CN112919533A - Nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material and a preparation method and application thereof. The method comprises the following steps: synthesizing amorphous titanium dioxide microporous nanospheres by using isopropyl titanate as a titanium source; calcining the amorphous titanium dioxide microporous nanospheres and sodium hypophosphite to obtain phosphorus-doped titanium dioxide nanospheres; and coating the phosphorus-doped titanium dioxide by using dopamine, and calcining to obtain the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanospheres. The method can effectively improve the phosphorus-doped amount and the crystallinity of the amorphous titanium dioxide and control the surface carbon coating content, the prepared composite material has excellent sodium storage performance, and meanwhile, the method can improve the conductivity and the structural stability of the composite material, further improve the rate capability and the long cycle performance of the material, so that the prepared nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material is more suitable to be used as an electrode material of a high-performance sodium ion battery.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material and a preparation method and application thereof.
Background
Because the reserve of sodium resources is abundant, the distribution is even, the cost is low, so that the sodium ion battery has great potential as an energy storage battery to be used as a large-scale energy storage system. However, due to the radius of sodium ions
Radius of lithium ion
Large, it remains a challenge to find negative electrodes capable of reversibly and efficiently storing sodium ions (adv. energy mater.2019,9,1901351). The titanium dioxide is used as a hot door material of the cathode of the sodium ion battery, and has the advantages of stable structure, high working voltage, environmental friendliness, low cost and the like in the process of embedding/removing sodium ions. However, titanium dioxide has poor sodium ion diffusion kinetics and conductivity, which greatly hampers its practical application (adv. mater.2019, 1904589). Research shows that the conducting capacity and specific capacity of the material can be effectively improved by carrying out heteroatom doping, particularly phosphorus doping on titanium dioxide (Angew. chem. int. Ed.2019,58, 1-6). In addition, carbon coating of phosphorus-doped titanium dioxide to construct a composite structure is an effective way to improve the sodium storage performance of titanium dioxide (J.Mater.chem.A., 2015,3, 18944-18952).
Examples of methods for preparing phosphorus-doped titanium dioxide include sol-gel methods (environ. sci. pollut. res.2019,26, 4180-4191) and gas phosphating methods (adv. mater.2018,30,1704337) using sodium hypophosphite as a phosphorus source. However, since the crystal structure of titanium dioxide is very stable, it becomes very difficult to prepare high phosphorus doping amount (ACS Nano 2019,13, 9247-9258). In addition, the use of a large amount of dopant to increase the doping amount may cause excessive doping, possibly destroying the crystal structure, and thus affecting the cycle stability of the material.
Disclosure of Invention
Aiming at the problem that the doping amount of phosphorus is difficult to increase when the crystalline titanium dioxide is doped with phosphorus, the invention provides a nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material and a preparation method and application thereof.
According to the method, firstly, amorphous titanium dioxide micro-porous spheres with high specific surface area are used as precursors, titanium dioxide with high phosphorus doping amount is prepared through condition control, and then nitrogen-doped carbon is used for coating the phosphorus-doped titanium dioxide, so that the crystallinity of the amorphous titanium dioxide is improved, and meanwhile, the high phosphorus doping amount is kept, and the sodium storage capacity of the composite material is improved. Meanwhile, the order of phosphorus doping and carbon coating has obvious influence on the sodium storage performance of the material, and the invention further discloses that the high-specific surface area amorphous titanium dioxide microporous nanospheres are necessary to improve the phosphorus doping amount by taking the high-specific surface area amorphous titanium dioxide microporous nanospheres as precursors.
The purpose of the invention is realized by at least one of the following technical solutions.
The preparation method of the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material provided by the invention comprises the following steps:
(1) adding ammonia water and deionized water into a mixed solution of ethanol and acetonitrile, uniformly stirring (the stirring time is preferably 30min), adding a surfactant, dropwise adding isopropyl titanate, and stirring to obtain an emulsion; centrifuging the emulsion, taking the precipitate, washing and drying to obtain the amorphous titanium dioxide microporous nanospheres with high specific surface area;
(2) placing sodium hypophosphite and the amorphous titanium dioxide microporous nanospheres with the high specific surface area obtained in the step (1) in a reactor (preferably a tubular furnace), heating to the decomposition temperature of the sodium hypophosphite in a protective atmosphere, closing an air inlet and an air outlet of the reactor, performing heating treatment (operation within a safe pressure range), naturally cooling to room temperature to obtain a heated product, washing, and drying to obtain phosphorus-doped titanium dioxide nanospheres;
(3) ultrasonically dispersing the phosphorus-doped titanium dioxide nanospheres in the step (2) into a buffer solution, adding dopamine, stirring, centrifuging, and taking precipitates to obtain phosphorus-doped titanium dioxide nanospheres coated with dopamine;
(4) and (4) heating the dopamine-coated phosphorus-doped titanium dioxide nanospheres in the step (3) under a protective atmosphere to perform calcination treatment, so as to obtain the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material (nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanospheres).
