn, me in water or absolute ethyl alcohol according to the stoichiometric ratio to form a precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
Placing the precursor gel in a crucible, and presintering for 2 hours in an air atmosphere at 200-500 ℃ to obtain a precursor;
Dispersing the precursor and AlNO 3,NH4H2PO4 and/or (NH 4)2HPO4) with required stoichiometric amount in water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain precursor powder;
And then carrying out heat treatment for 2-24 hours at 600-1000 ℃, and grinding the heat-treated powder to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
7. A method for preparing the aluminum phosphate/sodium phosphate modified surface nickel iron manganese base material according to any one of claims 1-3, comprising the steps of:
Mixing sodium carbonate with the required sodium stoichiometry of 100-108 wt% and NiO, fe 2O3 and/or Fe 3O4、Mn2O3 and/or MnO 2、MeOα/2 with the required stoichiometry in proportion to form a precursor; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2.ltoreq.α.ltoreq. +4;
Uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
dispersing the precursor powder and AlNO 3,(NH4)2HPO4 with required stoichiometric amount in absolute ethyl alcohol, heating, stirring and evaporating to dryness;
the product obtained after the evaporation is put into a muffle furnace and is heat treated for 2 to 24 hours in the air atmosphere at 600 to 1000 ℃;
Grinding the product after heat treatment to obtain the nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface.
8. A positive electrode tab of a sodium ion secondary battery, the positive electrode tab comprising:
A current collector, a conductive additive and binder coated on the current collector and a nickel-iron-manganese-based material with a modified surface of aluminum phosphate/sodium phosphate as claimed in any one of claims 1 to 3.
9. A sodium ion secondary battery comprising the positive electrode sheet of claim 8.
10. The sodium ion secondary battery of claim 9, wherein the sodium ion secondary battery is used in a large-scale energy storage device for solar power generation, wind power generation, smart grid peaking, distribution power station, backup power supply or communication base station.
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