CN115732663A - Preparation method and energy storage application of titanium dioxide/heterogeneous atom doped porous carbon material - Google Patents
Preparation method and energy storage application of titanium dioxide/heterogeneous atom doped porous carbon material Download PDFInfo
- Publication number
- CN115732663A CN115732663A CN202211579879.0A CN202211579879A CN115732663A CN 115732663 A CN115732663 A CN 115732663A CN 202211579879 A CN202211579879 A CN 202211579879A CN 115732663 A CN115732663 A CN 115732663A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon material
- doped porous
- atom
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method and energy storage application of a titanium dioxide/heterogeneous atom doped porous carbon material, which is used for thermally synthesizing titanium-based metal organic framework NH in a solvent 2 Adding an additive while MIL-125 (Ti), annealing in an inert atmosphere, and fully utilizing a product of in-situ decomposition of the additive in the annealing process to realize pore forming and/or realize hetero atom doping, so as to obtain the titanium dioxide/hetero atom doped porous carbon material with high specific surface area and high hetero atom doping amount. The high specific surface area can increase more active sites and provide abundant channels for ion storage; the heterogeneous atom doping can improve the ion diffusion kinetics and the conductivity, and furtherThe rate capability and the cycling stability of the material are improved.
Description
Technical Field
The invention belongs to the field of functional material preparation, and particularly relates to a preparation method and energy storage application of a titanium dioxide/hetero atom doped porous carbon material with a high specific surface area and a high hetero atom doping amount.
Background
With the increasing energy consumption and global warming, there is an increasing demand for green and efficient energy storage systems providing high energy and high power. Lithium ion batteries have the advantages of high voltage, high energy density, and the like, and have been widely applied to the fields of portable electronic devices, electric vehicles, energy storage, and the like. However, as demand increases, the problem of shortage of lithium resources becomes more and more prominent. Sodium is an evenly distributed and abundant element, and in recent years, sodium ion batteries are considered as an important lithium ion battery to replace a chemical power system and are widely researched. Titanium dioxide (TiO) 2 ) Because of its low cost, good circulation stability and high theoretical capacity (335 mAhg) -1 ) And is considered an ideal anode material with almost zero strain during charge and discharge. However, titanium dioxide has a relatively low conductivity (10. About. -12 Scm -1 )、Na + In TiO 2 The slow diffusion in the process results in poor specific capacity and rate capability of the material, and the practical application of the material is severely limited. Design of appropriate nanostructures to shorten Na + Improvement of TiO in diffusion paths or in combination with suitable carbon materials to increase its electronic conductivity 2 Strategy of electrochemical kinetics.
Disclosure of Invention
Based on the problems existing in the prior art, the invention aims to provide a preparation method and energy storage application of a titanium dioxide/hetero atom doped porous carbon material with high specific surface area and high hetero atom doping amount.
The invention adopts the following technical scheme for realizing the purpose:
a preparation method of a titanium dioxide/heterogeneous atom doped porous carbon material is characterized by comprising the following steps: thermal synthesis of titanium-based metal organic framework NH in solvent 2 Adding an additive while MIL-125 (Ti), annealing in an inert atmosphere, and fully utilizing a product of in-situ decomposition of the additive in the annealing process to realize pore forming and/or realize hetero atom doping, so that the titanium dioxide/hetero atom doped porous carbon material with high specific surface area and high hetero atom doping amount is obtained. The method specifically comprises the following steps:
Dissolving 0.8-1.6 g of organic ligand, 50-500 mg of additive and 0.5-1.0 mL of titanium salt in a mixed solution of 27-60 mLN-N Dimethylformamide (DMF) and methanol (the volume ratio of DMF to methanol is 9:1), uniformly stirring, carrying out solvothermal reaction, centrifuging, washing, drying and collecting a product to obtain NH 2 -MIL-125(Ti)；
Step 2, annealing under inert atmosphere to prepare titanium dioxide/heterogeneous atom doped porous carbon material
Weighing 50-200 mgNH 2 And (3) placing MIL-125 (Ti) in a tube furnace, annealing under a protective atmosphere, and then cooling to room temperature along with the furnace to obtain the titanium dioxide/hetero atom doped porous carbon material.
Preferably, the organic ligand is terephthalic acid or diaminoterephthalic acid.
Preferably, the titanium salt is tetraethyl titanate, isopropyl titanate or n-butyl titanate.
