CN114300658A - Doped coated sodium-ion battery positive electrode material and preparation method thereof - Google Patents
Doped coated sodium-ion battery positive electrode material and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 85
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 40
- 239000011572 manganese Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 23
- 238000007873 sieving Methods 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 10
- 238000000975 co-precipitation Methods 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012716 precipitator Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000008247 solid mixture Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 7
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000011265 semifinished product Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910005565 NiaMnb Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 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
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a doping-coated sodium ion battery anode material and a preparation method thereof, wherein the chemical structural formula of the material is NaNixMnyVzAl1‑x‑y‑zO2X is more than or equal to 0.1 and less than 0.9, y is more than or equal to 0.09 and less than or equal to 0.9, and z is more than or equal to 0.01 and less than or equal to 0.09; then using active oxygen remover MS2 to treat the positive electrode material of the sodium-ion batteryAnd (3) coating to prepare the doped and coated sodium-ion battery cathode material, and the doped and coated sodium-ion battery cathode material has good energy density and cycling stability.
Description
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a doped coated sodium ion battery anode material and a preparation method thereof.
Background
With the increasing global environmental pollution, the demand for new energy with high efficiency, cleanness and sustainable development is continuously expanding, wherein the lithium ion battery is widely concerned as a novel high-energy green battery, but the development of the lithium ion battery is probably limited in the future due to the problems of uneven distribution of lithium resources and resource shortage in the lithium ion battery. Sodium-ion batteries are most likely to be one of the alternatives to lithium-ion batteries because sodium has similar chemical properties to lithium. The working principle of the sodium ion battery is basically consistent with that of the lithium ion battery, and Na is added in the charging process+The ions are removed from the anode material and enter the cathode material through the electrolyte, and meanwhile, electrons flow from the anode to the cathode through an external circuit, and the discharging process is opposite to the discharging process.
The sodium element is abundant in nature, is arranged at the 6 th position in each element on the earth, has huge reserves in oceans and salt lakes, and has very simple method for obtaining the sodium element, so compared with a lithium ion battery, the sodium ion battery has very obvious cost advantage.
Although the sodium ion battery has unique advantages in terms of resources and cost, the radius (0.102nm) of sodium ions is larger than that (0.076nm) of lithium ions, so the sodium ions are relatively stable in a rigid structure and difficult to reversibly deintercalate. Even if the deintercalation can occur, the kinetics of the intercalation and deintercalation of sodium ions are slow, and the structure of the electrode material is easily caused to generate irreversible phase change, thereby reducing the cycle performance of the battery. At present, almost all the literature considers Na2/3Ni1/3Mn2/3O2O at 4.2V2-Will lose electrons and finally form O2Precipitates from the crystal lattice, densifying the surface lattice, resulting in irreversible capacity loss.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a doping-coated sodium ion battery positive electrode material and a preparation method thereof, which improve the transmission rate and the electronic conductivity of sodium ions, eliminate active oxygen formed in the charging and discharging process of the sodium ion battery positive electrode material, and improve the structural stability and the cycle performance.
The invention is realized by the following technical scheme.
The doped coated sodium-ion battery positive electrode material is characterized in that the chemical structural formula of the material is NaNixMnyVzAl1-x-y-zO2，0.1≤x＜0.9，0.09≤y＜0.9，0.01≤z≤0.09。
A method for preparing the above material, the method comprising:
(1) adding a nickel source, a manganese source, a vanadium source and an aluminum source into a reaction kettle, simultaneously adding a complexing agent and a precipitator, and carrying out coprecipitation reaction under an inert atmosphere to obtain a semi-finished product of a precursor of the sodium-ion battery;
(2) centrifugally filtering and separating the sodium-ion battery precursor semi-finished product obtained in the step (1), washing to be neutral, drying and sieving to obtain the molecular formula NiaMnbVcAl1-a-b-c(OH)2The precursor of the positive electrode material of the sodium-ion battery is that a is more than or equal to 0.1 and less than 0.9, b is more than or equal to 0.09 and less than 0.9, and c is more than or equal to 0.01 and less than or equal to 0.09;
(3) uniformly mixing the sodium ion battery positive electrode material precursor obtained in the step (2) with sodium carbonate, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain a vanadium-aluminum doped sodium ion battery positive electrode material;
(4) dissolving the vanadium-aluminum doped sodium ion battery anode material obtained in the step (3) and an active oxygen remover MS2 in absolute ethyl alcohol for ultrasonic dispersion, filtering, and drying the solid mixture in vacuum to obtain a dried product;
(5) and (4) placing the dried product obtained in the step (4) in a tubular furnace in a nitrogen atmosphere for roasting, cooling to room temperature, and sieving to obtain the vanadium-aluminum doped MS2 coated sodium ion battery positive electrode material.
