CN113659139A - Vanadium sodium phosphate electrode material of vanadium-position copper-doped composite carbon nanotube and preparation method and application thereof - Google Patents
Vanadium sodium phosphate electrode material of vanadium-position copper-doped composite carbon nanotube and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 63
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 52
- 239000007772 electrode material Substances 0.000 title claims abstract description 29
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 25
- 235000006408 oxalic acid Nutrition 0.000 claims description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 235000017281 sodium acetate Nutrition 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 12
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 12
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001431 copper ion Inorganic materials 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
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- 238000011056 performance test Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
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- 238000004146 energy storage Methods 0.000 description 5
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
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- 239000010405 anode material Substances 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
The invention belongs to the technical field of new energy materials, and provides a vanadium sodium phosphate electrode material of a vanadium-position copper-doped composite carbon nanotube, and a preparation method and application thereof. The electrode material is as follows: na (Na)3+xV2‑ xCux(PO4)3@5% CNTs, x =0.01, 0.04, 0.07, 0.1. Positive divalent copper ions replace positive trivalent vanadium ions, holes are introduced into NVP unit cells, the internal electronic conductivity of the material is improved, an ion transmission channel is widened, the unit cell structure is stabilized, the ionic conductivity of the material is remarkably improved, and the structure is stableAnd (4) sex. The carbon nano tubes with high electronic conductivity are compounded to form a conductive frame which is embedded layer by layer, so that the electronic conductivity among the active particles is improved. The intrinsic conductivity and the crystal structure stability of the NVP electrode material are comprehensively improved in multiple angles, and the obtained material serving as the positive electrode of the sodium ion battery has excellent rate performance and high-rate long-cycle stability. The preparation method is simple and convenient to operate, easy to control and considerable in yield.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a vanadium sodium phosphate electrode material of a vanadium-position copper-doped composite carbon nanotube, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in the field of portable electronic devices due to their significant advantages of high energy density, long cycle life, and the like, and are gradually being generalized to large-scale energy storage systems. However, based on the requirement of large-scale energy storage system popularization, the ideal energy storage system not only needs to have good energy storage characteristics, but also needs to meet the requirements of sustainable development such as low cost, wide raw material sources and the like. However, the widespread use of lithium batteries worldwide increases the consumption of lithium resources, and the cost and raw materials of lithium batteries will limit the future development of lithium batteries accompanied by the problems of uneven distribution of lithium ore resources and high exploitation difficulty. Sodium ion batteries are ideal large-scale energy storage systems due to cost and performance advantages. The sodium element is abundant in the earth crust, the raw materials are wide in source in the preparation process, and the price is low. And the sodium ion battery has the same rocking chair type charging and discharging mechanism as the lithium ion battery, and the electrochemical performance is equivalent to the lithium ion battery. However, the energy density of the sodium ion battery is slightly lower due to the larger ion radius and mass, so the research and development of sodium ion electrode materials which have high energy density, long cycle life and low cost and are suitable for industrialization is urgent.
As a carrier of sodium ions, the positive electrode material is one of the key elements of the sodium ion battery, is responsible for providing active sodium ions and a high-potential redox couple, and directly influences important parameters such as specific capacity, working voltage and the like of the battery.
Gather yinIonic compound Na3V2(PO4)3The (NVP for short) has a sodium super ion conductor (NASICON) type three-dimensional framework structure, provides stable sodium storage sites, and an open three-dimensional ion channel is favorable for the diffusion of sodium ions. Based on 2 Na simultaneously+Reversible deintercalation may provide 117.6 mAh g-1The sum of the theoretical specific capacity of (1) and (400 Wh kg)-1The energy density of (1). However, due to the large difference between the V3d and the O2p orbital level, the electron conductance and the ion conductivity of NVP are low; at the same time, in Na+Volume deformation is generated in the de-intercalation process, and the generated lattice stress can cause the particle surface to generate gaps and be unstable, thereby causing capacity loss and side reaction. Therefore, how to improve the electronic and ionic conductivity of the NVP, and meanwhile, the stability of the crystal structure of the material is enhanced, so that the intrinsic conductivity of the NVP is improved, and the method has great significance for promoting the industrial development of the NVP.