Further, the mass percentage concentration of the ammonia water in the step (1) is 25-28%, and the volume ratio of the isopropyl titanate, the ammonia water and the water is 5: 0.425: 0.31-0.91.
Further, in the mixed solution of ethanol and acetonitrile in the step (1), the volume ratio of ethanol to acetonitrile is 3: 1.5-3; the surfactant is polyvinylpyrrolidone (PVP), and the mass volume ratio of the surfactant to ammonia water is 0.1-0.2: 0.425 g/mL; the volume ratio of the water to the mixed solution of ethanol and acetonitrile is 0.31-0.91: 250-275.
Preferably, in the mixed solution of ethanol and acetonitrile in the step (1), the volume ratio of ethanol to acetonitrile is 3: 2.
further, the stirring treatment time in the step (1) is 4-8h, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
Preferably, the stirring treatment time of the step (1) is 6 h.
Preferably, the drying temperature in the step (1) is 60 ℃, and the drying time is 12 h.
Further, the mass ratio of the amorphous titanium dioxide microporous nanospheres to the sodium hypophosphite in the step (2) is 1: 10-20.
Further, the protective atmosphere in the step (2) is argon or nitrogen atmosphere; the rate of temperature rise is 1-5 ℃/min; the temperature of the heating treatment is 400-550 ℃, and the time of the heating treatment is 1-2 h; the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
Preferably, in the step (2), after the temperature is raised to the decomposition temperature of the sodium hypophosphite in the protective atmosphere, the introduction of the protective gas is stopped, and after the internal and external pressures of the reactor reach a balance, the gas inlet and the gas outlet of the reactor are closed for heating treatment.
Preferably, in the step (2), the reactor is heated to the decomposition temperature of the sodium hypophosphite, then the air inlet and the air outlet are closed to form a closed system, and then the temperature is continuously increased to 400-500 ℃ for heating treatment.
Preferably, in the step (2), sodium hypophosphite is placed near the air inlet of the reactor, and the amorphous titanium dioxide microporous nanospheres are placed near the air outlet of the reactor.
Preferably, the temperature rise rate of the step (2) is 2 ℃/min; the time of the heating treatment is 2 hours; the drying temperature is 60 ℃, and the drying time is 12 h.
Further, the buffer solution in the step (3) is a Tris buffer solution; the pH value of the buffer solution is 8-8.5; the mass ratio of the phosphorus-doped titanium dioxide nanospheres to the dopamine is 2-4: 1; the mass-to-volume ratio of the phosphorus-doped titanium dioxide nanospheres to the buffer solution is 0.2: 50-60 g/mL; the stirring treatment time is 3-12 h.
Preferably, the pH value of the buffer solution in the step (3) is 8.5; the mass-to-volume ratio of the phosphorus-doped titanium dioxide nanospheres to the buffer solution is 0.2: 50 g/mL.
Further, the protective atmosphere in the step (4) is nitrogen or argon atmosphere; the rate of temperature rise is 1-5 ℃/min; the temperature of the calcination treatment is 500-700 ℃, and the time of the calcination treatment is 1-2 hours.
Preferably, the temperature raising rate of the step (4) is 2 ℃/min, and the time of the calcination treatment is 2 hours.
The invention provides a nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material prepared by the preparation method.
The nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material provided by the invention is applied to the preparation of a sodium ion battery.
The technical scheme provided by the invention has the following advantages and beneficial effects:
(1) according to the preparation method provided by the invention, the amorphous titanium dioxide microporous nanospheres with high specific surface area prepared by a gel-sol method are used as precursors, and can easily react with phosphine generated in a pyrolysis process, so that titanium dioxide with high phosphorus doping amount can be prepared;
(2) the preparation method provided by the invention avoids the outstanding problems of material structure damage, excessive reagent consumption and the like caused by using excessive doping agent to obtain titanium dioxide with high phosphorus doping amount.
(3) In addition, the preparation method provided by the invention can improve the conductivity and structural stability of the composite material, further improve the rate capability and long cycle performance of the material, and enable the prepared nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material to be more suitable for being used as an electrode material of a high-performance sodium-ion battery.
Drawings
Fig. 1 is XRD patterns of nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material of example 1, amorphous titanium dioxide microporous nanospheres of comparative example 1, phosphorus-doped titanium dioxide nanospheres of comparative example 2, and nitrogen-doped carbon-coated titanium dioxide nanosphere material of comparative example 3;
FIG. 2 is a nitrogen adsorption and desorption graph and a pore size distribution graph of the amorphous titanium dioxide microporous nanospheres with high specific surface area prepared in step (1) of example 1;
fig. 3 is XRD charts of the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material of example 1, the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material of example 2, the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material of example 3, and the phosphorus-doped carbon-coated titanium dioxide nanospheres of comparative example 4;
FIG. 4 is a thermogravimetric analysis of the nitrogen doped carbon coated phosphorus doped titania materials of examples 1, 2 and 3;
fig. 5 is SEM images of nitrogen doped carbon coated phosphorus doped titanium dioxide materials of example 1, example 2 and example 3, amorphous titanium dioxide microporous nanospheres of comparative example 1, phosphorus doped titanium dioxide nanospheres of comparative example 2 and nitrogen doped carbon coated titanium dioxide nanosphere materials of comparative example 3;
FIG. 6 is a graph of the relative atomic ratios of the elements in the nitrogen doped carbon coated phosphorus doped titanium dioxide material of example 1 and the phosphorus doped titanium dioxide nanospheres of comparative example 2;
FIG. 7 is an XPS fine spectrum of the P, Ti, O and N elements of the nitrogen doped carbon coated phosphorus doped titanium dioxide material of example 1;
fig. 8 is a charge-discharge curve for the first three revolutions of a sodium ion battery assembled using the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material of example 1;
fig. 9 is a graph of rate performance of sodium ion batteries assembled using nitrogen doped carbon coated phosphorus doped titanium dioxide material of example 1, amorphous titanium dioxide microporous nanospheres assembled sodium ion batteries of comparative example 1, phosphorus doped titanium dioxide nanospheres assembled sodium ion batteries of comparative example 2, and nitrogen doped carbon coated titanium dioxide nanospheres assembled sodium ion batteries of comparative example 3;
fig. 10 is a graph of rate performance for sodium ion batteries assembled using nitrogen doped carbon coated phosphorus doped titanium dioxide material of example 1, and phosphorus doped carbon coated titanium dioxide nanospheres of comparative example 4;
fig. 11 is a graph of long cycle performance of sodium ion cells assembled with nitrogen doped carbon coated phosphorus doped titanium dioxide material of example 1, amorphous titanium dioxide microporous nanosphere assembled sodium ion cells of comparative example 1, phosphorus doped titanium dioxide nanosphere assembled sodium ion cells of comparative example 2, nitrogen doped carbon coated titanium dioxide nanosphere material assembled sodium ion cells of comparative example 3;
fig. 12 is a graph of rate performance of sodium ion batteries assembled using nitrogen doped carbon coated phosphorus doped titanium dioxide materials of examples 2, 3 and amorphous titanium dioxide microporous nanospheres of comparative example 1.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanospheres comprises the following steps:
(1) placing 150mL of ethanol and 100mL of acetonitrile in a 500mL beaker, stirring for 30min, uniformly stirring, then respectively adding 0.425mL of ammonia water and 0.46mL of deionized water, continuously stirring for 10min, uniformly stirring, adding 0.1g of surfactant (polyvinylpyrrolidone is selected) to obtain a mixed solution, then dropwise adding 5mL of isopropyl titanate into the mixed solution, and continuously stirring for 6h to obtain an emulsion; centrifuging the emulsion, collecting precipitates by centrifugation, washing the precipitates by ethanol and water respectively, and drying the precipitates for 12 hours at 60 ℃ to obtain amorphous titanium dioxide microporous nanospheres with high specific surface area;
(2) placing 200mg of the amorphous titanium dioxide microporous nanospheres in the step (1) on the gas-close downstream side of a quartz boat, placing 4g of sodium hypophosphite on the gas-close upstream side of the quartz boat, then under the condition of introducing argon gas, the gas flow rate is 20mL/min, raising the temperature to 300 ℃ at the temperature rise rate of 2 ℃/min (raising the temperature to the decomposition temperature of the sodium hypophosphite), continuing to raise the temperature at the same temperature rise rate, stopping introducing the argon gas into the tube furnace, closing the gas inlet and the gas outlet of the quartz tube, enabling the quartz tube to be a closed system, and further decomposing the sodium hypophosphite to generate phosphine gas (operating within the safe pressure range) along with the continuous temperature rise. And (3) continuously heating the tube furnace to 500 ℃, keeping the temperature for 2h, introducing argon into the tube after cooling to room temperature, discharging phosphine gas in the tube into an absorption bottle, finally obtaining gray black powder, washing the gray black powder by using 0.1M hydrochloric acid, deionized water and ethanol respectively, and drying the gray black powder for 12h at the temperature of 60 ℃ to obtain the phosphorus-doped titanium dioxide nanospheres.