Further, the nickel source in the step (1) is one of nickel sulfate, nickel chloride, nickel acetate and nickel nitrate; the manganese source is one of manganese sulfate, manganese chloride, manganese acetate and manganese nitrate; the vanadium source is a sodium vanadate solution prepared by dissolving vanadium pentoxide or ammonium metavanadate in sodium hydroxide; the aluminum source is sodium metaaluminate; the complexing agent is ammonia water solution, and the precipitator is sodium hydroxide solution.
Further, in the step (1), a nickel source and a manganese source are prepared into a salt solution with a molar ratio of nickel ions to manganese ions of 1: 9-9: 1, the prepared salt solution is injected into a reaction kettle with a rotation speed of 320-450 rpm at a speed of 4-15L/h, 0.2-0.5 mol/L of an aluminum source and 0.2-0.5 mol/L of a vanadium source (metal vanadium) are added into the reaction kettle at a speed of 1-4L/h, 2mol/L of a complexing agent and 4mol/L of a precipitating agent are added into the reaction kettle for coprecipitation reaction, the pH value is kept between 10 and 12, the reaction temperature is controlled at 48-60 ℃, and the reaction time is 40-100 hours.
Further, the drying temperature in the step (2) is 90-160 ℃, and the drying time is 8-20 h.
Further, the sodium ion battery positive electrode material precursor and sodium carbonate in the step (3) are mixed according to the molar ratio of 1: 1.05-1.2.
Further, the roasting temperature in the step (3) is controlled to be 500-.
Further, in the step (4), the positive electrode material of the sodium-ion battery and an active oxygen remover MS2 are subjected to ultrasonic dispersion for 15-30min according to the mass ratio (90-100) of 1, the obtained solid mixture is subjected to vacuum drying for 10-24h at 80-120 ℃ to obtain a dried product, and the active oxygen remover MS2 is at least one of NiS2, MnS2, CoS2 and VS 2.
Further, the dried product in the step (5) is placed in a tubular furnace under nitrogen atmosphere and roasted for 5-10h at the temperature of 600-800 ℃.
The invention has the beneficial technical effects that the transmission rate and the electronic conductivity of sodium ions are improved by replacing partial nickel and manganese with metal aluminum and vanadium, the polarization generated by electrode materials in the process of rapid charge and discharge is inhibited, and the structural stability of the sodium ion battery is improved; the active oxygen remover MS2 is coated on the surface of the positive electrode material of the sodium-ion battery, so that active oxygen formed in the positive electrode material of the sodium-ion battery in the charging and discharging process can be eliminated, the oxidative decomposition and gas generation of electrolyte can be inhibited, a stable coating layer can be formed to prevent the positive electrode material from contacting with the electrolyte, and the cycle performance and the stability are improved.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a doped coated sodium ion battery anode material and a preparation method thereof, wherein metal elements of aluminum and vanadium are doped to replace partial nickel and manganese during precursor preparation, so that the transmission rate and the electronic conductivity of sodium ions are improved; and then coating the positive electrode material of the sodium-ion battery by using an active oxygen remover MS2 to prepare the doped and coated positive electrode material of the sodium-ion battery, and the doped and coated positive electrode material of the sodium-ion battery has good energy density and cycling stability.