The improvement of the crystal structure of the material by bulk phase doping is studied to improve the ionic conductivity, and the introduction of high-conductivity carbon-based material to compound with NVP to improve the electronic conductivity of the material is also disclosed. However, a single modification method cannot effectively solve multiple problems of poor conductivity of NVP ions and electrons, weak structural stability and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a vanadium sodium phosphate electrode material which is doped with vanadium-position copper and simultaneously compounded with a conductive carbon nano tube, and a preparation method and application thereof. Positive divalent copper ions replace positive trivalent vanadium ions, and holes are introduced into NVP unit cells, so that the internal electronic conductivity of the material is improved; by utilizing the characteristic that the radius of bivalent copper ions is larger than that of trivalent vanadium ions, the ion transmission channel is widened by doping, the unit cell structure is stabilized, and the ionic conductivity and the structural stability of the material are obviously improved. In addition, the carbon nano tube material with high electronic conductivity is compounded to form a layer-by-layer embedded conductive frame, so that the electronic conductivity among the NVP active particles is further improved. The intrinsic conductivity and the crystal structure of the NVP electrode material are comprehensively improved from multiple angles, and the obtained NVP modified material as a sodium ion battery positive electrode shows excellent electrochemical performance: has excellent multiplying power performance and large multiplying power long cycle stability. Meanwhile, the preparation method is simple and convenient to operate, easy to control and considerable in yield.
The invention is realized by the following technical scheme: a vanadium sodium phosphate electrode material of a vanadium-position copper-doped composite carbon nanotube is characterized in that the vanadium sodium phosphate electrode material of the vanadium-position copper-doped composite carbon nanotube is as follows: na (Na)3+xV2-xCux(PO4)3@5% CNTs, x =0.01, 0.04, 0.07, 0.1; the electrode material is prepared from ammonium metavanadate, sodium acetate and sodium dihydrogen phosphate as raw materials, oxalic acid as a template and a carbon source and 5wt% of carbon nano tubes as auxiliary materials to obtain the carbon nano tubes and Na coated with carbon3V2(PO4)3And compounding the particles to form a three-dimensional conductive frame structure, wherein copper nitrate is used as a doping source, and the copper-doped sodium vanadium phosphate material is compounded and distributed in the carbon nano tube.
The method for preparing the vanadium sodium phosphate electrode material of the vanadium-position copper-doped composite carbon nano tube comprises the steps of preparing the vanadium sodium phosphate electrode material of the vanadium-position copper-doped composite carbon nano tube by using ammonium metavanadate, sodium acetate, ammonium dihydrogen phosphate, oxalic acid and the carbon nano tube as raw materials, copper nitrate as a doping source and deionized water as a solvent through a liquid phase method.
The method comprises the following specific steps:
(1) sequentially dissolving oxalic acid and sodium acetate in 50 mL of deionized water, respectively and sequentially adding ammonium metavanadate and sodium dihydrogen phosphate into the solution, heating the solution in a water bath kettle to 80 ℃, preserving the temperature, and stirring the solution for 12 hours to obtain black blue sol;
(2) adding carbon nanotubes into the black-blue sol, wherein the mass of the carbon nanotubes is 5% of that of the NVP sample, uniformly dispersing the carbon nanotubes in the sol by using a cell crusher, and freeze-drying the mixture for 48 hours to obtain a powdery sample;
(3) placing the powdery sample in a ceramic boat to carry out primary firing in a tube furnace, wherein the primary firing condition is that the temperature is kept at 450 ℃ for 4 hours in a nitrogen atmosphere, and the heating speed is 2 ℃/min;
(4) taking out a sample, grinding the sample in a mortar for 30min, pressing sample powder into a wafer by using a tablet machine, and carrying out final firing under the condition that the temperature is kept at 700 ℃ in a nitrogen atmosphere for 12 hours, wherein the temperature rising speed is 2 ℃/min;
(5) and grinding the sample after final burning for 30min to obtain the modified powdery sample.
The invention uses the stoichiometric ratio of 2-x: x: 3: x: 3 ammonium metavanadate, copper nitrate trihydrate, oxalic acid, sodium acetate trihydrate, sodium dihydrogen phosphate (x =0.01, 0.04, 0.07, 0.1) starting materials all doped samples were synthesized.
The vanadium sodium phosphate electrode material of the vanadium-position copper-doped composite carbon nano tube is applied to a sodium ion battery as a positive electrode material.
