CN115472800A - Potassium-doped sodium titanate electrode material and preparation method and application thereof - Google Patents
Potassium-doped sodium titanate electrode material and preparation method and application thereof Download PDFInfo
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- CN115472800A CN115472800A CN202211220673.9A CN202211220673A CN115472800A CN 115472800 A CN115472800 A CN 115472800A CN 202211220673 A CN202211220673 A CN 202211220673A CN 115472800 A CN115472800 A CN 115472800A
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- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000007772 electrode material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 29
- 239000013078 crystal Substances 0.000 abstract description 13
- 239000012071 phase Substances 0.000 abstract description 13
- 229910052700 potassium Inorganic materials 0.000 abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011591 potassium Substances 0.000 abstract description 11
- 239000007773 negative electrode material Substances 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 29
- 239000011734 sodium Substances 0.000 description 27
- 238000003837 high-temperature calcination Methods 0.000 description 8
- 238000000713 high-energy ball milling Methods 0.000 description 7
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 4
- 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 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
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- 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
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention belongs to the technical field of sodium ion batteries, and relates to a potassium-doped sodium titanate electrode material, and a preparation method and application thereof. The potassium-doped sodium titanate electrode material rod-like layered structure is synthesized by a simple solid phase method, and is obtained by ball-milling precursors of sodium carbonate, potassium carbonate and anatase phase titanium dioxide in proportion and then sintering the mixture in air by microwave; the addition of the potassium element increases the exposure of the crystal face of the sodium titanate (100) and reduces the exposure of the crystal face of the sodium titanate (003); the potassium-doped sodium titanate is used as a negative electrode material in the sodium ion battery, and the potassium element is added, so that the sodium ion diffusion channel is increased and shortened, the storage of sodium ions is facilitated, and the specific capacity and the rate capability of the sodium titanate material are improved.
Description
The technical field is as follows:
the invention belongs to the technical field of sodium ion batteries, and particularly relates to a potassium-doped sodium titanate electrode material, and a preparation method and application thereof.
Technical background:
in recent years, lithium ion batteries have enjoyed great success in the fields of portable electronic devices and electric automobiles, resulting in an increasing demand for lithium resources. With the great increase of the cost of lithium resources, sodium ion batteries are considered as ideal substitutes of lithium ion batteries due to the advantages of abundant resources, low cost, high efficiency and the like. For sodium ion batteries, one hasA large number of electrode materials have been explored but there is a serious lack of low voltage negative electrode materials that can compete with graphite negative electrodes in lithium ion batteries. The titanium-based material has moderate Ti due to the rich crystal form 3+ /Ti 4+ The low potential redox couple, and the low cost, have made it of great interest as a negative electrode material for sodium ion batteries.
In various sodium ion battery titanium-based negative electrode materials, na 2 Ti 3 O 7 0.3V (vs. Na/Na) due to its special titanium oxygen octahedron zigzag layered structure + ) Low sodium insertion platform and 177mAh g -1 Is considered to be a very potential anode material. Found that Na 2 Ti 3 O 7 Is not high, and in order to satisfy the principle of lowest energy, sodium ions preferably migrate along the zigzag layers, rather than through the layers, so that the number and length of sodium ion migration channels are Na-limiting 2 Ti 3 O 7 The migration and intercalation/deintercalation of sodium ions.
In recent years, na has been used for shortening the sodium ion migration path 2 Ti 3 O 7 The nano design is a mainstream strategy, but the preparation method is high in cost and low in yield, and is difficult to realize in industrial production. Ion doping by solid phase method has been widely used in material modification because of its simple preparation method, high yield, and easy realization of industrial production, but for Na doping by ion doping 2 Ti 3 O 7 The number of sodium ion migration channels is increased, and a method of shortening the migration length has not been reported.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provides a preparation method and application of a sodium-ion battery negative electrode material.
In order to achieve the purpose, the invention provides a potassium-doped sodium titanate electrode material which is in a nanorod structure and has the diameter of 100-300nm.
The microwave-assisted potassium-doped sodium titanate negative electrode material has preferred orientation, and the exposure of a (100) crystal plane is increased, and the exposure of a (003) crystal plane is reduced.
The invention also provides a preparation method of the potassium-doped sodium titanate electrode material, which comprises the following steps:
(1) And (3) performing ball milling and mixing on sodium carbonate, potassium carbonate and anatase phase titanium dioxide according to a certain proportion to obtain a precursor mixture which is uniformly mixed.
(2) And (3) placing the precursor mixture which is uniformly mixed in a microwave tube furnace, and calcining at a certain temperature in an air atmosphere to obtain the potassium-doped sodium titanate negative electrode material.