Preferably, the additive is at least one of sodium bicarbonate for pore-forming, melamine for pore-forming and nitrogen doping, rhodanine for sulfur doping, sodium dihydrogen phosphate for phosphorus doping, and ammonium selenocyanate for selenium doping.
Preferably, in step 1, the temperature of the solvothermal reaction is 100 to 200 ℃ and the holding time is 10 to 30 hours.
Preferably, in step 2, the annealing treatment is performedThe heating rate of (1) to (10) DEG C for min -1 The temperature is 500-900 ℃, and the heat preservation time is 90-360 min.
Preferably, in step 2, the protective atmosphere is argon, nitrogen or a hydrogen-argon mixture.
The titanium dioxide/heterogeneous atom doped porous carbon material prepared by the method can be used as an electrochemical energy storage material, such as a negative electrode material of a battery, and shows excellent rate capability. In addition, the method has universality and also has great potential in the fields of catalysis, pollutant adsorption, sensing and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. titanium-based metal organic framework material NH 2 MIL-125 (Ti) is a new porous crystalline material with a high surface area, porous structure. According to the invention, through annealing in an inert atmosphere, the titanium dioxide particles are uniformly dispersed in the in-situ derived carbon matrix, the composite structure is completely different from the traditional surface carbon coating on the titanium dioxide particles in the prior art, and the retained carbon matrix obviously improves the ion storage performance of the metal oxide. In addition, lattice distortion and electron redistribution caused by doping of heterogeneous atoms are common methods for adjusting the electronic structure of the electrode material and improving electrochemical performance. At present, the method for doping the heterogeneous atoms is single, two-step doping is mostly adopted, the doping amount of the heterogeneous atoms is low, and the operation is complex and tedious. The addition of the additive according to the invention makes it possible to intercalate NH 2 In the MIL-125 (Ti), the additive can decompose and release gas in the subsequent high-temperature annealing process, so that pore forming and high doping amount are realized, and the operation is simple. The doping of the hetero atoms can provide more structural vacancies and defects for the adsorption and diffusion paths of ions, and endow the electrode material with excellent rate performance and cycle stability.
2. According to the invention, annealing is carried out in the hydrogen-argon atmosphere to increase oxygen defects in titanium dioxide, the oxygen defects can induce more heterogeneous atom doping, high doping amount is realized, the heterogeneous atom doping rate is high, and the energy storage characteristic of the cathode material is further improved.
3. The doping of the hetero atoms in the titanium dioxide/hetero atom doped porous carbon material prepared by the invention can expose more active sites, and the doping of the hetero atoms can form lattice distortion so as to increase defects.
4. The preparation method can be applied to other metal organic framework materials to realize different heterogeneous atom doping.
5. The preparation method is simple, short in preparation time, low in cost and easy for large-scale production.
Drawings
FIG. 1 shows NH obtained in example 1 2 FESEM photograph of MIL-125 (Ti);
FIG. 2 is a FESEM photograph of the titania/nitrogen-doped porous carbon material obtained in example 2;
FIG. 3 is a FESEM photograph of the titania/nitrogen-doped porous carbon material obtained in example 3;
FIG. 4 is a FESEM photograph of the titania/nitrogen-doped porous carbon material obtained in example 4;
FIG. 5 shows NH obtained in examples 1, 3 and 4 2 -XRD pattern of MIL-125 (Ti);
FIG. 6 is an XRD pattern of the titanium dioxide/nitrogen-doped porous carbon material obtained in examples 2, 3 and 4;
FIG. 7 is a BET spectrum of the titanium dioxide/nitrogen-doped porous carbon material obtained in examples 2, 3 and 4;
FIG. 8 is a graph comparing the nitrogen contents of the titania/nitrogen-doped porous carbon materials obtained in examples 2, 3 and 4;
FIG. 9 shows the titanium dioxide/nitrogen-doped porous carbon materials obtained in examples 2, 3 and 4 under different current densities (50-10000 mAg) -1 ) The rate performance curve of (1).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof will be described in detail with reference to the following examples. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Dissolving 1.1g of diaminoterephthalic acid and 0.6mL of isopropyl titanate in a mixed solution of 40mLDMF and methanol (the volume ratio of DMF to methanol is 9:1), uniformly stirring, and then preserving heat for 24 hours in an electric heating constant-temperature air-blowing drying box at the temperature of 150 ℃; naturally cooling to room temperature, generating faint yellow precipitate in the reaction kettle, centrifuging, washing, drying and collecting a product to obtain NH 2 -MIL-125 (Ti) with FESEM photograph, XRD pattern as shown in fig. 1 and fig. 5, respectively.