Comparative example 1
Preparing a 2mol/L salt solution from a nickel sulfate solution and a manganese sulfate solution according to the molar ratio of nickel ions to manganese ions of 1: 2. Injecting the prepared salt solution into a reaction kettle with the rotating speed of 360rpm at the speed of 10L/h, simultaneously adding 2mol/L complexing agent ammonia water solution and 4mol/L precipitator sodium hydroxide solution into the reaction kettle to carry out coprecipitation reaction in an inert atmosphere, keeping the pH value between 11 and 12, controlling the reaction temperature to be about 55 ℃, reacting for 40 hours, then carrying out centrifugal filtration and separation, drying at 100 ℃ for 8 hours after washing to be neutral, and sieving to obtain the salt solution with the molecular formula of Ni1/3Mn2/3(OH)2The sodium ion battery precursor material of (1);
uniformly mixing the sodium ion battery precursor and sodium carbonate according to the ratio of 1:1.1, roasting in a muffle furnace at the roasting temperature of 600 ℃ for 10h, cooling, crushing and sieving after roasting to obtain the compound Na with the molecular formula2/3Ni1/3Mn2/3O2The positive electrode material for sodium ion batteries. And testing the discharge specific capacity, capacity retention rate after circulation, decomposition temperature and high-temperature circulation retention rate of the positive electrode material of the sodium-ion battery.
Comparative example 2
Nickel sulfate and manganese sulfate solution are mixed according to the molar ratio of nickel ions to manganese ions1:2 is prepared into a salt solution with the concentration of 2 mol/L. Injecting prepared salt solution into a reaction kettle with the rotating speed of 360rpm at the speed of 10L/h, adding 0.4mol/L sodium metaaluminate solution and 0.4mol/L sodium vanadate solution prepared by dissolving vanadium pentoxide or ammonium metavanadate in sodium hydroxide into the reaction kettle at the speed of 2.5L/h at the same time, simultaneously adding 2mol/L complexing agent ammonia water solution and 4mol/L precipitator sodium hydroxide solution into the reaction kettle to carry out coprecipitation reaction under inert atmosphere, keeping the pH value between 11.4 and 12, controlling the reaction temperature to be about 60 ℃, reacting for 60h, then centrifugally filtering and separating, drying for 8h at 160 ℃ after washing to be neutral, and sieving to obtain Ni with the molecular formula of Ni0.3Mn0.6V0.05Al0.05(OH)2The sodium ion battery precursor material of (1);
uniformly mixing the sodium ion battery precursor and sodium carbonate according to the ratio of 1:1.15, roasting in a muffle furnace at the roasting temperature of 750 ℃ for 11 hours, cooling, crushing and sieving after roasting to obtain the NaNi molecular formula0.3Mn0.6V0.05Al0.05O2The positive electrode material for sodium ion batteries. And testing the specific discharge capacity, the capacity retention rate after circulation, the decomposition temperature and the high-temperature circulation retention rate of the doped sodium-ion battery anode material.
Example 1
Preparing a 2mol/L salt solution from a nickel sulfate solution and a manganese sulfate solution according to the molar ratio of nickel ions to manganese ions of 1: 2. Injecting prepared salt solution into a reaction kettle with the rotating speed of 360rpm at the speed of 10L/h, adding 0.4mol/L sodium metaaluminate solution and 0.4mol/L sodium vanadate solution prepared by dissolving vanadium pentoxide in sodium hydroxide into the reaction kettle at the speed of 2.5L/h at the same time, simultaneously adding 2mol/L complexing agent ammonia water solution and 4mol/L precipitator sodium hydroxide solution into the reaction kettle to carry out coprecipitation reaction under inert atmosphere, keeping the pH value between 11.4 and 12, controlling the reaction temperature to be about 60 ℃, reacting for 60h, then centrifugally filtering and separating, drying for 8h at 160 ℃ after washing to be neutral, and sieving to obtain the molecular formula of Ni0.3Mn0.6V0.05Al0.05(OH)2The sodium ion battery precursor material of (1);
uniformly mixing the sodium ion battery precursor and sodium carbonate according to the molar ratio of 1:1.15, roasting in a muffle furnace at the roasting temperature of 750 ℃ for 11h, cooling, crushing and sieving to obtain the NaNi molecular formula0.3Mn0.6V0.05Al0.05O2The positive electrode material for sodium ion batteries.