The sodium carbonate is: potassium carbonate: the molar ratio of anatase phase titanium dioxide = (1.7-2.3): (0.01-0.5): 6.
the heating rate of the calcination in the microwave tube furnace is 5-10 ℃ per minute, the calcination temperature is 800-1100 ℃, and the calcination time is 20-60 minutes.
The invention also provides application of the potassium-doped sodium titanate electrode material in a sodium ion battery.
The rated power of the microwave tube type oven used in the invention is 4kW, the microwave output power is 0.01-1.40kW, and the microwave tube type oven is continuously adjustable; the microwave frequency is 2.45GHz, and the temperature measuring range is as follows: 0 to 1650 ℃.
Compared with the prior art, the invention has the following advantages:
(1) The precursor of the electrode material is low-cost sodium carbonate, potassium carbonate and titanium dioxide;
(2) The preparation method of the material is simple, the material is synthesized by a solid phase method, and the precursor is obtained by ball milling in proportion and microwave sintering in air;
(3) The addition of the potassium element increases the exposure of the crystal face of the sodium titanate (100) and reduces the exposure of the crystal face of the sodium titanate (003);
(4) The material is used as a negative electrode material and applied to a sodium ion battery, and the addition of the potassium element enables the sodium ion diffusion channel to be increased and shortened, so that the storage of sodium ions is facilitated, and the specific capacity and the rate capability of the sodium titanate material are improved.
Description of the drawings:
FIG. 1 shows potassium-doped sodium titanate prepared in example 4Electrode material Na 1.9 K 0.1 Ti 3 O 7 And Na 2 Ti 3 O 7 X-ray diffraction pattern of (a).
Fig. 2 is an X-ray photoelectron spectrum of the potassium-doped sodium titanate electrode material prepared in example 4.
FIG. 3 is a scanning electron micrograph of the potassium-doped sodium titanate electrode material prepared in example 4.
Fig. 4 is a high-resolution transmission electron micrograph of the potassium-doped sodium titanate electrode material prepared in example 4.
Fig. 5 is a graph of first charge and discharge voltage versus specific capacity of the potassium-doped sodium titanate electrode material prepared in example 1.
Fig. 6 is a graph of first charge-discharge voltage versus specific capacity for the potassium-doped sodium titanate electrode material prepared in example 2.
Fig. 7 is a graph of first charge-discharge voltage versus specific capacity for the potassium-doped sodium titanate electrode material prepared in example 3.
Fig. 8 is a graph of first charge-discharge voltage versus specific capacity for the potassium-doped sodium titanate electrode material prepared in example 4.
Fig. 9 is a graph of first charge-discharge voltage versus specific capacity for the potassium-doped sodium titanate electrode material prepared in example 5.
Fig. 10 is a graph of first charge-discharge voltage versus specific capacity for the potassium-doped sodium titanate electrode material prepared in example 6.
Fig. 11 is a graph of first charge-discharge voltage versus specific capacity for the potassium-doped sodium titanate electrode material prepared in example 7.
Fig. 12 is a graph of first charge-discharge voltage versus specific capacity for the sodium titanate electrode material prepared in example 8.
FIG. 13 is a graph of rate performance for potassium-doped sodium titanate electrode materials and sodium titanate electrode materials prepared in examples 4 and 8 (square shape: example 4; round shape: example 8).
The specific implementation mode is as follows:
the invention is further illustrated by the following specific examples in combination with the accompanying drawings.
Example 1:
the present example relates to potassium-doped sodium titanateThe preparation method of the electrode material comprises the following steps: placing 1.049g of sodium carbonate, 0.014g of potassium carbonate and 2.397g of anatase phase titanium dioxide in a high-energy ball milling tank for ball milling for 1 hour at room temperature to obtain a precursor which is uniformly mixed; then placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rise rate is set to be 10 ℃ per minute, and the mixture is calcined for 20 minutes at 850 ℃ in the air atmosphere to obtain the potassium-doped sodium titanate electrode material (Na) 1.98 K 0.02 Ti 3 O 7 )。
Example 2:
the embodiment relates to a preparation method of a potassium-doped sodium titanate electrode material, which comprises the following steps: at room temperature, 1.044g of sodium carbonate, 0.021g of potassium carbonate and 2.397g of anatase-phase titanium dioxide are placed in a high-energy ball milling tank for ball milling for 1 hour to obtain a precursor which is uniformly mixed. Placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rise rate is set to be 10 ℃ per minute, and the mixture is calcined for 20 minutes at 850 ℃ in the air atmosphere to obtain the potassium-doped sodium titanate electrode material (Na) 1.96 K 0.04 Ti 3 O 7 )。
Example 3:
the embodiment relates to a preparation method of a potassium-doped sodium titanate electrode material, which comprises the following steps: 1.018g of sodium carbonate, 0.063g of potassium carbonate and 2.397g of anatase phase titanium dioxide were ball milled in a high energy ball mill jar for 1 hour at room temperature to obtain a uniformly mixed precursor. Placing the precursor in a microwave tube furnace, and carrying out high-temperature calcination, specifically: the temperature rise rate is set to be 10 ℃ per minute, and the mixture is calcined for 20 minutes at 850 ℃ in the air atmosphere to obtain the potassium-doped sodium titanate electrode material (Na) 1.92 K 0.08 Ti 3 O 7 )。
Example 4:
the embodiment relates to a preparation method of a potassium-doped sodium titanate electrode material, which comprises the following steps: at room temperature, 1.007g of sodium carbonate, 0.070g of potassium carbonate and 2.397g of anatase phase titanium dioxide are placed in a high-energy ball milling tank for ball milling for 1 hour to obtain a precursor which is uniformly mixed. Placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: ramp rate set to 10 shotsCalcining the mixture for 20 minutes at 850 ℃ in air atmosphere to obtain the potassium-doped sodium titanate electrode material (Na) 1.9 K 0.1 Ti 3 O 7 )。
For the potassium-doped sodium titanate electrode material Na prepared in this example 1.9 K 0.1 Ti 3 O 7 And (6) performing characterization. The material was structurally characterized by an X-ray diffractometer and the results are shown in figure 1. As can be seen from FIG. 1, the diffraction peak of the prepared material is associated with Na 2 Ti 3 O 7 The DFT standard card shows consistent crystal phase, which indicates that the pure-phase potassium-doped sodium titanate material (Na) is successfully prepared in the embodiment 1.9 K 0.1 Ti 3 O 7 ). In fig. 1, it can be seen that the diffraction intensity of 10.527 ° (100) crystal plane is enhanced, and the diffraction intensity of 29.929 ° (003) crystal plane is relatively reduced, indicating that the addition of potassium element causes the preferred orientation of crystal, so that the exposure of (100) crystal plane is increased, and the exposure of (003) crystal plane is relatively reduced, which makes the diffusion channel of sodium ions shorter while increasing, and is beneficial to the diffusion and storage of sodium ions.
By X-ray photoelectron spectroscopy (XPS) for Na 1.9 K 0.1 Ti 3 O 7 The material was subjected to elemental characterization, and the results are shown in fig. 2. As can be seen from FIG. 2, the material contains four elements of Na, K, ti and O, which indicates that K is successfully doped into the material.
By field emission scanning electron microscopy (FE-SEM) on Na 1.9 K 0.1 Ti 3 O 7 The morphology of the material was characterized and the results are shown in fig. 3. As can be seen from FIG. 3, the material was prepared in a rod-like structure with a diameter of about 100nm.
By high resolution transmission electron microscopy (HR-TEM) on Na 1.9 K 0.1 Ti 3 O 7 The morphology of the material was characterized and the results are shown in fig. 4. As can be further confirmed from FIG. 4, the prepared material has a rod-like structure with a diameter of about 100nm.
