CN111082059A - V-doped P2 type sodium ion battery positive electrode material and preparation method thereof - Google Patents
V-doped P2 type 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 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910016614 MnaMb Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000011572 manganese Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 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 6
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a V-doped P2 type sodium ion battery anode material and a preparation method thereof. The chemical formula of the positive electrode material of the sodium-ion battery is as follows: na (Na)xMnaMbVcO2(wherein x, a, b and c are mole numbers, x is more than 0.44 and less than 1, a is more than or equal to 0.4 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 0.4, c is more than 0 and less than or equal to 0.2, and M is one or more of metal ions of Ni, Co, Mg, Al, Zn, Ti, Cu and Fe). The V-doped P2 type sodium ion battery anode material is prepared by preparing a precursor by a simple sol-gel method and performing high-temperature solid-phase sintering reaction. The V-doped P2 type sodium ion battery anode material can inhibit the material from generating irreversible phase transformation, improve the conductivity and the sodium ion diffusion coefficient, and effectively improve the cycle performance, the rate capability and the safety performance of the materialThe method is low in cost, environment-friendly and easy to realize industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of preparation of sodium ion battery electrode materials, and particularly relates to a V-doped P2 type sodium ion battery positive electrode material and a preparation method thereof.
Background
With the rapid development of lithium ion battery technology in recent years, lithium ion batteries have been applied to various aspects of our lives, including portable devices such as mobile phones and computers, power batteries of new energy vehicles, energy storage devices of wind energy and solar power stations, and the like, and the huge energy demand makes people focus on the research of sodium ion batteries. The layered transition metal oxide is widely noticed as a positive electrode material of a sodium ion battery due to easy synthesis and high electrochemical activity, wherein the positive electrode material of the P2 type sodium ion battery is researched more due to high capacity, but irreversible phase transition can also occur in the circulation process, so that the capacity attenuation is fast, and the application of the positive electrode material of the P2 type sodium ion battery is limited.
The current methods for improving the electrochemical performance of the positive electrode material of the P2 type sodium ion battery mainly comprise surface coating and bulk phase doping. The surface coating is to coat a layer of protective film on the surface of the material, thereby preventing the anode material from directly contacting and reacting with the electrolyte and improving the stability of the material. Bulk doping, i.e. using metal ions (Al)3+、Mg2+Or Fe2+Etc.) to replace partial ions in the body of the anode material, thereby stabilizing the material structure, inhibiting the phase transformation problem and improving the cycle stability performance. In recent years, although there are many patents disclosing the improvement of the performance of the lithium ion battery by V doping, no report is found on the research of the positive electrode material of the P2 type sodium ion battery by V doping.
Disclosure of Invention
The invention aims to provide a V-doped P2 type sodium ion battery anode material and a preparation method thereof, which improve the preparation process of the existing sodium ion battery anode material, can inhibit the irreversible phase transformation of the material, improve the conductivity and the sodium ion diffusion coefficient, effectively improve the cycle performance, the rate capability and the safety performance of the material, and are suitable for industrial application.
The purpose of the invention is realized by the following technical scheme.
The V-doped P2 type sodium ion battery positive electrode material has a chemical formula of NaxMnaMbVcO2Wherein x, a, b and c are mole numbers, x is more than 0.44 and less than 1, a is more than or equal to 0.4 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 0.4, c is more than 0 and less than or equal to 0.2, and M is one or more of metal ions of Ni, Co, Mg, Al, Zn, Ti, Cu and Fe.
The preparation method of the V-doped P2 type sodium ion battery positive electrode material comprises the following steps:
1) according to the chemical formula NaxMnaMbVcO2Weighing manganese salt, metal M salt and vanadium source according to the molar ratio of Mn, M and V elements, dissolving the manganese salt, the metal M salt and the vanadium source in a proper amount of water, adding 1-5 mol% of excessive sodium salt, stirring and dissolving to prepare a mixed solution;
2) heating and stirring the mixed solution obtained in the step 1), adding an additive, stirring and evaporating to dryness to obtain gel;
3) drying and crushing the gel obtained in the step 2), pre-burning in the air atmosphere, then sintering, and cooling to room temperature to obtain the V-doped P2 type sodium ion battery anode material.
Further, the sodium salt, the manganese salt and the metal M salt in the step 1) are one or more of sulfate, nitrate and acetate.