(3) And (3) adding 200mg of the phosphorus-doped titanium dioxide nanosphere obtained in the step (2) into a 50mL Tris buffer solution (pH 8.5) for ultrasonic dispersion for 30min, uniformly dispersing, then adding 70mg of dopamine, stirring for 3h, finally centrifuging to obtain a precipitate, and drying at 60 ℃ for 12h to obtain the dopamine-coated phosphorus-doped titanium dioxide.
(4) And (3) placing the dopamine-coated phosphorus-doped titanium dioxide in the step (3) into a tubular furnace, and calcining in an argon atmosphere at the heating rate of 2 ℃/min at the calcining temperature of 600 ℃ for 2 h. Finally obtaining the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanosphere material (the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material).
Example 2
A preparation method of nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanospheres comprises the following steps:
(1) placing 150mL of ethanol and 100mL of acetonitrile in a 500mL beaker, stirring for 30min, uniformly stirring, then respectively adding 0.425mL of ammonia water and 0.31mL of deionized water, continuously stirring for 10min, uniformly stirring, adding 0.15g of surfactant (polyvinylpyrrolidone is selected) to obtain a mixed solution, then dropwise adding 5mL of isopropyl titanate into the mixed solution, and continuously stirring for 6h to obtain an emulsion; centrifuging the emulsion, collecting precipitates by centrifugation, washing the precipitates by ethanol and water respectively, and drying the precipitates for 12 hours at 60 ℃ to obtain amorphous titanium dioxide microporous nanospheres with high specific surface area;
(2) placing 200mg of the amorphous titanium dioxide microporous nanospheres in the step (1) on the gas-close downstream side of a quartz boat, placing 3g of sodium hypophosphite on the gas-close upstream side of the quartz boat, then under the condition of introducing argon gas, the gas flow rate is 20mL/min, raising the temperature to 300 ℃ at the temperature rise rate of 2 ℃/min (raising the temperature to the decomposition temperature of the sodium hypophosphite), continuing to raise the temperature at the same temperature rise rate, stopping introducing the argon gas into the tube furnace, closing the gas inlet and the gas outlet of the quartz tube, enabling the quartz tube to be a closed system, and further decomposing the sodium hypophosphite to generate phosphine gas (operating within the safe pressure range) along with the continuous temperature rise. And (3) continuously heating the tube furnace to 400 ℃, preserving heat for 2h, introducing argon into the tube after cooling to room temperature, and discharging phosphine gas in the tube into an absorption bottle. And finally, obtaining gray black powder, washing with 0.1M hydrochloric acid, deionized water and ethanol respectively, and drying at 60 ℃ for 12h to obtain the phosphorus-doped titanium dioxide nanospheres.
(3) And (3) adding 200mg of the phosphorus-doped titanium dioxide nanosphere obtained in the step (2) into a 50mL Tris buffer solution (pH 8.5) for ultrasonic dispersion for 30min, uniformly dispersing, then adding 100mg of dopamine, stirring for 6h, finally centrifuging to obtain a precipitate, and drying at 60 ℃ for 12h to obtain the dopamine-coated phosphorus-doped titanium dioxide.
(4) And (3) placing the dopamine-coated phosphorus-doped titanium dioxide in the step (3) into a tubular furnace, and calcining in an argon atmosphere at the heating rate of 2 ℃/min at the calcining temperature of 500 ℃ for 2 h. Finally obtaining the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanosphere material (the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material).