Example 2
Dissolving 1.1g of diaminoterephthalic acid and 0.6mL of isopropyl titanate in a mixed solution of 40mLDMF and methanol (the volume ratio of DMF to methanol is 9:1), uniformly stirring, and then preserving heat for 24 hours in an electric heating constant-temperature air-blowing drying box at the temperature of 150 ℃; naturally cooling to room temperature, generating light yellow precipitate in the reaction kettle, centrifuging, washing, drying and collecting a product to obtain NH 2 -MIL-125(Ti)。
Step 2, preparing titanium dioxide/nitrogen-doped porous carbon material through high-temperature annealing treatment
Weighing 100mgNH 2 Placing MIL-125 (Ti) in a tube furnace, and annealing under hydrogen-argon mixed gas atmosphere (hydrogen volume percent is 5%), wherein the temperature rise rate of the annealing is 5 ℃ for min -1 The temperature is 600 ℃, and the heat preservation time is 2 hours. And then cooling to room temperature along with the furnace to obtain the titanium dioxide/nitrogen doped porous carbon material, wherein the FESEM picture and the XRD pattern are respectively shown in figure 2 and figure 6.
Example 3
1.1g of diaminoterephthalic acid, 67mg of sodium bicarbonate (pore-forming agent) and 0.6mL of isopropyl titanate were dissolved in 40mL of a mixture of DMF and methanol (the volume ratio of DMF to methanol was 9:1), and after stirring, the mixture was heated at a constant temperature of 150 ℃ under electric heatingKeeping the temperature in the air-blowing drying box for 24 hours; naturally cooling to room temperature, generating light yellow precipitate in the reaction kettle, centrifuging, washing, drying and collecting the product to obtain modified NH 2 -MIL-125 (Ti) having an XRD pattern as shown in figure 5.
Step 2, preparing titanium dioxide/nitrogen-doped porous carbon through high-temperature annealing treatment
100mg of modified NH are weighed 2 Placing MIL-125 (Ti) in a tube furnace, and annealing under hydrogen-argon mixed gas atmosphere (hydrogen volume percent is 5%), wherein the temperature rise rate of the annealing is 5 ℃ for min -1 The temperature is 600 ℃, and the heat preservation time is 2 hours. And then cooling to room temperature along with the furnace to obtain the titanium dioxide/nitrogen doped porous carbon material, wherein the FESEM picture and the XRD pattern are respectively shown in figure 3 and figure 6.
Example 4
Dissolving 1.1g of diaminoterephthalic acid, 201mg of melamine (pore-forming agent/nitrogen doped) and 0.6mL of isopropyl titanate in a mixed solution of 40mLDMF and methanol (the volume ratio is 9:1), uniformly stirring, and then preserving heat for 24 hours in an electric heating constant-temperature air blowing drying box at the temperature of 150 ℃; naturally cooling to room temperature, generating faint yellow precipitate in the reaction kettle, centrifuging, washing, drying and collecting a product to obtain the modified NH 2 -MIL-125 (Ti) having an XRD pattern as shown in figure 5.
Step 2, preparing titanium dioxide/nitrogen-doped porous carbon through high-temperature annealing treatment
100mg of modified NH are weighed 2 Placing MIL-125 (Ti) in a tube furnace, and annealing under hydrogen-argon mixed gas atmosphere (hydrogen volume percent is 5%), wherein the temperature rise rate of the annealing is 5 ℃ for min -1 The temperature is 600 ℃, and the heat preservation time is 2 hours. And then cooling to room temperature along with the furnace to obtain the titanium dioxide/nitrogen doped porous carbon material, wherein the FESEM photos and the XRD patterns are respectively shown in figures 4 and 6.
Referring to the above examples, the present invention has studied the effects of different additives on the microstructure, phase composition and electrochemical properties of titania/nitrogen-doped porous carbon, as can be seen from fig. 1 to 4The addition of the sodium hydrogen carbonate and the melamine has no influence on the appearance of the alloy, and the alloy inherits the original appearance after high-temperature annealing treatment in protective gas atmosphere. From fig. 5 to 6, it can be seen that the addition of sodium bicarbonate and melamine did not change the phases. As can be seen from FIGS. 7 to 8, the specific surface areas of the titania/nitrogen-doped porous carbon materials obtained in examples 2, 3 and 4 were 102.67m 2 g -1 、175.12m 2 g -1 、185.58m 2 g -1 The relative nitrogen contents were 4.96%, 4.97%, and 6.91%, respectively.