Further, the vanadium source in the step 1) is one or more of ammonium metavanadate, vanadyl sulfate and vanadyl oxalate.
Further, the additive in the step 2) is one or more of citric acid, glycol and tartaric acid; the dosage of the additive is 20-50% of the mass of the manganese salt, the metal M salt and the vanadium source.
Further, the temperature for evaporating in the step 2) is 80-100 ℃.
Further, the drying in the step 3) is vacuum drying at the temperature of 100-120 ℃.
Further, the pre-sintering in the step 3) is carried out by heating to 400-600 ℃ at a heating rate of 1-5 ℃/min and preserving the heat for 4-6 hours.
Further, in the step 3), the temperature is raised to 900-.
Compared with the prior art, the invention has the following advantages and technical effects:
1. the preparation method disclosed by the invention is simple to operate, low in cost, environment-friendly and easy to realize industrial large-scale production.
2. According to the invention, by using the V-doped P2 type sodium ion battery anode material, irreversible phase transformation of the material can be inhibited, the conductivity and the sodium ion diffusion coefficient are improved, and the cycle performance, the rate capability and the safety performance of the material are effectively improved.
Drawings
FIG. 1 shows the positive electrode material Na of the V-doped P2 type Na-ion battery obtained in example 1 of the present invention0.65Mn0.72Ni0.17Co0.1V0.01O2And XRD pattern of pure NaNCM material in comparative example.
FIG. 2a and FIG. 2b are respectively a positive electrode material Na of the V-doped P2 type Na-ion battery obtained in example 1 of the present invention0.65Mn0.72Ni0.17Co0.1V0.01O2SEM image of pure NaNCM material in comparison example.
FIG. 3a and FIG. 3b show the positive electrode material Na of the V-doped P2 type Na-ion battery obtained in example 1 of the present invention0.65Mn0.72Ni0.17Co0.1V0.01O2The graph is compared with the first charge and discharge curves of the pure NaNCM material in the comparative example at 0.1C and 1C rates respectively.
FIG. 4 shows the positive electrode material Na of the V-doped P2 type Na-ion battery obtained in example 1 of the present invention0.65Mn0.72Ni0.17Co0.1V0.01O2Compare the graph with the cycle performance curve of the pure NaNCM material in the comparative example at 1C rate.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to the following examples and drawings, but the present invention is not limited thereto.
Example 1:
(1) according to the synthesis of 10g of Na0.65Mn0.72Ni0.17Co0.1V0.01O2And weighing manganese nitrate, nickel nitrate, cobalt nitrate and ammonium metavanadate according to the molar ratio of Mn, Ni, Co and V elements, dissolving the manganese nitrate, the nickel nitrate, the cobalt nitrate and the ammonium metavanadate in 200mL of deionized water, adding 1 mol% of excessive sodium nitrate, continuously stirring, weighing 2g of citric acid after metal salts are dissolved, adding the citric acid into the solution, stirring and evaporating at 80 ℃ to dryness, and thus obtaining the gel substance.
(2) Drying the gel obtained in the step (1) at 120 ℃ in vacuum, crushing, heating to 450 ℃ at the heating rate of 1 ℃/min in the air atmosphere for pre-sintering for 6 hours, then heating to 950 ℃ for sintering for 15 hours, and cooling to room temperature to obtain the positive electrode material Na of the V-doped P2 type sodium-ion battery0.65Mn0.72Ni0.17Co0.1V0.01O2。
(3) X-ray powder diffraction (XRD) analysis shows that the obtained product has the same structure with pure NaNCM, has high crystallinity, belongs to P2-type layered structure and has a space group of P63And/mmc (as shown in figure 1). It can be seen from the Scanning Electron Microscope (SEM) image that the material has a sheet-like morphology, and the morphology does not change before and after doping (as shown in fig. 2 a).
(4) V-doped P2 type sodium-ion battery positive electrode material Na at 25 DEG C0.65Mn0.72Ni0.17Co0.1V0.01O2The specific first discharge capacity of the capacitor is 156.0mAh/g at the multiplying power of 0.1C and between 1.5 and 4.2V, the specific first discharge capacity of the capacitor is 139.8mAh/g at the multiplying power of 1C (shown in figure 3 a), the specific discharge capacity of the capacitor is 115.3mAh/g after the capacitor is cycled for 100 circles at the multiplying power of 1C, and the capacity retention rate of the capacitor is 85 percent (shown in figure 4). From the above results, it was found that the positive electrode material Na of the V-doped P2 type sodium ion battery was used0.65Mn0.72Ni0.17Co0.1V0.01O2Stable structure, high specific capacity, good cycling stability and excellent electrochemical performance.