Dissolving the obtained positive electrode material of the sodium-ion battery and an active oxygen remover NiS2 in absolute ethyl alcohol according to the mass ratio of 90:1, performing ultrasonic dispersion for 30min, filtering, and performing vacuum drying on a solid mixture at 110 ℃ for 14h to obtain a dried product;
placing the dried product in a tubular furnace in nitrogen atmosphere, roasting at 600 ℃ for 10h, cooling to room temperature, and sieving to obtain the NiS2 coated NaNi with the molecular formula of0.3Mn0.6V0.05Al0.05O2The positive electrode material for sodium ion batteries. And testing the specific discharge capacity, capacity retention rate after circulation, decomposition temperature and high-temperature circulation retention rate of the doped coated sodium-ion battery anode material.
Example 2
Preparing a 2mol/L salt solution from a nickel chloride solution and a manganese chloride solution according to the molar ratio of nickel ions to manganese ions of 1: 9. Injecting prepared salt solution into a reaction kettle with the rotation speed of 450rpm at the speed of 15L/h, adding 0.2mol/L sodium metaaluminate solution and 0.2mol/L sodium vanadate solution prepared by dissolving ammonium metavanadate in sodium hydroxide into the reaction kettle at the speed of 1.5L/h at the same time, simultaneously adding 2mol/L complexing agent ammonia water solution and 4mol/L precipitator sodium hydroxide solution into the reaction kettle to carry out coprecipitation reaction in an inert atmosphere, keeping the pH value between 11.0 and 11.8, controlling the reaction temperature to be about 48 ℃, reacting for 100h, then centrifugally filtering and separating, washing to be neutral, drying for 14h at 100 ℃, and sieving to obtain the molecular formula Ni0.1Mn0.88V0.01Al0.01(OH)2The sodium ion battery precursor material of (1);
uniformly mixing the sodium ion battery precursor and sodium carbonate according to the molar ratio of 1:1.14, and roasting in a muffle furnace at the roasting temperature of 800 DEG CRoasting for 5 hours, cooling, crushing and sieving to obtain the NaNi molecular formula0.1Mn0.88V0.01Al0.01O2The positive electrode material for sodium ion batteries.
Dissolving the obtained positive electrode material of the sodium-ion battery and an active oxygen remover CoS2 in absolute ethyl alcohol according to the mass ratio of 100:1, performing ultrasonic dispersion for 25min, filtering, and performing vacuum drying on a solid mixture at 100 ℃ for 12h to obtain a dried product;
placing the dried product in a tubular furnace in nitrogen atmosphere, roasting at 650 ℃ for 9h, cooling to room temperature, and sieving to obtain the product of which the CoS2 coated molecular formula is NaNi0.1Mn0.88V0.01Al0.01O2The positive electrode material for sodium ion batteries. And testing the specific discharge capacity, capacity retention rate after circulation, decomposition temperature and high-temperature circulation retention rate of the doped coated sodium-ion battery anode material.
Example 3
Preparing a 2mol/L salt solution from a nickel acetate solution and a manganese acetate solution according to the molar ratio of nickel ions to manganese ions of 4: 1. Injecting prepared salt solution into a reaction kettle with the rotating speed of 400rpm at the speed of 6L/h, adding 0.5mol/L sodium metaaluminate solution and 0.2mol/L sodium vanadate solution prepared by dissolving vanadium pentoxide in sodium hydroxide into the reaction kettle at the speed of 4.0L/h at the same time, simultaneously adding 2mol/L complexing agent ammonia water solution and 4mol/L precipitator sodium hydroxide solution into the reaction kettle for coprecipitation reaction in an inert atmosphere, keeping the pH value between 10.6 and 11.0, controlling the reaction temperature to be about 50 ℃, reacting for 80 hours, then centrifugally filtering and separating, drying at 90 ℃ for 20 hours after washing to be neutral, and sieving to obtain the solution with the molecular formula of Ni0.72Mn0.18V0.01Al0.09(OH)2The sodium ion battery precursor material of (1);
uniformly mixing the sodium ion battery precursor and sodium carbonate according to the molar ratio of 1:1.2, roasting in a muffle furnace at the roasting temperature of 650 ℃ for 9 hours, cooling, crushing and sieving to obtain the NaNi molecular formula0.72Mn0.18V0.01Al0.09O2Sodium ion batteryAnd (3) a positive electrode material.