Example 3
A preparation method of nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanospheres comprises the following steps:
(1) placing 150mL of ethanol and 100mL of acetonitrile in a 500mL beaker, stirring for 30min, uniformly stirring, then respectively adding 0.425mL of ammonia water and 0.91mL of deionized water, continuously stirring for 10min, uniformly stirring, adding 0.2g of surfactant (polyvinylpyrrolidone is selected) to obtain a mixed solution, then dropwise adding 5mL of isopropyl titanate into the mixed solution, and continuously stirring for 6h to obtain an emulsion; centrifuging the emulsion, collecting precipitates by centrifugation, washing the precipitates by ethanol and water respectively, and drying the precipitates for 12 hours at 60 ℃ to obtain amorphous titanium dioxide microporous nanospheres with high specific surface area;
(2) 200mg of the amorphous titanium dioxide microporous nanospheres in the step (1) are placed on the gas-close downstream side of a quartz boat, 2g of sodium hypophosphite is placed on the gas-close upstream side of the quartz boat, then under the condition of introducing argon, the gas flow rate is 20mL/min, the temperature is increased to 300 ℃ at the temperature increase rate of 2 ℃/min (the temperature is increased to the decomposition temperature of the sodium hypophosphite), the temperature is continuously increased at the same temperature increase rate, the introduction of the argon into the tube furnace is stopped, and the gas inlet and the gas outlet of the quartz tube are closed, so that the quartz tube becomes a closed system, and the sodium hypophosphite can be further decomposed to generate phosphine gas (the operation is carried out within the safe pressure range) along with the continuous increase of the temperature. And (3) continuously heating the tube furnace to 550 ℃, preserving heat for 2h, introducing argon into the tube after cooling to room temperature, and discharging phosphine gas in the tube into an absorption bottle. And finally, obtaining gray black powder, washing with 0.1M hydrochloric acid, deionized water and ethanol respectively, and drying at 60 ℃ for 12h to obtain the phosphorus-doped titanium dioxide nanospheres.
(3) And (3) adding 200mg of the phosphorus-doped titanium dioxide nanosphere obtained in the step (2) into a 50mL Tris buffer solution (pH 8.5) for ultrasonic dispersion for 30min, uniformly dispersing, then adding 50mg of dopamine, stirring for 12h, finally centrifuging to obtain a precipitate, and drying at 60 ℃ for 12h to obtain the dopamine-coated phosphorus-doped titanium dioxide.
(4) And (3) placing the dopamine-coated phosphorus-doped titanium dioxide in the step (3) into a tubular furnace, and calcining in an argon atmosphere at the heating rate of 2 ℃/min at the calcining temperature of 700 ℃ for 2 h. Finally obtaining the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanosphere material (the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material).
Comparative example 1
Placing 150mL of ethanol and 100mL of acetonitrile in a 500mL beaker, stirring for 30min, uniformly stirring, then respectively adding 0.425mL of ammonia water and 0.46mL of deionized water, continuously stirring for 10min, uniformly stirring, adding 0.1g of surfactant (polyvinylpyrrolidone is selected) to obtain a mixed solution, then dropwise adding 5mL of isopropyl titanate into the mixed solution, and continuously stirring for 6h to obtain an emulsion; and centrifuging the emulsion, collecting precipitates by centrifugation, washing the precipitates by using ethanol and water respectively, and drying the precipitates for 12 hours at the temperature of 60 ℃ to obtain the amorphous titanium dioxide microporous nanospheres with high specific surface area.
Comparative example 2
(1) Placing 150mL of ethanol and 100mL of acetonitrile in a 500mL beaker, stirring for 30min, uniformly stirring, then respectively adding 0.425mL of ammonia water and 0.46mL of deionized water, continuously stirring for 10min, uniformly stirring, adding 0.1g of surfactant (polyvinylpyrrolidone is selected) to obtain a mixed solution, then dropwise adding 5mL of isopropyl titanate into the mixed solution, and continuously stirring for 6h to obtain an emulsion; centrifuging the emulsion, collecting precipitates by centrifugation, washing the precipitates by ethanol and water respectively, and drying the precipitates for 12 hours at 60 ℃ to obtain amorphous titanium dioxide microporous nanospheres with high specific surface area;
(2) placing 200mg of the amorphous titanium dioxide microporous nanospheres in the step (1) on the gas-close downstream side of a quartz boat, placing 4g of sodium hypophosphite on the gas-close upstream side of the quartz boat, then under the condition of introducing argon gas, the gas flow rate is 20mL/min, raising the temperature to 300 ℃ at the temperature rise rate of 2 ℃/min (raising the temperature to the decomposition temperature of the sodium hypophosphite), continuing to raise the temperature at the same temperature rise rate, stopping introducing the argon gas into the tube furnace, closing the gas inlet and the gas outlet of the quartz tube, enabling the quartz tube to be a closed system, and further decomposing the sodium hypophosphite to generate phosphine gas (operating within the safe pressure range) along with the continuous temperature rise. And (3) continuously heating the tube furnace to 500 ℃, keeping the temperature for 2h, introducing argon into the tube after cooling to room temperature, discharging phosphine gas in the tube into an absorption bottle, finally obtaining gray black powder, washing the gray black powder by using 0.1M hydrochloric acid, deionized water and ethanol respectively, and drying the gray black powder for 12h at the temperature of 60 ℃ to obtain the phosphorus-doped titanium dioxide nanospheres.
Comparative example 3
(1) Placing 150mL of ethanol and 100mL of acetonitrile in a 500mL beaker, stirring for 30min, uniformly stirring, then respectively adding 0.425mL of ammonia water and 0.46mL of deionized water, continuously stirring for 10min, uniformly stirring, adding 0.1g of surfactant (polyvinylpyrrolidone is selected) to obtain a mixed solution, then dropwise adding 5mL of isopropyl titanate into the mixed solution, and continuously stirring for 6h to obtain an emulsion; centrifuging the emulsion, collecting precipitates by centrifugation, washing the precipitates by ethanol and water respectively, and drying the precipitates for 12 hours at 60 ℃ to obtain amorphous titanium dioxide microporous nanospheres with high specific surface area;
(2) adding 200mg of the amorphous titanium dioxide microporous nanospheres obtained in the step (1) into a Tris buffer solution (with the pH value of 8.5) for ultrasonic dispersion for 30min, then adding 70mg of dopamine, stirring for 3h, finally filtering and collecting, and drying at 60 ℃ for 12h to obtain dopamine-coated titanium dioxide nanospheres;
(3) and (3) placing the dopamine coated titanium dioxide nanospheres in the step (2) into a tubular furnace, and calcining in an argon atmosphere at the heating rate of 2 ℃/min at the calcining temperature of 600 ℃ for 2 h. Finally obtaining the nitrogen-doped carbon-coated titanium dioxide nanosphere material.
Comparative example 4
(1) Placing 150mL of ethanol and 100mL of acetonitrile in a 500mL beaker, stirring for 30min, uniformly stirring, then respectively adding 0.425mL of ammonia water and 0.46mL of deionized water, continuously stirring for 10min, uniformly stirring, adding 0.1g of surfactant (polyvinylpyrrolidone is selected) to obtain a mixed solution, then dropwise adding 5mL of isopropyl titanate into the mixed solution, and continuously stirring for 6h to obtain an emulsion; centrifuging the emulsion, collecting precipitates by centrifugation, washing the precipitates by ethanol and water respectively, and drying the precipitates for 12 hours at 60 ℃ to obtain amorphous titanium dioxide microporous nanospheres with high specific surface area;
(2) adding 200mg of the amorphous titanium dioxide microporous nanospheres obtained in the step (1) into a Tris buffer solution (with the pH value of 8.5) for ultrasonic dispersion for 30min, then adding 70mg of dopamine, stirring for 3h, finally filtering and collecting, and drying at 60 ℃ for 12h to obtain dopamine-coated titanium dioxide nanospheres;
(3) and (3) placing the dopamine coated titanium dioxide nanospheres in the step (2) into a tubular furnace, and calcining in an argon atmosphere at the heating rate of 2 ℃/min at the calcining temperature of 600 ℃ for 2 h. Finally obtaining the nitrogen-doped carbon-coated titanium dioxide nanosphere material;
(4) and (3) placing 200mg of the nitrogen-doped carbon-coated titanium dioxide nanosphere material in the step (3) on the gas-close downstream side of the quartz boat, placing 4g of sodium hypophosphite on the gas-close upstream side of the quartz boat, then introducing argon gas, wherein the gas flow rate is 20mL/min, raising the temperature to 300 ℃ at the temperature rise rate of 2 ℃/min (raising the temperature to the decomposition temperature of the sodium hypophosphite), continuing to raise the temperature at the same temperature rise rate, stopping introducing the argon gas into the tube furnace, closing the gas inlet and the gas outlet of the quartz tube, enabling the quartz tube to be a closed system, and further decomposing the sodium hypophosphite to generate phosphine gas (operating within the safe pressure range) along with the continuous temperature rise. And (3) continuously heating the tube furnace to 500 ℃, keeping the temperature for 2h, introducing argon into the tube after cooling to room temperature, discharging phosphine gas in the tube into an absorption bottle, finally obtaining gray black powder, washing the gray black powder by using 0.1M hydrochloric acid, deionized water and ethanol respectively, and drying the gray black powder for 12h at the temperature of 60 ℃ to obtain the phosphorus-doped titanium dioxide nanospheres.
Effect verification
Comparative example 1, comparative example 2, comparative example 3, and comparative exampleProportion 4, example 2 and example 3 the components therein were qualitatively examined with an X-ray powder diffractometer (Bruker D8 ADVANCE, Germany). The scan angle was 10-80 ° and their composition was obtained by alignment with a standard card. As shown in fig. 1 and 3, the XRD data of comparative example 1 has a broad peak at 25.3 °, indicating that comparative example 1 is amorphous titanium dioxide. All diffraction peaks of example 1, example 2, example 3, comparative example 2, comparative example 3, and comparative example 4 may correspond to anatase TiO2The standard diffraction data of (JCPDS: 21-1272). It is shown that amorphous titanium dioxide is converted into anatase titanium dioxide by the calcination treatment.
FIG. 2 is a nitrogen adsorption and desorption graph and a pore size distribution graph of the amorphous titanium dioxide microporous nanospheres with high specific surface area prepared in step (1) of example 1, and Table 1 is a table of specific surface area and pore size data of the amorphous titanium dioxide microporous nanospheres with high specific surface area in step (1) of example 1. As shown in FIG. 2 and Table 1, the amorphous titanium dioxide nanospheres synthesized in example 1 have a specific surface area as high as 426.39m2g-1The pore size distribution is mainly concentrated in micropores, demonstrating that the amorphous titanium dioxide nanospheres synthesized in example 1 are amorphous titanium dioxide microporous nanospheres with high specific surface area.
TABLE 1
FIG. 4 is a thermogravimetric plot of examples 1, 2 and 3 for the purpose of exploring the carbon content in each example. As can be seen from the figure, the weight of the material of each example decreased at 100 ℃ due to the evaporation of water in the material. A slight increase in the weight of the material follows, which may be caused by the combination of P and oxygen in the material. When the temperature reaches 400 ℃, the carbon layer coated on the material begins to decompose, and when the temperature reaches 600 ℃, the carbon layer on the material is completely decomposed. The carbon contents of example 1, example 2 and example 3 were calculated to be 2.3%, 4.9% and 6.9%, respectively. This demonstrates that the carbon content of the material can be varied by controlling the reaction time of the phosphorus doped titanium dioxide in the dopamine buffer solution.
Fig. 5 is an SEM image of example 1, comparative example 2, and comparative example 3. Each material is a nanosphere with a smooth surface and a diameter of about 300-400 nm. The original morphology of example 1 is maintained after calcination and phosphating. The relative atomic proportions of the different components in example 1 and comparative example 2 can be calculated semi-quantitatively from fig. 6, where it is seen that the atomic percentage of phosphorus in the material of example 1 is as high as 6.05% and there is no significant reduction in phosphorus content compared to comparative example 2, demonstrating the feasibility of a phosphorus-first-then-carbon route to maintain high phosphorus doping levels.
FIG. 7 is an XPS fine spectrum of the P, Ti, O and N elements of the nitrogen doped carbon coated phosphorus doped titanium dioxide material of example 1; according to the XPS fine spectrum result of phosphorus element, the two signal peaks of 2P orbital splitting are respectively 134.4eV (P2P 1/2) and 133.6eV (P2P 3/2), which belong to the peaks of phosphates. And XPS fine spectrum results of oxygen element show peaks at 530.9, 532.1 and 533.6eV which are signal peaks of O-Ti, P-O-Ti and O-P bonds, respectively. XPS fine spectrogram of titanium element shows Ti4+Oxidation state, and the presence of lattice oxygen, O-Ti4+And Ti-OH. The XPS fine spectrum of the nitrogen element shows four signal peaks, 398.8, 399.9, 400.9 and 402.8eV, which are identified as pyridine N, pyrrole N, graphite N and O-N bonds in turn. Further proves that the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide nanosphere material is successfully prepared by the preparation method.
The materials obtained in example 1, example 2, example 3, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 were used as active materials, respectively, to prepare electrode sheets. The preparation process of the electrode plate comprises the following steps of mixing an active substance (such as the material in example 1), acetylene black and PVDF according to the mass ratio of 8:1:1, coating the obtained slurry on a copper foil with the diameter of 14mm, and drying in an oven to obtain the electrode plate. And then, assembling the prepared electrode slice as a working electrode and the metal sodium as a counter electrode into a sodium ion battery and testing the sodium storage performance of the sodium ion battery. Example 1 negative electrode for sodium ion battery at 0.05Ag-1The first three circles of charging and dischargingThe electrical curves are shown in fig. 8. The discharge specific capacity and the charge specific capacity of the first ring are 414.5 mAhg and 225.9mAhg respectively-1And the corresponding first turn coulombic efficiency was 54.5%, which is probably due to the formation of the SEI film and the decomposition of the electrolyte. And the coulombic efficiency was higher than 95% in both the subsequent second and third rounds. As can be seen from fig. 9, the sodium ion battery assembled as the working electrode in example 1 was operated at different current densities (0.05, 0.1, 0.2, 0.5, 1.0, 2.0, and 5.0Ag-1) 213.8, 191.9, 173.8, 145.6, 127.9, 100.9 and 61.9mAhg are provided respectively-1The reversible capacity of (a).