Example 2:
(1) according to the synthesis of 10g of Na0.45Mn0.66Ni0.22Fe0.08V0.04O2Manganese sulfate, nickel sulfate, ferric sulfate and vanadyl sulfate are weighed according to the molar ratio of Mn, Ni, Fe and V elements and dissolved in 250mL of deionized water, 2 mol% of excessive sodium sulfate is added, stirring is continuously carried out, after metal salts in the step are dissolved, 3g of tartaric acid is weighed, added into the solution, stirred and evaporated to dryness at 85 ℃, and the gel substance is obtained.
(2) Drying the gel obtained in the step (1) at 115 ℃ in vacuum, crushing, heating to 500 ℃ at the heating rate of 2 ℃/min in the air atmosphere for presintering for 5 hours, then heating to 925 ℃ for sintering for 16 hours, and cooling to room temperature to obtain the Na-doped P2 type sodium ion battery positive electrode material0.45Mn0.66Ni0.22Fe0.08V0.04O2。
(3) Activating at 25 deg.C for three times at 0.1C rate of 1.5-4.2V, performing charge-discharge cycle at 1C rate for 100 times, and doping Na as positive electrode material of P2 type sodium-ion battery with V0.45Mn0.66Ni0.22Fe0.08V0.04O2Stable structure, high specific capacity, good cycling stability and excellent electrochemical performance.
Example 3:
(1) according to the synthesis of 10g of Na0.67Mn0.7Ni0.22V0.08O2Weighing manganese acetate, nickel acetate and vanadyl oxalate according to the molar ratio of Mn, Ni and V elements, dissolving the manganese acetate, the nickel acetate and the vanadyl oxalate in 150mL of deionized water, adding 3 mol% of sodium acetate in excess, continuously stirring, weighing 1g of citric acid after the metal salts are dissolved, adding the citric acid into the solution, stirring and evaporating at 90 ℃ to dryness, and obtaining the gel substance.
(2) Drying the gel obtained in the step (1) at 100 ℃ in vacuum, crushing, heating to 600 ℃ at the heating rate of 3 ℃/min in the air atmosphere for presintering for 4 hours, then heating to 900 ℃ for sintering for 18 hours, and cooling to room temperature to obtain the positive electrode material Na of the V-doped P2 type sodium-ion battery0.67Mn0.7Ni0.22V0.08O2。
(3) Activating at 25 deg.C for three times at 0.1C rate of 1.5-4.2V, performing charge-discharge cycle at 1C rate for 100 times, and doping Na as positive electrode material of P2 type sodium-ion battery with V0.67Mn0.7Ni0.22V0.08O2Stable structure, high specific capacity, good cycling stability and excellent electrochemical performance.
Example 4:
(1) according to the synthesis of 10g of Na0.67Mn0.95V0.05O2Weighing manganese nitrate and ammonium metavanadate according to the molar ratio of Mn and V elements, respectively dissolving the manganese nitrate and the ammonium metavanadate in 300mL of deionized water, adding 5 mol% of sodium nitrate in excess, continuously stirring, weighing 5g of citric acid after the metal salts are dissolved in the step, adding the citric acid into the solution, stirring and evaporating at 100 ℃ to dryness, and thus obtaining the gel substance.
(2) Drying the gel obtained in the step (1) at 110 ℃ in vacuum, crushing, heating to 400 ℃ at the heating rate of 5 ℃/min in the air atmosphere for presintering for 6 hours, then heating to 1000 ℃ for sintering for 12 hours, and cooling to room temperature to obtain the positive electrode material Na of the V-doped P2 type sodium-ion battery0.67Mn0.95V0.05O2。
(3) Activating at 25 deg.C for three times at 0.1C rate of 1.5-4.2V, performing charge-discharge cycle at 1C rate for 100 times, and doping Na as positive electrode material of P2 type sodium-ion battery with V0.67Mn0.95V0.05O2Stable structure, high specific capacity, good cycling stability and excellent electrochemical performance.