Example 5:
the embodiment relates to a preparation method of a potassium-doped sodium titanate electrode material, which comprises the following steps: 0.954g of sodium carbonate and 0.14g of carbonic acid were added at room temperaturePutting potassium and 2.397g of anatase phase titanium dioxide into a high-energy ball milling tank for ball milling for 1 hour to obtain a precursor which is uniformly mixed; placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rise rate is set to be 10 ℃ per minute, and the mixture is calcined for 20 minutes at 850 ℃ in the air atmosphere to obtain the potassium-doped sodium titanate electrode material (Na) 1.8 K 0.2 Ti 3 O 7 )。
Example 6:
the embodiment relates to a preparation method of a potassium-doped sodium titanate electrode material, which comprises the following steps: at room temperature, placing 0.900g of sodium carbonate, 0.21g of potassium carbonate and 2.397g of anatase phase titanium dioxide in a high-energy ball milling tank for ball milling for 1 hour to obtain a uniformly mixed precursor; placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rise rate is set to be 10 ℃ per minute, and the mixture is calcined for 20 minutes at 850 ℃ in the air atmosphere to obtain the potassium-doped sodium titanate electrode material (Na) 1.7 K 0.3 Ti 3 O 7 )。
Example 7:
the embodiment relates to a preparation method of a potassium-doped sodium titanate electrode material, which comprises the following steps: placing 0.848g of sodium carbonate, 0.28g of potassium carbonate and 2.397g of anatase phase titanium dioxide in a high-energy ball milling tank for ball milling for 1 hour at room temperature to obtain a uniformly mixed precursor; placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the temperature rise rate is set to be 10 ℃ per minute, and the mixture is calcined for 20 minutes at 850 ℃ in the air atmosphere to obtain the potassium-doped sodium titanate electrode material (Na) 1.6 K 0.4 Ti 3 O 7 )。
Example 8:
the embodiment relates to a preparation method of a sodium titanate electrode material, which comprises the following steps: placing 1.06g of sodium carbonate and 2.397g of anatase phase titanium dioxide in a high-energy ball milling tank for ball milling for 1 hour at room temperature to obtain a precursor which is uniformly mixed; placing the precursor in a microwave tube furnace for high-temperature calcination, specifically: the heating rate is set to 10 ℃ per minute, and the mixture is calcined at 850 ℃ for 20 minutes in the air atmosphere to obtain the sodium titanate electrode material (Na) 2 Ti 3 O 7 )。
Example 9:
the embodiment relates to an electrochemical performance test experiment of a potassium-doped sodium titanate electrode material, which comprises the following specific steps:
the potassium-doped sodium titanate and sodium titanate materials obtained in examples 1 to 8 were used as a negative electrode of a sodium ion battery, metal sodium as a counter electrode, glass fiber as a separator, and sodium perchlorate (NaClO) was used 4 ) And (3) as an electrolyte, packaging the electrolyte in a CR2032 button cell case in an argon atmosphere glove box to obtain a potassium-doped sodium titanate electrode material half cell and a sodium titanate electrode material half cell. At 0.1C (1C=177mA g -1 ) The specific capacity obtained by electrochemical performance test in the voltage range of 0.01-2.5V with the multiplying power is shown in Table 1. Electrochemical rate performance tests were performed at 0.1, 0.2, 0.5, 1 and 2C rates, with a voltage range of 0.01-2.5V, and the resulting rate performance is shown in fig. 13.
TABLE 1 specific Capacity (mAh g) of microwave-assisted potassium-doped sodium titanate electrode materials described in examples 1-8 -1 )
The first charge-discharge voltage and specific capacity test results of the potassium-doped sodium titanate electrode materials and the sodium titanate electrode materials of examples 1-8 are shown in fig. 5-12.
As can be seen from Table 1, the specific capacities of the potassium-doped sodium titanate materials prepared from the precursor materials with different ratios are different, and the Na prepared in example 4 1.9 K 0.1 Ti 3 O 7 The material has the largest specific capacity and is compared with Na not doped with potassium element prepared in example 8 2 Ti 3 O 7 The specific capacity of the material is large. As can be seen from FIG. 13, na prepared in example 4 was obtained at different magnifications 1.9 K 0.1 Ti 3 O 7 Materials comparison of Na undoped with Potassium element prepared in example 8 2 Ti 3 O 7 The specific capacity of the material is large, which shows that the existence of potassium element enables the specific capacity of the potassium-doped sodium titanate material under the same multiplying power to be compared with that of the potassium-doped sodium titanate material without dopingThe potassium element sodium titanate material is increased. Namely, the potassium-doped sodium titanate electrode material prepared according to the application has better specific capacity and rate capability when applied to a sodium ion battery than the sodium titanate material without potassium doping.
Claims (5)
1. A potassium-doped sodium titanate electrode material is characterized in that the structure of the electrode material is a nano rod, and the diameter of the electrode material is 100-300nm.
2. A preparation method of a potassium-doped sodium titanate electrode material is characterized by comprising the following steps:
(1) And carrying out ball milling and mixing on sodium carbonate, potassium carbonate and anatase phase titanium dioxide to obtain a precursor mixture which is uniformly mixed.
(2) And placing the precursor mixture which is uniformly mixed in a microwave tube furnace, and calcining in the air atmosphere to obtain the potassium-doped sodium titanate electrode material.
3. The method of preparing a potassium-doped sodium titanate electrode material of claim 2, wherein the sodium carbonate: potassium carbonate: anatase phase titanium dioxide molar ratio = (1.7-2.3): (0.01-0.5): 6.
4. the method for preparing the potassium-doped sodium titanate electrode material of claim 2, wherein the temperature rise rate of the calcination in the microwave tube furnace is 5-10 ℃ per minute, the calcination temperature is 800-1100 ℃, and the calcination time is 20-60 minutes.
5. The use of the potassium-doped sodium titanate electrode material of claim 1 in a sodium ion battery.
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