As shown in fig. 9, it can be seen that the rate performance of example 1 is greatly improved compared to comparative examples 1, 2 and 3. Example 1 also shows that phosphorus doping and carbon coating have synergistic effects, and the performance of the material can be further improved. Meanwhile, fig. 12 further shows that the rate capability of the amorphous titanium dioxide material subjected to phosphorus doping and carbon coating treatment as the negative electrode of the sodium-ion battery is greatly improved. As shown in FIG. 11, after phosphorus doping and carbon coating, the long cycle performance of the material of example 1 is greatly improved to 0.1Ag-1177.8mAhg is remained after the current density is circulated for 100 circles-1The reversible capacity of (a).
In addition, the sequence of phosphorus doping and carbon coating has obvious influence on the material performance. When the carbon coating treatment is performed first as shown in fig. 10, carbon-coated anatase nanospheres (comparative example 3) are obtained, and if phosphorus doping is performed subsequently, the phosphorus doping amount cannot be increased, and even the crystal structure of anatase is destroyed, so that the performance of the material is deteriorated. Therefore, the embodiment of the invention adopts amorphous titanium dioxide as the phosphorus-doped precursor, which is beneficial to improving the doping amount so as to improve the specific capacity of the material, and then the sodium storage performance and the cycle performance of the material are further improved after nitrogen-doped carbon coating, so that the material is more suitable to be used as the electrode material of a high-performance sodium ion battery.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material is characterized by comprising the following steps:
(1) adding ammonia water and water into a mixed solution of ethanol and acetonitrile, uniformly mixing, adding a surfactant, dropwise adding isopropyl titanate, and stirring to obtain an emulsion; centrifuging the emulsion, taking the precipitate, washing and drying to obtain the amorphous titanium dioxide microporous nanospheres;
(2) placing sodium hypophosphite and the amorphous titanium dioxide microporous nanospheres obtained in the step (1) into a reactor, heating to the decomposition temperature of the sodium hypophosphite in a protective atmosphere, closing an air inlet and an air outlet of the reactor, performing heating treatment to obtain a heated product, washing, and drying to obtain phosphorus-doped titanium dioxide nanospheres;
(3) ultrasonically dispersing the phosphorus-doped titanium dioxide nanospheres in the step (2) into a buffer solution, adding dopamine, stirring, centrifuging, and taking precipitates to obtain phosphorus-doped titanium dioxide nanospheres coated with dopamine;
(4) and (4) heating the dopamine-coated phosphorus-doped titanium dioxide nanospheres in the step (3) under a protective atmosphere to perform calcination treatment, so as to obtain the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material.
2. The method for preparing the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material according to claim 1, wherein the ammonia water in the step (1) is 25-28% by mass, and the volume ratio of isopropyl titanate, ammonia water and water is 5: 0.425: 0.31-0.91.
3. The method for preparing nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material according to claim 1, wherein in the mixed solution of ethanol and acetonitrile in the step (1), the volume ratio of ethanol to acetonitrile is 3: 1.5-3; the surfactant is polyvinylpyrrolidone, and the mass volume ratio of the surfactant to ammonia water is (0.1-0.2): 0.425 g/mL; the volume ratio of the water to the mixed solution of the ethanol and the acetonitrile is 0.31-0.91: 250-275.
4. The method for preparing nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material according to claim 1, wherein the stirring treatment in the step (1) is carried out for 4-8 h; the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
5. The method for preparing nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material according to claim 1, wherein the mass ratio of the amorphous titanium dioxide microporous nanospheres and sodium hypophosphite in step (2) is 1: 10-20.
6. The method of claim 1, wherein the protective atmosphere in step (2) is an argon or nitrogen atmosphere; the rate of temperature rise is 1-5 ℃/min; the temperature of the heating treatment is 400-550 ℃, and the time of the heating treatment is 1-2 h; the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
7. The method of claim 1, wherein the buffer solution of step (3) is a Tris buffer solution; the pH value of the buffer solution is 8-8.5; the mass ratio of the phosphorus-doped titanium dioxide nanospheres to the dopamine is 2-4: 1; the mass-to-volume ratio of the phosphorus-doped titanium dioxide nanospheres to the buffer solution is 0.2: 50-60 g/mL; the stirring treatment time is 3-12 h.
8. The method of claim 1, wherein the protective atmosphere in step (4) is a nitrogen or argon atmosphere; the rate of temperature rise is 1-5 ℃/min; the temperature of the calcination treatment is 500-700 ℃, and the time of the calcination treatment is 1-2 hours.
9. A nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material produced by the production method according to any one of claims 1 to 8.
10. Use of the nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material of claim 9 in the preparation of a sodium ion battery.
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