Dissolving the obtained positive electrode material of the sodium-ion battery and an active oxygen remover MnS2 in absolute ethyl alcohol according to the mass ratio of 95:1, performing ultrasonic dispersion for 15min, filtering, and performing vacuum drying on a solid mixture at 80 ℃ for 24h to obtain a dried product;
placing the dried product in a tubular furnace in nitrogen atmosphere, roasting at 700 ℃ for 8h, cooling to room temperature, and sieving to obtain the MnS2 coated NaNi with the molecular formula of NaNi0.72Mn0.18V0.01Al0.09O2The positive electrode material for sodium ion batteries. And testing the specific discharge capacity, capacity retention rate after circulation, decomposition temperature and high-temperature circulation retention rate of the doped coated sodium-ion battery anode material.
Example 4
Preparing a 2mol/L salt solution from a nickel nitrate solution and a manganese nitrate solution according to the molar ratio of nickel ions to manganese ions of 9: 1. Injecting prepared salt solution into a reaction kettle with the rotating speed of 320rpm at the speed of 10L/h, adding 0.2mol/L sodium metaaluminate solution and 0.5mol/L sodium vanadate solution prepared by dissolving ammonium metavanadate in sodium hydroxide into the reaction kettle at the speed of 1.5L/h at the same time, simultaneously adding 2mol/L complexing agent ammonia water solution and 4mol/L precipitator sodium hydroxide solution into the reaction kettle for coprecipitation reaction under inert atmosphere, keeping the pH value between 10.0 and 10.8, controlling the reaction temperature to be about 52 ℃, reacting for 70h, then centrifugally filtering and separating, washing to be neutral, drying at 120 ℃ for 12h, and sieving to obtain the molecular formula Ni0.72Mn0.18V0.01Al0.09(OH)2The sodium ion battery precursor material of (1);
uniformly mixing the sodium ion battery precursor and sodium carbonate according to the molar ratio of 1:1.05, roasting in a muffle furnace at the roasting temperature of 500 ℃ for 15h, cooling, crushing and sieving to obtain the NaNi with the molecular formula0.72Mn0.18V0.01Al0.09O2The positive electrode material for sodium ion batteries.
Dissolving the obtained positive electrode material of the sodium-ion battery and an active oxygen remover VS2 in absolute ethyl alcohol according to the mass ratio of 92:1, performing ultrasonic dispersion for 20min, filtering, and performing vacuum drying on the solid mixture at 120 ℃ for 10h to obtain a dried product;
placing the dried product in a tubular furnace in nitrogen atmosphere, roasting for 5h at 800 ℃, cooling to room temperature, and sieving to obtain NaNi with the VS2 coating molecular formula0.72Mn0.18V0.01Al0.09O2The positive electrode material for sodium ion batteries. And testing the specific discharge capacity, capacity retention rate after circulation, decomposition temperature and high-temperature circulation retention rate of the doped coated sodium-ion battery anode material.