The specific application method comprises the following steps: na (Na)3+xV2-xCux(PO4)3The 2016 type button cell is assembled by using @5% CNTs as active substances of positive electrode materials and sodium sheets as negative electrodes, and the electrolyte is 1 mol L-1NaClO (sodium chloride)4Dissolving in PC solvent, adding 5wt% of FEC as additive, and the diaphragm is ceramic diaphragm.
Oxalic acid is used as a carbon source, not only is the carbon source finally formed into amorphous carbon coating coated on the surface of product particles, but also is used as a reducing agent and a chelating agent to carry out the reaction of V5+Reduction to V3+. The addition of the carbon material is beneficial to constructing a carbon network in the preparation process, and the addition of the carbon material can also enhance the dispersion among particles and reduce agglomeration.
The invention synthesizes Na uniformly coated on the tubular carbon nano tube by using oxalic acid as a template and a carbon source assisted by 5wt% of the carbon nano tube3V2(PO4)3the/C-CNT composite material is doped with divalent copper ions on the basis, so that the electrochemistry of the material is further improved, the anode material is further nanocrystallized by using a liquid phase method, and a foundation is laid for further research of the anode material of the sodium ion battery.
The vanadium phosphate sodium electrode material of the vanadium-position copper-doped composite carbon nano tube is prepared by a simple and easily-obtained sol-gel method and is applied as a positive electrode material of a sodium ion battery. The divalent copper ions are adopted for doping, and the high-conductivity carbon nano tube is compounded, so that the advantages of the double modification strategy are obvious.
According to the invention, positive divalent copper ions are used for replacing positive trivalent vanadium ions, and holes are introduced into NVP unit cells by utilizing the semiconductor acceptor doping principle, so that the electron conductivity characteristics in the material can be obviously improved; meanwhile, by utilizing the characteristic that the radius of the divalent copper ions is larger than that of the trivalent vanadium ions, the ion transmission channel can be effectively widened by substitution; the doped copper ions can be used as the crystal structure of the pillar ion stabilizing material, and the ionic conductivity and the structural stability of the material are obviously improved.
The copper-doped vanadium sodium phosphate active particles are uniformly distributed in the carbon nano tube, and the carbon nano tube can keep a fiber hollow tubular structure without collapsing, so that the sodium ion transmission is facilitated. Proper amount of carbon nano tube and carbon-coated Na3V2(PO4)3The particles are compounded to form a three-dimensional conductive frame structure, and the layer-by-layer embedded conductive structure remarkably enhances the electronic conductivity, thereby improving the multiplying power performance of the electronic conductive frame structure.
The NVP electrode material obtained after modification treatment is assembled into a button cell to test electrochemical performance, the NVP electrode material is cycled for 100 circles under the condition of 1C medium and high multiplying power, and the reversible specific capacity of the modified cell is improved by 40 mAh g-1(ii) a Under different charge-discharge multiplying power cycle tests, the high-multiplying power performance is remarkably improved, and the specific capacity of the modified battery is improved by 50 mAh g under the condition of 21C high multiplying power-1。
The synthesis process of the doped sample is simple and easy to regulate and control, and is suitable for large-scale preparation. The raw materials used in the invention have low cost, good reproducibility and simple preparation process, and are suitable for commercial production.