Comparative example:
(1) according to the synthesis of 10g of Na0.65Mn0.72Ni0.17Co0.11O2Weighing manganese nitrate, nickel nitrate and cobalt nitrate according to the molar ratio of Mn, Ni and Co elements, respectively dissolving the manganese nitrate, the nickel nitrate and the cobalt nitrate in 200mL of deionized water, adding 1 mol% of sodium nitrate in excess, continuously stirring, weighing 2g of citric acid after the metal salts are dissolved, adding the citric acid into the solution, stirring and evaporating at 80 ℃ to dryness, and obtaining the gel substance.
(2) Drying the gel obtained in the step (1) in vacuum at 120 ℃, crushing, and carrying out air atmosphereHeating to 450 ℃ at the heating rate of 1 ℃/min for presintering for 6 hours, then heating to 950 ℃ for sintering for 15 hours, and cooling to room temperature to obtain the positive electrode material Na of the P2 type sodium-ion battery0.65Mn0.72Ni0.17Co0.11O2。
(3) X-ray powder diffraction (XRD) analysis shows that the obtained product is a pure-phase NaNCM, belongs to a P2-type lamellar structure, and has a space group of P63And/mmc (as shown in figure 1). It can be seen in the Scanning Electron Microscope (SEM) image that the material exhibits a plate-like morphology (as shown in fig. 2 b).
(4) The positive electrode material Na of the P2 type sodium ion battery is used when the charge-discharge cycle is carried out at 25 ℃ and the multiplying power of 0.1C between 1.5V and 4.2V0.65Mn0.72Ni0.17Co0.11O2The first discharge specific capacity of (1) was 148.3mAh/g, and the first discharge specific capacity at 1C rate was 134.1mAh/g (as shown in FIG. 3 b). The specific capacity after 100 cycles was 85.7mAh/g and the capacity retention rate was only 64% when charging and discharging were performed at a rate of 1C at 25 deg.C (as shown in FIG. 4).
Claims (10)
1. The V-doped P2 type sodium-ion battery positive electrode material is characterized in that the chemical formula of the V-doped P2 type sodium-ion battery positive electrode material is NaxMnaMbVcO2Wherein x, a, b and c are mole numbers, x is more than 0.44 and less than 1, a is more than or equal to 0.4 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 0.4, c is more than 0 and less than or equal to 0.2, and M is one or more of metal ions of Ni, Co, Mg, Al, Zn, Ti, Cu and Fe.
2. The method for preparing the positive electrode material of the V-doped P2 type sodium-ion battery of claim 1, which is characterized by comprising the following steps:
1) according to the chemical formula NaxMnaMbVcO2Weighing manganese salt, metal M salt and vanadium source according to the molar ratio of Mn, M and V elements, dissolving the manganese salt, the metal M salt and the vanadium source in water, adding sodium salt, stirring and dissolving to prepare a mixed solution;
2) heating and stirring the mixed solution obtained in the step 1), adding an additive, stirring and evaporating to dryness to obtain gel;
3) drying and crushing the gel obtained in the step 2), pre-burning in the air atmosphere, then sintering, and cooling to room temperature to obtain the V-doped P2 type sodium ion battery anode material.
3. The preparation method of claim 2, wherein the sodium salt, the manganese salt and the metal M salt in the step 1) are one or more of sulfate, nitrate and acetate.
4. The preparation method according to claim 2, wherein the vanadium source in step 1) is one or more of ammonium metavanadate, vanadyl sulfate and vanadyl oxalate.
5. The preparation method of claim 2, wherein the additive in step 2) is one or more of citric acid, ethylene glycol and tartaric acid; the dosage of the additive is 20-50% of the mass of the manganese salt, the metal M salt and the vanadium source.
6. The method according to claim 2, wherein the temperature for evaporating in step 2) is 80-100 ℃.
7. The method as claimed in claim 2, wherein the drying in step 3) is performed under vacuum at 100-120 ℃.
8. The method as claimed in claim 2, wherein the pre-sintering in step 3) is performed by raising the temperature to 400-600 ℃ at a temperature raising rate of 1-5 ℃/min and maintaining the temperature for 4-6 hours.
9. The method as claimed in claim 2, wherein the sintering in step 3) is performed by raising the temperature to 900-1000 ℃ at a temperature raising rate of 1-5 ℃/min, and maintaining the temperature for 12-18 hours.
10. The method according to claim 2, wherein the sodium salt is added in an excess of 1 mol% to 5 mol% in step 1).
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