Assembling a button cell and detecting:
the positive electrode materials of the sodium ion batteries obtained in comparative examples 1-2 and examples 1-4 are respectively assembled into 6 button batteries to carry out charge and discharge comparison tests, and the detection results are as follows:
table 1 shows specific discharge capacity test data of the positive electrode materials of the batteries obtained in comparative examples 1 to 2 and examples 1 to 4 and the positive electrode material of the conventional battery
From table 1, it can be derived: the button cell assembled by adopting the sodium ion battery anode material as the anode can achieve 113.5mAh/g of initial discharge specific capacity under 0.1C multiplying power, the capacity retention rate is 98.9% after 100 charge-discharge cycles, the initial efficiency can reach 96.32%, while the initial discharge specific capacity of the common sodium ion battery anode material is 105.8mAh/g, the initial efficiency is only 75.11%, the capacity retention rate is 80.8% after 100 charge-discharge cycles, the initial discharge specific capacity of the sodium ion battery anode material which is not coated by MS2 is 112.6mAh/g, the initial efficiency is 94.74%, and the capacity retention rate is 81.5% after 100 charge-discharge cycles; therefore, the battery prepared from the doped and coated positive electrode material for the sodium-ion battery has better discharge specific capacity, first efficiency, cycle performance and overall comprehensive performance than the conventional positive electrode material for the sodium-ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (9)
1. The doped coated sodium-ion battery positive electrode material is characterized in that the chemical structural formula of the material is NaNixMnyVzAl1-x-y-zO2，0.1≤x＜0.9，0.09≤y＜0.9，0.01≤z≤0.09。
2. A method of making the material of claim 1, comprising:
(1) adding a nickel source, a manganese source, a vanadium source and an aluminum source into a reaction kettle, simultaneously adding a complexing agent and a precipitator, and carrying out coprecipitation reaction under an inert atmosphere to obtain a semi-finished product of a precursor of the sodium-ion battery;
(2) centrifugally filtering and separating the sodium-ion battery precursor semi-finished product obtained in the step (1), washing to be neutral, drying and sieving to obtain the molecular formula NiaMnbVcAl1-a-b-c(OH)2The precursor of the positive electrode material of the sodium-ion battery is that a is more than or equal to 0.1 and less than 0.9, b is more than or equal to 0.09 and less than 0.9, and c is more than or equal to 0.01 and less than or equal to 0.09;
(3) uniformly mixing the sodium ion battery positive electrode material precursor obtained in the step (2) with sodium carbonate, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain a vanadium-aluminum doped sodium ion battery positive electrode material;
(4) dissolving the vanadium-aluminum doped sodium ion battery anode material obtained in the step (3) and an active oxygen remover MS2 in absolute ethyl alcohol for ultrasonic dispersion, filtering, and drying the solid mixture in vacuum to obtain a dried product;
(5) and (4) placing the dried product obtained in the step (4) in a tubular furnace in a nitrogen atmosphere for roasting, cooling to room temperature, and sieving to obtain the vanadium-aluminum doped MS2 coated sodium ion battery positive electrode material.
3. The preparation method according to claim 2, wherein the nickel source in the step (1) is one of nickel sulfate, nickel chloride, nickel acetate and nickel nitrate; the manganese source is one of manganese sulfate, manganese chloride, manganese acetate and manganese nitrate; the vanadium source is a sodium vanadate solution prepared by dissolving vanadium pentoxide or ammonium metavanadate in sodium hydroxide; the aluminum source is sodium metaaluminate; the complexing agent is ammonia water solution, and the precipitator is sodium hydroxide solution.
4. The preparation method of claim 2, wherein in the step (1), a nickel source and a manganese source are prepared into a 2mol/L salt solution according to a molar ratio of nickel ions to manganese ions of 1: 9-9: 1, the prepared salt solution is injected into a reaction kettle with a rotation speed of 320-450 rpm at a speed of 4-15L/h, meanwhile, 0.2-0.5 mol/L aluminum source and 0.2-0.5 mol/L vanadium source are added into the reaction kettle at a speed of 1-4L/h, meanwhile, 2mol/L complexing agent and 4mol/L precipitant are added into the reaction kettle for coprecipitation reaction, the pH is kept between 10 and 12, the reaction temperature is controlled at 48-60 ℃, and the reaction time is 40-100 h.
5. The preparation method according to claim 2, wherein the drying temperature in the step (2) is 90-160 ℃ and the drying time is 8-20 h.
6. The preparation method according to claim 2, wherein the sodium ion battery positive electrode material precursor and sodium carbonate in the step (3) are mixed in a molar ratio of 1: 1.05-1.2.
7. The preparation method as claimed in claim 2, wherein the step (3) is carried out at a roasting temperature of 500 ℃ and 800 ℃ for a roasting time of 5-15 h.
8. The preparation method of claim 2, wherein in the step (4), the positive electrode material of the sodium-ion battery and an active oxygen remover MS2 are subjected to ultrasonic dispersion for 15-30min according to a mass ratio (90-100) of 1, the obtained solid mixture is subjected to vacuum drying at 80-120 ℃ for 10-24h to obtain a dried product, and the active oxygen remover MS2 is at least one of NiS2, MnS2, CoS2 and VS 2.
9. The preparation method of claim 2, wherein the dried product in the step (5) is placed in a tube furnace under nitrogen atmosphere and roasted at 600-800 ℃ for 5-10 h.
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