CN112242525B - Nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped carbon-coated sodium vanadium manganese phosphate composite material, a preparation method and application thereof4MnV(PO4)3The diameter is about 1 μm, and the thickness of the carbon coating layer is 5-10 nm. The method is characterized in that oleic acid is used as a surfactant and a carbon source, paraffin is used as a non-polar solvent, a cheap sodium source, a phosphorus source, a manganese source, a vanadium source and a nitrogen source are adopted, and Na with a waxberry-shaped special appearance is prepared in a high yield by a simple ball milling method4MnV(PO4)3@ NC. When the material is used as the positive electrode of the sodium ion battery, the advantages of high working voltage, good cycling stability, good rate performance and the like are shown, and meanwhile, the preparation of the material lays a foundation for the development and scale application of the sodium ion energy storage battery with low cost and high performance.
Description
Technical Field
The invention relates to the field of material chemistry and high-energy battery material technology, in particular to a myrica nitrogen-doped carbon-coated vanadium manganese sodium phosphate positive electrode material for a high-performance sodium ion battery and a preparation method thereof.
Background
Energy and environmental issues have become a significant challenge facing the human 21 st century. The development of green renewable clean energy sources such as water energy, solar energy, wind energy, tidal energy, biological energy and the like to replace fossil energy is an effective way for realizing sustainable development and solving increasingly serious environmental problems. However, the instability and intermittency of these new energy sources greatly limit their grid-connected use, and the development of efficient energy storage systems for their use becomes especially important. Lithium ion batteries have been widely used in portable electronic devices and electric vehicles, and have good application prospects in the field of large-scale energy storage. However, lithium resources are limited and cannot meet large-scale energy storage requirements. In recent years, room temperature rechargeable sodium ion batteries have attracted renewed attention and are considered to be a next generation energy storage technology that can replace lithium ion batteries. At present, research aiming at the sodium ion battery mainly focuses on development of novel high-energy-density electrode materials, optimization of an electrolyte system and the like. The positive electrode material is a core factor directly influencing the overall performance of the battery and is the most important factor determining the cost of the sodium-ion battery, so that the development of the high-performance positive electrode material has important significance.
Currently, most of the positive electrode materials of sodium ion batteries include transition metal oxides, prussian blue analogues, polyanion compounds, and the like. The polyanion compound with the NASICON structure is a three-dimensional framework structure formed by strong covalent bonds, has high structural stability and rapid sodium ion diffusion rate, and has small volume change and less phase change in the ion de-intercalation process, thereby ensuring good cycle stability and excellent safety in the sodium ion battery. Na (Na)3V2(PO4)3Is a typical NASICON structural material which is researched more and has higher theoretical capacity (118mAh g)-1) And energy density (370Wh kg)-1). Although Na is present3V2(PO4)3Has the advantages of stable structure, etc., but the high price and high toxicity of vanadium still are the main obstacles of commercial application. For this, doping of elements to replace V is to solve Na3V2(PO4)3An effective means of solving a number of problems. Recently, Goodenough et al have introduced Na3V2(PO4)3Half of the middle V is substituted by other transition metals to synthesize a series of Na with NASICON structurexMV(PO4)3(M ═ Fe, Mn, Ni) compounds. Analysis from energy density and cost points of view, Na4MnV(PO4)3Has high theoretical capacity (111mAh g)-1) The working voltage is high (3.6V), and the manganese is low in price and low in toxicity. Thus, with Na3V2(PO4)3In contrast, Na4MnV(PO4)3Is a high specific energy anode material with wide application prospect. However, Na4MnV(PO4)3The conductivity of (2) is poor, resulting in difficulty in achieving the theoretical capacity. At the same time, for Na4MnV(PO4)3The research on the mechanism of sodium intercalation and the like is relatively lacking, and needs to be urgently neededThe deep understanding is realized.
The method improves Na by means of morphology design, surface modification and the like4MnV(PO4)3The electron/ion transmission rate of the material resolves the relevant sodium intercalation mechanism. This Na salt4MnV(PO4)3The @ NC composite material has good cycling stability, the capacity can be kept at 90.2% after 1000 cycles under the multiplying power of 5C, and the multiplying power performance is also very excellent.
Disclosure of Invention
The first purpose of the invention is to provide waxberry-shaped nitrogen-doped carbon-coated sodium vanadium manganese phosphate (Na)4MnV(PO4)3@ NC) composite material, aiming at providing a brand new positive electrode material of a sodium ion battery with unique appearance, good stability and excellent electrochemical performance. The material is coated with Na by a nitrogen-doped carbon layer4MnV(PO4)3The waxberry-shaped particle composite material is formed. The diameter of the composite material is 800-1200nm, and the thickness of the nitrogen-doped carbon coating layer is 5-10 nm.
The second purpose of the invention is to provide Na with waxberry-shaped appearance, which is simple to operate and low in cost4MnV(PO4)3The method of the @ NC cathode material enables large-scale production and industrial application of the cathode material.
Na4MnV(PO4)3The preparation method of the @ NC composite material comprises the following specific steps:
dissolving a vanadium source and oxalic acid in deionized water, heating and stirring until the solvent is completely volatilized, drying to obtain vanadyl oxalate, sequentially placing a phosphorus source, a carbon source, paraffin, vanadyl oxalate, a manganese source, a sodium source and a nitrogen source in a ball mill for ball milling, and heating and sintering the uniformly mixed materials in an inert atmosphere to obtain the vanadyl oxalate.
The vanadium source comprises: at least one of vanadium pentoxide and ammonium metavanadate; vanadium pentoxide is preferred.
The phosphorus source comprises: at least one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid, preferably ammonium dihydrogen phosphate.
The sodium source comprises: at least one of sodium acetate, sodium carbonate, sodium bicarbonate and sodium hydroxide, preferably sodium acetate.
The nitrogen source comprises: thiourea, allylthiourea, melamine, dicyandiamide, thiourea being preferred.
The manganese source comprises: at least one of manganese acetate, manganese carbonate, manganese nitrate hexahydrate, manganese acetylacetonate; manganese acetate is preferred.
The carbon source comprises: at least one of oleic acid, carbon nanotube and phenolic resin, preferably oleic acid.
The molar ratio of the vanadium source to the oxalic acid is 1: 2.9-3.1, preferably 1: 3.0; the sodium source, the vanadyl oxalate, the manganese source and the phosphorus source are mixed according to a molar ratio of Na to V to Mn to P of 3.8-4.2: 0.8-1.2: 0.8-1.2: 2.8-3.2, preferably 4: 1: 1: 3; the mass ratio of the sodium vanadium manganese phosphate to the paraffin to the carbon source to the nitrogen source is 0.8-1.2: 3.4-3.8: 1.7-2.1: 1.4-1.8, preferably 1: 3.6: 1.9: 1.6.
the temperature of the heating sintering treatment is 650-800 ℃; sintering for 2-8 h, preferably 800 ℃; sintering for 5 h.
The rotation speed of the ball milling is 300-400r/min, the ball milling time is 3-5 h, the preferred ball milling rotation speed is 360r/min, and the ball milling time is 4 h.
The heating rate of the heating sintering treatment is 1-5 ℃/min, preferably 2 ℃/min.
The inert atmosphere is Ar and H2The mixed gas of (3); h2H in mixed gas with Ar2The volume fraction is 3-20%, preferably 10%.
Na produced by the above method4MnV(PO4)3The @ NC material has a particle size of about 1 micron and is in a waxberry shape.
Na4MnV(PO4)3The carbon layer of the @ NC material is doped with nitrogen, so that the rapid transmission of sodium ions and electrons can be realized, and the material has excellent electrochemical performance.
The third purpose of the invention is to provide the Na with the brand-new waxberry-like morphology prepared by the method4MnV(PO4)3@ NC material in the field of sodium ion batteriesThe application of the domain, in particular to the technical field of the positive electrode material of the sodium-ion battery.
Na of the invention4MnV(PO4)3The @ NC composite material is used as a positive electrode material of the sodium-ion battery, the battery is assembled by adopting the existing method, and the electrochemical performance test is carried out: weighing Na according to the mass ratio of 7:2:14MnV(PO4)3The method comprises the following steps of @ NC composite material, acetylene black (conductive agent) and polyvinylidene fluoride (binder), fully and uniformly grinding in an agate mortar, adding N-methylpyrrolidone (NMP) to form uniform slurry, coating the slurry on an aluminum foil current collector to serve as a test electrode, assembling a button cell by using a metal sodium counter electrode, and adopting 1.0M NaClO electrolyte4in PC with 5% FEC, 1C ═ 111mA g when testing electrochemical performance-1。
Principle of the invention
The positive electrode material is a core factor directly influencing the overall performance of the battery and is the most important factor determining the cost of the sodium-ion battery. Na (Na)3V2(PO4)3Is a typical NASICON structural material, and is widely researched as a sodium ion positive electrode material due to high structural stability and rapid sodium ion diffusion rate. But the defects of poor electronic conductivity, low specific energy, expensive vanadium price, high toxicity and the like of the material limit the practical application of the material. Doping elements to replace V to solve Na3V2(PO4)3An effective means of solving a number of problems. The invention adopts transition metal Mn with low price and low toxicity to convert Na3V2(PO4)3Half of the medium V is substituted to synthesize a high-specific-energy anode material Na with wide application prospect4MnV(PO4)3. The nano material has excellent electrochemical performance due to the high specific surface area and the short ion transmission path, so the material nanocrystallization technology is an important way for greatly improving the electrochemical performance of the electrode material. Due to Na4MnV(PO4)3The electron conductivity of the material is low, and the carbon material coating can effectively improve the electron conductivity of the material and prevent the material from agglomerating. Nitrogen doping can introduce defects into the coated carbon layerSinking and promoting Na+Transportation and storage. Researches find that the carbon forming amount of different carbon sources after sintering is obviously different, the final electrochemical performance of the material is directly influenced by the coating quality of the carbon layer, and the electrochemical performance of the material is greatly different due to the difference of the nitrogen sources.
In addition, the invention improves the electron/ion transmission rate of the material by means of morphology design, surface modification and the like, and simultaneously reduces the cost and toxicity of the material, so that the material has good stability and excellent electrochemical performance. The preparation method has simple flow and convenient operation, and is suitable for large-scale production. The composite material prepared by the method has excellent electrochemical performance, and solves the problems of low capacity and short cycle life of the materials in the prior art.
Therefore, the invention designs a simple and easy ball milling method with high yield through means of bulk phase structure regulation, morphology design, surface modification optimization and the like, and the prepared novel waxberry-shaped Na with high energy density and excellent electrochemical performance4MnV(PO4)3@ NC electrode material.
The invention has the following beneficial effects:
1. the invention provides brand-new waxberry-shaped Na4MnV(PO4)3The material stability is improved by the @ NC composite material, and Na can be solved by the material3V2(PO4)3Low specific energy and high toxicity.
2. Na of the invention4MnV(PO4)3The @ NC composite material is in Na4MnV(PO4)3The carbon layer is uniformly coated on the particle surface, and nitrogen is doped on the carbon layer, so that the electron/ion transmission rate is favorably improved, and the electrochemical performance is excellent.
3. Na of the invention4MnV(PO4)3Carbon layer for Na in @ NC composite4MnV(PO4)3The cladding and the nitrogen-doped carbon-in layer are formed in one step in the sintering process, so that the process steps are greatly simplified.
4. Na of the invention4MnV(PO4)3The preparation process of the @ NC composite material is simple, the cheap sodium source, the phosphorus source, the manganese source, the carbon source and the like are adopted as raw materials, and the raw materials are uniformly mixed by ball milling, so that the cost is reduced, and the @ NC composite material is expected to be applied to large-scale production and industrialization.
5. Na of the invention4MnV(PO4)3The @ NC composite material shows high working voltage, good cycle stability and rate capability when being used as a positive electrode material of a sodium-ion battery.
Drawings
FIG. 1: XRD patterns of the composite materials prepared in examples 1, 6, 7 and comparative example 1;
FIG. 2: na prepared in example 14MnV(PO4)3SEM picture (a) and HRTEM picture (b) of @ NC-1 material;
FIG. 3: na prepared in comparative example 24MnV(PO4)3@ NC-9(a) and Na prepared in comparative example 94MnV(PO4)3SEM of @ NC-16 (b);
FIG. 4: XPS plot of example 1;
FIG. 5: cyclic voltammograms of example 1(a) and comparative example 1 (b).
FIG. 6: sodium ion batteries assembled from the materials prepared in examples 1 and 2 and comparative examples 2 and 9 were operated at 5C (1C 111mA · g)-1) Cycle performance graph below.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
Firstly 200mg V2O5And 416mg H2C2O4 .2H2Dissolving O in 25mL of deionized water, heating and stirring at 70 ℃ until the solution is completely volatilized to obtain vanadyl oxalate, and drying the vanadyl oxalate in an oven at 80 ℃ for 24 hours. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2And 1.5g of sulfurBall milling for 3H at 360r/min, oven drying the uniformly mixed material in a 105 deg.C oven for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@NC-1。
When the button cell is prepared, 35mg of active substance, 10mg of acetylene black and 5mg of polyvinylidene fluoride are weighed according to the mass ratio of 7:2:1, fully and uniformly ground in an agate mortar, a plurality of drops of N-methylpyrrolidone (NMP) are added, and smeared after uniform stirring. And (3) drying the electrode plates in a vacuum drying oven at the temperature of 80 ℃ for 6 hours, and then punching the electrode plates into electrode plates with the diameter of about 12mm, wherein the mass of active substances in each electrode plate is about 1.5 mg. 1.0M NaClO prepared by taking metal sodium as a negative electrode material4in PC with 5% FEC mixed solution as electrolyte, assembling button half cell (CR2016) in inert gas glove box (UNILAB MBRAUN, Germany), the glove box operating system is high purity argon. Activating in 30 deg.C thermostat for more than 6h, and testing its electrochemical data with Xinwei battery charging and discharging instrument. And a constant-current charging and discharging mode is adopted, and the voltage range is 2.5-3.8V. And performing cyclic voltammetry test on the Shanghai Chenghua electrochemical workstation at a scanning speed of 0.2 mV/s.
Example 2
Compared with the example 1, the difference is that the dosage of the oleic acid is reduced, and the specific steps are as follows:
vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.5g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@NC-2。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Example 3
Compared with the example 1, the difference is that the dosage of the oleic acid is increased, and the specific steps are as follows:
vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing the mixture and 2.5g of oleic acid in a ball milling tank for ball milling for 1 hour, adding 3.5g of paraffin into the ball milling tank for ball milling for 1 hour, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@NC-3。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Example 4
Compared with the example 1, the difference is that the dosage of thiourea is reduced, which is specifically as follows:
vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2And 0.5g of thiourea for 3 hours, wherein the ball milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@NC-4。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Example 5
Compared with the example 1, the difference is that the dosage of thiourea is increased, and the specific steps are as follows:
vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2Ball-milling 2.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@ NC-5. The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Example 6
Compared with the embodiment 1, the difference is that the sintering temperature is reduced, and the specific steps are as follows:
vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 700 ℃, and the heat preservation time is 5h4MnV(PO4)3@ NC-6. The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Example 7
Compared with the example 1, the difference is that the sintering time is reduced, and the specific steps are as follows:
vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4With 1.8g of oilAcid is put in a ball milling tank for ball milling for 1h, 3.5g of paraffin is added into the ball milling tank for ball milling for 1h, and vanadyl oxalate and 656mg of CH are sequentially added3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 2h to obtain the nano material named Na4MnV(PO4)3@ NC-7. The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Comparative example 1 (Nitrogen free source)
Vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa and 490mg Mn (CH)3COO)2Ball milling is carried out for 3 hours, and the ball milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@NC-8。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Comparative example 2 (without carbon source)
Vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the heating rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5hThe nano material is named as Na4MnV(PO4)3@NC-9。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Comparative example 3 (other carbon sources)
Vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Putting 1.8g of glucose into a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@ NC-10. The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Comparative example 4 (other Nitrogen sources)
Vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2And 1.5g of melamine are ball milled for 3 hours, and the ball milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@ NC-11. The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
COMPARATIVE EXAMPLE 5 (other phosphorus sources)
Vanadyl oxalate was prepared by the method described in example 1. 720mg of NaH2PO4Ball-milling with 1.8g oleic acid in a ball-milling jar for 1h3.5g of paraffin is added into the ball milling tank for ball milling for 1 hour, and then vanadyl oxalate and 164mg of CH are sequentially added3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@ NC-12. The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
COMPARATIVE EXAMPLE 6 (other sodium sources)
Vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and sequentially adding vanadyl oxalate and 424mg of Na2CO3、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@NC-13。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
COMPARATIVE EXAMPLE 7 (other manganese sources)
Vanadyl oxalate was prepared by the method described in example 1. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、230mg MnCO3Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the heating rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is prolongedThe nano material prepared for 5h is named as Na4MnV(PO4)3@NC-14。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
COMPARATIVE EXAMPLE 8 (other vanadium sources)
First 234mg NH4VO3And 416mg H2C2O4 .2H2Dissolving O in 25mL of deionized water, heating and stirring at 70 ℃ until the solution is completely volatilized to obtain vanadyl oxalate, and drying the vanadyl oxalate in an oven at 80 ℃ for 24 hours. 690mg of NH4H2PO4Placing 1.8g of oleic acid in a ball milling tank for ball milling for 1h, adding 3.5g of paraffin into the ball milling tank for ball milling for 1h, and then sequentially adding vanadyl oxalate and 656mg of CH3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours, wherein the ball-milling rotating speed is 360 r/min; placing the uniformly mixed material in an oven at 105 deg.C, baking for 30min, and adding 10% H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the temperature rise rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5h, so that the prepared nano material is named as Na4MnV(PO4)3@NC-15。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
COMPARATIVE EXAMPLE 9 (No Paraffin)
Firstly 200mg V2O5And 416mg H2C2O4 .2H2Dissolving O in 25mL of deionized water, heating and stirring at 70 ℃ until the solution is completely volatilized to obtain vanadyl oxalate, and drying the vanadyl oxalate in an oven at 80 ℃ for 24 hours. 690mg of NH4H2PO4Placing the mixture and 1.8g of oleic acid in a ball milling tank for ball milling for 2h, and then adding vanadyl oxalate and 656mg of CH in sequence3COONa、490mg Mn(CH3COO)2Ball-milling with 1.5g of thiourea for 3 hours at the ball-milling speed of 360r/min, placing the uniformly mixed material in a drying oven at 105 ℃ for drying for 30min, and drying in a drying oven containing 10% of H2Ar/H of (1)2Sintering the sample at high temperature in the atmosphere, wherein the heating rate is 2 ℃/min, the temperature is controlled at 800 ℃, and the heat preservation time is 5hMaterial name is Na4MnV(PO4)3@NC-16。
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Table 1 shows electrochemical properties of sodium ion batteries assembled with the target materials prepared in examples 1 to 7 and comparative examples 1 to 9 as positive electrodes at a current density of 5C.
TABLE 1
Claims (5)
1. The nitrogen-doped carbon-coated sodium vanadium manganese phosphate composite material is characterized in that a nitrogen-doped carbon layer coats Na4MnV(PO4)3The waxberry-like particle composite material is formed; the preparation method of the nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material comprises the following steps:
dissolving a vanadium source and oxalic acid in deionized water, heating and stirring until the solvent is completely volatilized, drying to obtain vanadyl oxalate, sequentially placing a phosphorus source, a carbon source, paraffin, vanadyl oxalate, a manganese source, a sodium source and a nitrogen source in a ball mill for ball milling, and heating and sintering the uniformly mixed materials in an inert atmosphere to obtain the vanadyl oxalate;
the vanadium source is vanadium pentoxide;
the phosphorus source is ammonium dihydrogen phosphate;
the sodium source is sodium acetate;
the nitrogen source is thiourea;
the manganese source is manganese acetate;
the carbon source is oleic acid;
the molar ratio of the vanadium source to the oxalic acid is 1: 2.9-3.1, wherein the molar ratio of the sodium source, the vanadyl oxalate, the manganese source and the phosphorus source in terms of Na: V: Mn: P is 3.8-4.2: 0.8-1.2: 0.8-1.2: 2.8-3.2, wherein the mass ratio of sodium vanadium manganese phosphate, paraffin, carbon source and nitrogen source is 0.8-1.2: 3.4-3.8: 1.7-2.1: 1.4 to 1.8;
the temperature of the heating sintering treatment is 650-800 ℃; sintering for 2-8 h.
2. The N-doped carbon-coated vanadium manganese sodium phosphate composite material as claimed in claim 1, wherein the diameter of the composite material is 800-1200nm, and the thickness of the N-doped carbon coating layer is 5-10 nm.
3. The N-doped carbon-coated vanadium manganese sodium phosphate composite material as claimed in claim 1, wherein the rotation speed of ball milling is 300-400r/min, and the ball milling time is 3-5 h.
4. The nitrogen-doped carbon-coated sodium vanadium manganese phosphate composite material of claim 1, wherein the inert atmosphere is Ar and H2The mixed gas of (3); h2H in mixed gas with Ar2The volume fraction is 3-20%.
5. The method for using the nitrogen-doped carbon-coated sodium vanadium manganese phosphate composite material according to any one of claims 1 to 4, wherein the nitrogen-doped carbon-coated sodium vanadium manganese phosphate composite material is used as a sodium ion battery positive electrode material.
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