The materials synthesized in examples 2, 3 and 4 were respectively slurried with acetylene black and polyvinylidene fluoride PVDF in a mass ratio of 8 -1 NaPF 6 And a 2320 type polypropylene microporous membrane is taken as a diaphragm, and the diaphragm is assembled into a 2032 type button battery in a glove box. The LANDCT-2001A test system is adopted to test the voltage of 50-10000 mAg within the range of 0.01-3.0V at room temperature -1 Constant current charge and discharge tests were performed at the current density of (1).
FIG. 9 shows that the materials prepared in examples 2, 3 and 4 have different current densities (50-10000 mAg) -1 ) The rate performance curve of (2). Example 2 the material prepared was at 50mAg -1 Has a specific discharge capacity of 210.3mAhg at a current density of -1 At 10000mAg -1 Has a specific discharge capacity of 79.1mAhg at a current density of -1 (ii) a Example 3 the material prepared was at 50mAg -1 The specific discharge capacity of the current density of (2) was 242.8mAhg -1 At 10000mAg -1 Has a specific discharge capacity of 120.8mAhg at a current density of -1 (ii) a Example 4 the material prepared at 50mAg -1 The specific discharge capacity of the current density of (a) is 282.5mAhg -1 At 10000mAg -1 Has a specific discharge capacity of 178.2mAhg at a current density of -1 . Compared with examples 2 and 3, the material prepared in example 4 has more excellent rate capability, and can be used as an ideal sodium-ion battery negative electrode material.
Claims (10)
1. Titanium dioxide/titanium dioxideThe preparation method of the atomic-doped porous carbon material is characterized by comprising the following steps: thermal synthesis of titanium-based metal organic framework NH in solvent 2 Adding an additive while adding MIL-125 (Ti), then annealing in an inert atmosphere, and fully utilizing products of in-situ decomposition of the additive in the annealing process to realize pore forming and/or realize heterogeneous atom doping, thus obtaining the titanium dioxide/heterogeneous atom doped porous carbon material.
2. The method for preparing the titanium dioxide/hetero atom doped porous carbon material according to claim 1, comprising the steps of:
step 1, preparing NH by solvothermal method 2 -MIL-125(Ti)
Dissolving 0.8-1.6 g of organic ligand, 50-500 mg of additive and 0.5-1.0 mL of titanium salt in a mixed solution of 27-60 mLN-N dimethylformamide and methanol, uniformly stirring, carrying out solvothermal reaction, centrifuging, washing, drying and collecting a product to obtain NH 2 -MIL-125(Ti)；
Step 2, annealing under inert atmosphere to prepare titanium dioxide/heterogeneous atom doped porous carbon material
Weighing 50-200 mgNH 2 And (3) placing MIL-125 (Ti) in a tube furnace, annealing under a protective atmosphere, and then cooling to room temperature along with the furnace to obtain the titanium dioxide/hetero atom doped porous carbon material.
3. The method for preparing a titania/hetero atom-doped porous carbon material according to claim 2, wherein: the organic ligand is terephthalic acid or diamino terephthalic acid.
4. The method for preparing a titania/hetero-atom-doped porous carbon material according to claim 2, characterized in that: the titanium salt is tetraethyl titanate, isopropyl titanate or n-butyl titanate.
5. The method for preparing a titania/hetero atom-doped porous carbon material according to claim 1 or 2, characterized in that: the additive is at least one of sodium bicarbonate for realizing pore forming, melamine for realizing pore forming and nitrogen doping, rhodanine for realizing sulfur doping, sodium dihydrogen phosphate for realizing phosphorus doping and ammonium selenocyanate for realizing selenium doping.
6. The method for preparing a titania/hetero-atom-doped porous carbon material according to claim 2, characterized in that: in the step 1, the temperature of the solvothermal reaction is 100-200 ℃, and the heat preservation time is 10-30 h.
7. The method for preparing a titania/hetero-atom-doped porous carbon material according to claim 2, characterized in that: in step 2, the temperature rise rate of the annealing treatment is 1-10 ℃ for min -1 The temperature is 500-900 ℃, and the heat preservation time is 90-360 min.