Drawings
In FIG. 1, a is pure-phase NVP, and b is Na3.01V1.99Cu0.01(PO4)3SEM image of @5% CNTs material; c is Na3.04V1.96Cu0.04(PO4)3SEM image of @5% CNTs material; d is Na3.07V1.93Cu0.07(PO4)3SEM image of @5% CNTs material; e is Na3.1V1.9Cu0.1(PO4)3SEM image of @5% CNTs material;
f to h are Na3.07V1.93Cu0.07(PO4)3TEM images of @ CNTs samples at different magnifications;
i is an EDS diagram of each element on the surface of the active particle;
FIG. 2 shows Na prepared in example 33.07V1.93Cu0.07(PO4)3An XRD space occupying fine modification pattern of a @ CNTs sample;
fig. 3 is a plot of constant current charge and discharge at 0.1C current density for each of the samples of examples 1, 2, 3, 4 and comparative example 1 when assembled as a 2016 type coin cell;
fig. 4 is a graph of cycle performance testing of samples of examples 1, 2, 3, 4 and comparative example 1 at 1C current density when assembled into a 2016 type coin cell;
fig. 5 shows the specific capacity test results of the samples of examples 1, 2, 3, 4 and comparative example 1 at different charge and discharge current densities (1C, 8C, 13C, 16C, 21C, 1C) when assembled into a 2016 type coin cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: na (Na)3.01V1.99Cu0.01(PO4)3Preparation of/C @ CNTs positive electrode material (Cu0.01-NVP/C @ CNTs)
1.5312 g of ammonium metavanadate, 2.3673 g of sodium dihydrogen phosphate, 0.00895 g of sodium acetate trihydrate, 0.01589 g of copper nitrate trihydrate, 4.9750 g of oxalic acid and 0.15 g of carbon nano tube are taken, the oxalic acid and the sodium acetate are sequentially dissolved in deionized water, the ammonium vanadate and the sodium dihydrogen phosphate are respectively and sequentially added into the solution, and the solution is heated to 80 ℃ by a water bath kettle, kept warm and stirred for 12 hours to obtain black blue sol.
Adding carbon nano tubes into the black blue sol, uniformly dispersing the carbon nano tubes into the sol by using a cell crusher, and freeze-drying for 48 hours to obtain a powdery sample. Grinding the obtained product into powder, placing the sample in a ceramic boat to carry out primary firing in a tube furnace under the condition that the temperature rising speed is 2 ℃/min, keeping the temperature at 450 ℃ for 4 hours in nitrogen atmosphere, taking out the sample to grind in a mortar for 30 minutes, and pressing the sample powder into a wafer by a tablet press to be left for final firing. The final burning condition is that the temperature rising speed is 2 ℃/min, and the temperature is kept for 12 hours at 700 ℃ in the nitrogen atmosphere to obtain the final sample.
The obtained sample is used as a positive electrode material to prepare a button cell and test the electrochemical performance of the button cell, and the process is as follows:
na prepared in this example was dissolved in 1.4 mL of N-methylpyrrolidone (NMP)3.01V1.99Cu0.01(PO4)3The material is prepared from @ CNTs active substance, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7: 2: 1 were mixed and added to NMP solvent. The mixture was ball milled for four hours to obtain a homogeneous slurry. And uniformly coating the mixture on a clean current collector by using a coating machine. Then, after four hours of blast drying at 45 ℃ and vacuum drying at 120 ℃ overnight, the electrode sheet is finally obtained. Using metal sodium as a negative electrode, a ceramic diaphragm Celgard as a diaphragm and 1M NaClO4A CR2016 type button cell was assembled in a vacuum glove box as an electrolyte.
The assembled battery is placed at room temperature for constant current charge-discharge cycle performance test, the voltage range is 2.3-4.1V, the first charge-discharge curve is shown in figure 3, the cycle performance is shown in figure 4, and the rate performance is shown in figure 5. The reversible specific capacity of the material under the multiplying power of 0.1C is 115 mAh g-1The first circle capacity under 1C multiplying power is 106.4 mAh g-187.1 mAh g after circulating for 100 circles-1(ii) a The specific discharge capacity under 21C super-high rate is 82.7 mAh g-1. It can be seen that after copper doping and carbon nanotube compounding, the discharge specific capacity and the cycle performance of the material are obviously improved.
Example 2: na (Na)3.04V1.96Cu0.04(PO4)3@ CNTs positive electrode materialPreparation of Material (Cu0.04-NVP/C @ CNTs)
1.5046 g of ammonium vanadate, 2.3619 g of sodium dihydrogen phosphate, 0.03572 g of sodium acetate trihydrate, 0.0634 g of copper nitrate trihydrate, 4.9636 g of oxalic acid and 0.15 g of carbon nanotubes were dissolved in deionized water. The specific preparation method is the same as that described in example 1.
The obtained sample is used as a positive electrode material to prepare a button cell and test the electrochemical performance of the button cell, and the process is as follows:
1.4 mL of N-methylpyrrolidone (NMP) is used as a solvent, and the mass ratio of the N-methylpyrrolidone to the NMP is 7: 2: 1 Na prepared in this example3.01V1.99Cu0.01(PO4)3@ CNTs active substance, acetylene black, polyvinylidene fluoride (PVDF) were mixed and added thereto. The mixture was ball milled for four hours to obtain a homogeneous slurry. And uniformly coating the mixture on a clean current collector by using a coating machine. Then, after four hours of blast drying at 45 ℃ and vacuum drying at 120 ℃ overnight, the electrode sheet is finally obtained. Using metal sodium as a negative electrode, a ceramic diaphragm Celgard as a diaphragm and 1M NaClO4A CR2016 type button cell was assembled in a vacuum glove box as an electrolyte.
The assembled battery is placed at room temperature for constant current charge-discharge cycle performance test, the voltage range is 2.3-4.1V, the first charge-discharge curve is shown in figure 3, the cycle performance is shown in figure 4, and the rate performance is shown in figure 5. The reversible specific capacity of the material under the multiplying power of 0.1C is 119.8 mAh g-1The first circle capacity under 1C multiplying power is 114.2 mAh g-1100.8 mAh g after 100 cycles-1(ii) a The specific discharge capacity of the 21C ultrahigh rate is 88.7 mAh g-1。
Example 3: na (Na)3.07V1.93Cu0.07(PO4)3Preparation of @ CNTs positive electrode material (Cu0.07-NVP/C @ CNTs)
1.4782 g of ammonium vanadate, 2.3564g of sodium dihydrogen phosphate, 0.06236 g of sodium acetate trihydrate, 0.1107 g of copper nitrate trihydrate, 4.9520 g of oxalic acid and 0.15 g of carbon nanotubes are dissolved in deionized water. The specific preparation method is the same as the preparation method described in example 1.
The obtained sample is used as a positive electrode material to prepare a button cell and test the electrochemical performance of the button cell, and the process is as follows:
1.4 mL of N-methylpyrrolidone (NMP) was used as a solvent, and the mass ratio was 7: 2: 1 Na prepared in this example3.01V1.99Cu0.01(PO4)3@ CNTs active substance, acetylene black, polyvinylidene fluoride (PVDF) were mixed and added thereto. The mixture was ball milled for four hours to obtain a homogeneous slurry. And uniformly coating the mixture on a clean current collector by using a coating machine. Then, after four hours of blast drying at 45 ℃ and vacuum drying at 120 ℃ overnight, the electrode sheet is finally obtained. Using metal sodium as a negative electrode, a ceramic diaphragm Celgard as a diaphragm and 1M NaClO4A CR2016 type button cell was assembled in a vacuum glove box as an electrolyte.
The assembled battery is placed at room temperature for constant current charge-discharge cycle performance test, the voltage range is 2.3-4.1V, the first charge-discharge curve is shown in figure 3, the cycle performance is shown in figure 4, and the rate performance is shown in figure 5. The reversible specific capacity of the material under the multiplying power of 0.1C is 121.4 mAh g-1The first circle capacity under 1C multiplying power is 114.5 mAh g-1After circulating for 100 circles, 102.8 mAh g-1(ii) a The specific discharge capacity of the 21C ultrahigh rate is 88.7 mAh g-1。
Example 4: na (Na)3.1V1.9Cu0.1(PO4)3Preparation of @ CNTs positive electrode material (Cu0.1-NVP/C @ CNTs)
1.4518 g of ammonium vanadate, 2.3509 g of sodium dihydrogen phosphate, 0.08888 g of sodium acetate trihydrate, 0.1578 g of copper nitrate trihydrate, 4.9405 g of oxalic acid and 0.15 g of carbon nanotubes are dissolved in deionized water. The specific preparation method is the same as the preparation method described in example 1.
The obtained sample is used as a positive electrode material to prepare a button cell and test the electrochemical performance of the button cell, and the process is as follows:
1.4 mL of N-methylpyrrolidone (NMP) was used as a solvent, and the mass ratio was 7: 2: 1 Na prepared in this example3.01V1.99Cu0.01(PO4)3@ CNTs active material, acetylene black, polyvinylidene fluorideThe limonene (PVDF) was mixed and added. The mixture was ball milled for four hours to obtain a homogeneous slurry. And uniformly coating the mixture on a clean current collector by using a coating machine. Then, after four hours of blast drying at 45 ℃ and vacuum drying at 120 ℃ overnight, the electrode sheet is finally obtained. Using metal sodium as a negative electrode, a ceramic diaphragm Celgard as a diaphragm and 1M NaClO4A CR2016 type button cell was assembled in a vacuum glove box as an electrolyte.
The assembled battery is placed at room temperature for constant current charge-discharge cycle performance test, the voltage range is 2.3-4.1V, the first charge-discharge curve is shown in figure 3, the cycle performance is shown in figure 4, and the rate performance is shown in figure 5. The reversible specific capacity of the material under the multiplying power of 0.1C is 103.3 mAh g-1(ii) a The first circle capacity under 1C multiplying power is 103.3 mAh g-188.5 mAh g after circulating for 100 circles-1(ii) a The specific discharge capacity of 21C under super-high rate is 86.7 mAh g-1。
Comparative example 1: unmodified sodium vanadium phosphate Na was prepared according to the procedure of the examples3V2(PO4)3Positive electrode material (NVP/C).
1.5394 g of ammonium metavanadate, 2.3684 g of sodium dihydrogen phosphate and 4.9860 g of oxalic acid were dissolved in deionized water. Heating to 80 ℃ by a water bath kettle, preserving the temperature and stirring for 12 hours to obtain black blue sol. After freeze-drying for 48 hours, a powdery sample was obtained. Grinding the obtained product into powder, placing the sample in a ceramic boat to carry out primary firing in a tube furnace, wherein the primary firing condition is that the sample is kept at 450 ℃ for 4 hours in nitrogen atmosphere, taking out the sample to grind in a mortar for 30min, and pressing the sample powder into a wafer by a tablet press to be left for final firing. The final burning condition is that the temperature is kept for 12 hours at 700 ℃ in the nitrogen atmosphere to obtain the final sample.
The obtained sample is used as a positive electrode material to prepare a button cell and test the electrochemical performance of the button cell, and the process is as follows:
1.4 mL of N-methylpyrrolidone (NMP) was used as a solvent, and the mass ratio was 7: 2: 1 Na prepared in this example3.01V1.99Cu0.01(PO4)3@ CNTs active substance, acetylene black, polyvinylidene fluoride (PVD)F) Mixed and added thereto. The mixture was ball milled for four hours to obtain a homogeneous slurry. And uniformly coating the mixture on a clean current collector by using a coating machine. Then, after four hours of blast drying at 45 ℃ and vacuum drying at 120 ℃ overnight, the electrode sheet is finally obtained. Using metal sodium as a negative electrode, a ceramic diaphragm Celgard as a diaphragm and 1M NaClO4A CR2016 type button cell was assembled in a vacuum glove box as an electrolyte.
The assembled battery is placed at room temperature for constant current charge-discharge cycle performance test, the voltage range is 2.3-4.1V, the first charge-discharge curve is shown in figure 3, the cycle performance is shown in figure 4, and the rate performance is shown in figure 5. The reversible specific capacity of the material under the multiplying power of 0.1C is 81.6 mAh g-1(ii) a The first circle capacity under 1C multiplying power is 73.6 mAh g-168.5 mAh g after circulation for 100 circles-1(ii) a The specific discharge capacity of 21C under the super-high rate is only 46.7 mAh g-1。
FIG. 1a shows pure-phase NVP, b to e show Na with different doping amounts3+xV2-xCux(PO4)3The SEM image of the @5% CNTs material shows that the high-temperature agglomeration phenomenon of particles is weakened along with the increase of the doping amount, and an obvious carbon nanotube cluster can be found. In FIG. 1 f-h are Na3.07V1.93Cu0.07(PO4)3TEM images of @ CNTs samples at different magnifications. It can be seen that the carbon nano tube is partially coated on the surface of the active particles and partially embedded in the active substance particles, which is beneficial to obviously improving the electronic conductivity of the material.
FIG. 2 shows Na prepared in example 33.07V1.93Cu0.07(PO4)3The XRD space occupying fine modification pattern of the @ CNTs sample shows that: after Cu doping and carbon nano tube compounding are introduced, the crystal structure of the sodium vanadium phosphate is basically not changed and other impurity phases are introduced.
The above examples illustrate: the invention successfully introduces copper ions and carbon nano tubes into a vanadium sodium phosphate material system by using a simple liquid phase method, and obviously improves the ionic and electronic conductivity and the crystal structure stability of the vanadium sodium phosphate electrode material. Electrochemical performance tests show that the product has excellent rate performance and high-rate long-cycle stability, and the method is simple in process, low in cost and suitable for industrial application.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A vanadium sodium phosphate electrode material of a vanadium-position copper-doped composite carbon nanotube is characterized in that: the vanadium phosphate sodium electrode material of the vanadium-position copper-doped composite carbon nanotube is as follows: na (Na)3+xV2-xCux(PO4)3@5% CNTs, x =0.01, 0.04, 0.07, 0.1; the electrode material is prepared from ammonium metavanadate, sodium acetate and sodium dihydrogen phosphate as raw materials, oxalic acid as a template and a carbon source and 5wt% of carbon nano tubes as auxiliary materials to obtain the carbon nano tubes and Na coated with carbon3V2(PO4)3And compounding the particles to form a three-dimensional conductive frame structure, wherein copper nitrate is used as a doping source, and the copper-doped sodium vanadium phosphate material is compounded and distributed in the carbon nano tube.
2. The method for preparing the vanadium phosphate sodium electrode material of the vanadium site copper doped composite carbon nano tube, which is characterized by comprising the following steps: ammonium metavanadate, sodium acetate, ammonium dihydrogen phosphate, oxalic acid and carbon nano tubes are used as raw materials, copper nitrate is used as a doping source, deionized water is used as a solvent, and the vanadium sodium phosphate electrode material of the vanadium-position copper-doped composite carbon nano tube is prepared by a liquid phase method.
3. The method for preparing the vanadium sodium phosphate electrode material of the vanadium-site copper-doped composite carbon nanotube according to claim 2, wherein the method comprises the following steps: the method comprises the following specific steps:
(1) sequentially dissolving oxalic acid and sodium acetate in 50 mL of deionized water, and sequentially adding copper nitrate, ammonium metavanadate and sodium dihydrogen phosphate into the solution respectively, heating the solution in a water bath kettle to 80 ℃, preserving the temperature and stirring the solution for 12 hours to obtain black blue sol;
(2) adding carbon nanotubes into the black-blue sol, wherein the mass of the carbon nanotubes is 5% of that of the NVP sample, uniformly dispersing the carbon nanotubes in the sol by using a cell crusher, and freeze-drying the mixture for 48 hours to obtain a powdery sample;
(3) placing the powdery sample in a ceramic boat to carry out primary firing in a tube furnace, wherein the primary firing condition is that the temperature is kept at 450 ℃ for 4 hours in a nitrogen atmosphere, and the heating speed is 2 ℃/min;
(4) taking out a sample, grinding the sample in a mortar for 30min, pressing sample powder into a wafer by using a tablet machine, and carrying out final firing under the condition that the temperature is kept at 700 ℃ in a nitrogen atmosphere for 12 hours, wherein the temperature rising speed is 2 ℃/min;
(5) and grinding the sample after final burning for 30min to obtain the modified powdery sample.
4. The method for preparing the vanadium sodium phosphate electrode material of the vanadium-site copper-doped composite carbon nanotube according to claim 3, wherein the method comprises the following steps: ammonium metavanadate, copper nitrate trihydrate, oxalic acid, sodium acetate trihydrate and sodium dihydrogen phosphate, wherein the mass ratio of the ammonium metavanadate to the copper nitrate trihydrate is 2-x: x: 3: x: and 3, x =0.01, 0.04, 0.07 and 0.1, and synthesizing the vanadium sodium phosphate electrode material of the vanadium site copper doped composite carbon nano tube.
5. The application of the vanadium sodium phosphate electrode material of the vanadium-position copper-doped composite carbon nanotube in the sodium ion battery, which is characterized in that: the vanadium sodium phosphate electrode material of the vanadium-position copper-doped composite carbon nanotube is used as a positive electrode material and applied to a sodium ion battery.
6. Use according to claim 5, characterized in that: the specific application method comprises the following steps: na (Na)3+xV2-xCux(PO4)3@5% CNTs as active material of positive electrode material, and sodium sheet as negative electrodeAssembling into 2016 type button cell with 1 mol L electrolyte-1NaClO (sodium chloride)4Dissolving in PC solvent, adding 5wt% of FEC as additive, and the diaphragm is ceramic diaphragm.
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