8. The method for preparing a titania/hetero-atom-doped porous carbon material according to claim 2, characterized in that: in the step 2, the protective atmosphere is argon, nitrogen or a hydrogen-argon mixed gas.
9. A titania/hetero atom-doped porous carbon material produced by the production method according to any one of claims 1 to 8.
10. An energy storage application of the titania/hetero-atom-doped porous carbon material of claim 9, wherein: the material is used for electrochemical energy storage materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211579879.0A CN115732663A (en) | 2022-12-09 | 2022-12-09 | Preparation method and energy storage application of titanium dioxide/heterogeneous atom doped porous carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211579879.0A CN115732663A (en) | 2022-12-09 | 2022-12-09 | Preparation method and energy storage application of titanium dioxide/heterogeneous atom doped porous carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115732663A true CN115732663A (en) | 2023-03-03 |
Family
ID=85300934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211579879.0A Pending CN115732663A (en) | 2022-12-09 | 2022-12-09 | Preparation method and energy storage application of titanium dioxide/heterogeneous atom doped porous carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115732663A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282007A (en) * | 2023-03-24 | 2023-06-23 | 西南科技大学 | Preparation method and application of biomass carbon microsphere material |
-
2022
- 2022-12-09 CN CN202211579879.0A patent/CN115732663A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282007A (en) * | 2023-03-24 | 2023-06-23 | 西南科技大学 | Preparation method and application of biomass carbon microsphere material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110492081B (en) | Preparation method and application of cobalt selenide/zinc selenide @ nitrogen-doped porous carbon nanotube | |
| EP3353841B1 (en) | Method of preparing and application of carbon-selenium composites | |
| CN109755545B (en) | Porous carbon material and preparation method thereof, porous carbon/sulfur composite material, battery positive electrode material, lithium-sulfur battery and application thereof | |
| CN108232142B (en) | Zinc sulfide/graphene composite material, and preparation method and application thereof | |
| CN105280897B (en) | A kind of preparation method of lithium ion battery negative material C/ZnO/Cu composites | |
| CN111710860B (en) | Nitrogen-phosphorus co-doped carbon composite material modified by cobalt-molybdenum phosphide particles and preparation method and application thereof | |
| CN112551540B (en) | Silicon-aluminum molecular sieve additive for lithium-rich manganese-based positive electrode and preparation method and application thereof | |
| CN112280051A (en) | Preparation method and application of cobalt-based metal organic framework Co-MOF material | |
| CN105390677A (en) | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof | |
| CN109802129A (en) | A kind of metallic sodium cell negative electrode material and its preparation method and application | |
| CN112919533A (en) | Nitrogen-doped carbon-coated phosphorus-doped titanium dioxide material and preparation method and application thereof | |
| CN115732663A (en) | Preparation method and energy storage application of titanium dioxide/heterogeneous atom doped porous carbon material | |
| CN110400918B (en) | Preparation method of cobalt-sulfur compound/sulfur-doped carbon composite material | |
| CN109455764B (en) | Preparation method of MnOOH | |
| CN111653750A (en) | Preparation method of carbon nitride modified molybdenum disulfide lithium ion battery cathode material | |
| CN111106332A (en) | Preparation method of carbon nano material, positive electrode material and preparation method thereof | |
| Cheng et al. | Porous ZnO/Co3O4/N-doped carbon nanocages synthesized via pyrolysis of complex metal–organic framework (MOF) hybrids as an advanced lithium-ion battery anode | |
| CN114890403A (en) | Nitrogen-doped polymer derived carbon material and application thereof in sodium ion battery | |
| CN109473634B (en) | Method for solid-phase co-thermal synthesis of molybdenum diselenide/nitrogen-doped carbon rod | |
| CN109494365A (en) | A kind of preparation method of the LDH- porous charcoal sulphur composite material for lithium-sulphur cell positive electrode | |
| CN110790252B (en) | MOF (Metal organic framework) derived porous carbon material for liquid-phase encapsulation of multi-phosphorus molecules as well as preparation method and application thereof | |
| CN110010893B (en) | Sulfur-rich carbon material for sodium ion battery negative electrode and preparation method thereof | |
| CN114695861B (en) | Preparation method of sulfur and nitrogen co-doped porous carbon material, prepared carbon material and application thereof | |
| CN113206226B (en) | Double-transition metal carbide compound and preparation method and application thereof | |
| CN110518194B (en) | Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |