CN112701260B - In-situ carbon-coated titanium niobate composite material and preparation method and application thereof - Google Patents

In-situ carbon-coated titanium niobate composite material and preparation method and application thereof Download PDF

Info

Publication number
CN112701260B
CN112701260B CN202011561540.9A CN202011561540A CN112701260B CN 112701260 B CN112701260 B CN 112701260B CN 202011561540 A CN202011561540 A CN 202011561540A CN 112701260 B CN112701260 B CN 112701260B
Authority
CN
China
Prior art keywords
carbon
niobium
titanium
source
heat treatment
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.)
Active
Application number
CN202011561540.9A
Other languages
Chinese (zh)
Other versions
CN112701260A (en
Inventor
孙永明
詹仁明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN202011561540.9A priority Critical patent/CN112701260B/en
Publication of CN112701260A publication Critical patent/CN112701260A/en
Application granted granted Critical
Publication of CN112701260B publication Critical patent/CN112701260B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • 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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H—ELECTRICITY
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention belongs to the field of energy storage devices, and particularly relates to an in-situ carbon-coated titanium niobate composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) dissolving a niobium source, sequentially adding a titanium source and a carbon source, and uniformly stirring to obtain a mixed solution; (2) drying the mixed solution, and removing the solvent to obtain a powder mixture; (3) carrying out primary heat treatment on the powder mixture to obtain a primary product; (4) and carrying out secondary heat treatment on the primary product in an oxygen-containing atmosphere. According to the invention, the carbon source is added in the first step of material mixing process to limit excessive growth of the primary particles of the titanium niobate, the first heat treatment is carried out in the inert gas to lead the uniformly distributed carbon source to be thermally decomposed into carbon, and the second heat treatment is carried out to lead the redundant carbon to be oxidized and removed, so that the problem of performance reduction caused by excessive carbon introduced by carbon wrapping is solved, the excessive growth of the titanium niobate is limited, and the performance of the material is comprehensively improved.

Description

In-situ carbon-coated titanium niobate composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of energy storage devices, and particularly relates to an in-situ carbon-coated titanium niobate composite material as well as a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs), one of the most widely used energy storage systems, have been widely used in consumer electronics products in the last two decades, and their applications have been expanded in recent decades into emerging fields such as Electric Vehicles (EVs), Hybrid Electric Vehicles (HEVs), and grid energy storage. The negative electrode is one of the key components of the battery. Most of the commercial lithium ion batteries at present adopt graphite carbon materials as negative electrodes, and the graphite materials have the problems of low lithium ion migration rate, low working voltage, poor charge-discharge rate performance, poor working safety at low temperature and the like, and cannot meet the application requirements of high rate and high safety working conditions. Therefore, the development of a negative electrode material for a lithium ion battery with both high rate and high safety is urgently needed.
Titanium niobate (Ti)xNbyOz) Due to its high working potential (>1V vs.Li+Li) to effectively avoid the safety problem caused by the precipitation of metallic lithium on the surface of the electrode during rapid charging or working at low temperature, and the material has the theoretical specific capacity equivalent to that of graphite. However, TixNbyThe inherent low electronic conductivity of the Oz material severely limits the actual electrochemical lithium storage specific capacity, cycle life and rate capability. The current research generally adopts the processes of secondary carbon coating, surface modification and the like to improve the conductivity, evenElectrochemical lithium storage performance. These methods tend to be complex, costly and not amenable to large-scale production.
CN110911666A discloses a method for synthesizing a nitrogenous carbon-coated titanium niobate material for a lithium battery cathode, which specifically discloses the following operations: mixing TiNb2O7And putting PVP (polyvinyl pyrrolidone) and the alcohol solvent into the alcohol solvent to prepare solution A, mixing the zinc nitrate alcohol solution and the 2-methylimidazole alcohol solution to react to obtain solution B, mixing the A, B solutions to perform a coating reaction, recovering a precipitate after the coating reaction is finished, purifying to obtain an intermediate product A, calcining the intermediate product A, and calcining to obtain the nitrogen-containing carbon-coated titanium niobate material. The technical proposal selects the metal organic framework compound pair TiNb with high nitrogen content2O7The coating is carried out to form the nitrogen-containing carbon-coated titanium niobate composite material, the nitrogen-containing carbon in the sample can improve the conductivity of the electrode material, so that the requirements of quick charge and discharge and prolonged service life are met, however, the technical scheme cannot solve the problem of possible excessive carbon coating, so that the performance of the product is unstable, and an improvement space is provided.
Therefore, the prior art is still lack of a preparation method of the titanium niobate composite material, which can overcome the defects of excessive carbon coating, and has simple preparation process and low cost.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method of an in-situ carbon-coated titanium niobate composite material, which can effectively promote the diffusion of lithium ions in a porous electrode by a pore structure generated in the process of removing a proper amount of carbon through secondary heat treatment, solve the problem of excessive carbon coating, and effectively inhibit the domain-limiting effect of a carbon source into Ti in the phase-forming processxNbyOzThe overgrowth of the primary particles effectively shortens the migration distance of the current carriers in the primary particles, and can effectively improve the electronic conductivity of the material. The detailed technical scheme of the invention is as follows.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing an in-situ carbon-coated titanium niobate composite material, comprising the steps of:
(1) dissolving a niobium source, sequentially adding a titanium source and a carbon source, and uniformly stirring to obtain a mixed solution;
(2) drying the mixed solution, and removing the solvent to obtain a powder mixture;
(3) carrying out primary heat treatment on the powder mixture to obtain a primary product;
(4) and carrying out secondary heat treatment on the primary product in an oxygen-containing atmosphere to obtain the in-situ carbon-coated titanium niobate composite material.
Preferably, the second heat treatment can adjust the carbon content and porosity of the in-situ carbon-coated titanium niobate composite material by controlling the treatment temperature, the treatment time and the oxygen concentration of the oxygen-containing atmosphere.
Preferably, the treatment temperature of the second heat treatment is 250-500 ℃, the treatment time is 0.2-20 hours, and the heating rate is 0.5-20 ℃ per minute.
Preferably, in the step (1), a solvent is added to dissolve the niobium source, the concentration of niobium ions is 0.001-20mol/L, and the solvent is one or a mixture of water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, n-propanol, isobutanol and n-butanol.
Preferably, the niobium source is one or more of niobium pentachloride, ammonium niobium oxalate, niobium ethoxide, niobium hydroxide, niobium pentoxide, niobium dioxide, niobium fluoride and niobium iodide; the titanium source is one or more of isopropyl titanate, titanium sulfate, titanium tetrachloride, titanium trichloride, titanyl sulfate, titanium tetraisopropoxide, butyl titanate, titanium tetrafluoride, titanium potassium oxalate and titanium dioxide, and the carbon source is one or more of ascorbic acid, citric acid, glucose, sucrose and polyvinylpyrrolidone.
Preferably, the titanium/niobium atomic ratio in step (1) is 0.0417-1; the mass ratio of the carbon source/niobium source is 0.02-0.1.
Preferably, the drying in step (2) is one of forced air drying, vacuum drying, freeze drying and spray drying.
Preferably, the treatment temperature of the first heat treatment is 500-1300 ℃, the treatment time is 2-80 hours, and the heating rate is 1-10 ℃/min.
According to a second aspect of the present invention, there is provided an in-situ carbon-coated titanium niobate composite material prepared according to the preparation method described above.
According to the third aspect of the invention, the application of the in-situ carbon-coated titanium niobate composite material as the negative pole piece of the lithium ion battery is provided.
The invention has the following beneficial effects:
(1) according to the invention, the carbon source is added in the first step of material mixing process, in-situ carbon wrapping is realized, excessive growth of the primary particles of the titanium niobate is limited, the first heat treatment is carried out in inert gas to thermally decompose the uniformly distributed carbon source into carbon, the second heat treatment is carried out to remove the excessive carbon by oxidation, the diffusion distance of ions in the primary particles is shortened, the rate capability of the material is improved, the treatment steps are connected in front and back, the problem of performance reduction caused by excessive carbon introduced by the carbon wrapping is solved, the excessive growth of the titanium niobate is limited, and the performance of the material is comprehensively improved.
(2) According to the titanium niobate composite material prepared by the invention, the pore structure generated in the process of removing a proper amount of carbon can effectively promote the diffusion of lithium ions in the porous electrode, the electronic conductivity of the material can be effectively improved by coating the material with a proper amount of carbon, and the carbon coating layer can effectively isolate the direct contact of the material and electrolyte, so that the generation of side reactions such as the decomposition of metal-catalyzed electrolyte is avoided; thereby improving the cycle life of the material, having excellent rate performance and cycle life electron as the lithium ion battery cathode material, and having wide market application prospect.
(3) The invention can regulate and control the carbon content of the composite material according to the actual application requirement, the carbon content of the material can be regulated and controlled by secondary oxygen-containing atmosphere low-temperature (250-500 ℃) heat treatment without further increasing the size of primary crystal grains, and the invention has the advantages of simple process, excellent performance and low cost.
Drawings
FIG. 1 shows TiNb prepared in example 1 of the present invention2O7XRD pattern of @ C.
FIG. 2 shows TiNb prepared in example 1 of the present invention2O7Thermogravimetric analysis Test (TGA) profile of @ C.
FIG. 3 shows TiNb prepared in example 1 of the present invention2O7Scanning Electron Microscope (SEM) picture of @ C.
FIG. 4 shows TiNb prepared in example 1 of the present invention2O7First charge and discharge performance curve of @ C.
FIG. 5 shows TiNb prepared in example 1 of the present invention2O7The cycling performance of @ C.
FIG. 6 shows TiNb prepared in example 1 of the present invention2O7Rate capability of @ C.
FIG. 7 shows TiNb prepared in example 2 of the present invention2O7The cycling performance of @ C.
FIG. 8 is a TiNb prepared in comparative example 12O7The cycling performance of @ C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
An in-situ carbon-coated titanium niobate composite material is prepared by the following method:
(1) weighing 2.11g Nb (OC)2H5)5Dissolved in 40mL of absolute ethanol, sufficiently stirred, and then 1.13g of Ti (OC) was weighed4H9)4Adding the mixture into the solution, and stirring vigorously for 1 hour to obtain a mixed solution;
(2) then adding 0.1g of ascorbic acid, quickly stirring for 2 hours, and carrying out vacuum drying on the obtained suspension for 12 hours at 150 ℃ to obtain a powder mixture;
(3) placing the obtained powder mixture in a tubular furnace, introducing nitrogen, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 10 hours, and naturally cooling to normal temperature to obtain an initial product;
(4) placing the primary product in a muffle furnace, heating to 350 ℃ at a speed of 5 ℃/min under the air atmosphere, preserving the heat for 1 hour, and naturally cooling to normal temperature to obtain a target product TiNb2O7@C。
Example 2
An in-situ carbon-coated titanium niobate composite material is prepared by the following method:
(1) weighing 5.4g NbCl5Dissolved in 80mL of absolute ethanol, sufficiently stirred, and then 2.84g of Ti (OC) was weighed3H7)4Adding the mixture into the solution, and stirring vigorously for 2 hours to obtain a mixed solution;
(2) then adding 0.4g of cane sugar, quickly stirring for 3 hours, and freeze-drying the obtained suspension for 24 hours to obtain a powder mixture;
(3) placing the powder mixture in a tubular furnace, introducing nitrogen, heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 5 hours, and naturally cooling to normal temperature to obtain a primary product;
(4) placing the primary product in a muffle furnace, heating to 400 ℃ at a speed of 3 ℃/min under the atmosphere of pure oxygen, preserving the heat for 0.5 hour, and naturally cooling to normal temperature to obtain a target product TiNb2O7@C。
Example 3
An in-situ carbon-coated titanium niobate composite material is prepared by the following method:
(1) 7.986g of TiO were weighed2Dispersed in 1000mL of water, stirred well, and then 318.972g of Nb were weighed2O5Adding the mixture into the mixture, and stirring vigorously for 1 hour to obtain a target mixture;
(2) 31.897g of glucose was then added and rapidly stirred for 2 hours, and the resulting suspension was spray-dried to give a powder mixture;
(3) placing the obtained powder mixture in a tube furnace, introducing nitrogen, heating to 1300 ℃ at the speed of 10 ℃/min, preserving the heat for 10 hours, and naturally cooling to normal temperature to obtain an initial product;
(4) placing the primary product in a muffle furnace, heating to 500 ℃ at a rate of 20 ℃/min under the air atmosphere, preserving the heat for 0.2 hour, and naturally cooling to normal temperature to obtain a target product TiNb24O62@C。
Example 4
An in-situ carbon-coated titanium niobate composite material is prepared by the following method:
(1) 15.972g of TiO were weighed2Dispersed in 100mL of ethylene glycol, stirred well, and then 63.642g C was weighed2H6NbO is added into the mixture and stirred vigorously for 5 hours to obtain a target mixture;
(2) then adding 1.27g of polyvinylpyrrolidone, quickly stirring for 4 hours, and carrying out forced air drying on the obtained suspension for 20 hours at 150 ℃ to obtain a powder mixture;
(3) placing the obtained powder mixture in a tubular furnace, introducing nitrogen, heating to 1000 ℃ at the speed of 1 ℃/min, keeping the temperature for 15 hours, and naturally cooling to normal temperature to obtain an initial product;
(4) placing the primary product in a muffle furnace, heating to 250 ℃ at a rate of 0.5 ℃/min under the air atmosphere, preserving the heat for 2 hours, and naturally cooling to normal temperature to obtain a target product Ti2Nb2O9@C。
Comparative example 1
An in-situ carbon-coated titanium niobate composite material is prepared by the following method:
(1) weighing 5.4g NbCl5Dissolved in 80mL of absolute ethanol, sufficiently stirred, and then 2.84g of Ti (OC) was weighed3H7)4The resulting suspension was then added to the above solution and vigorously stirred for 2 hours, and the resulting suspension was freeze-dried for 24 hours to obtain a powder mixture.
Placing the obtained powder mixture in a muffle furnace, heating to 1000 ℃ at a speed of 3 ℃/min under the atmosphere of pure oxygen, preserving the heat for 5 hours, and naturally cooling to normal temperature to obtain a TiNb product2O7。
The obtained product TiNb2O7Dispersing in water, adding 0.4g of cane sugar, quickly stirring for 3 hours, drying the obtained suspension, introducing nitrogen, heating to 700 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and naturally cooling to normal temperature to obtain a TiNb product2O7@C。
Test examples
The crystalline phase structure of the electrode materials prepared in all examples was characterized by an X-ray diffractometer and analyzed to determine the molecular formula of the material.
In electrochemical tests, the electrode materials prepared in all the examples have the mass ratio of the active substances in the electrode sheet of 91 percent, the mass ratio of the conductive agent of 5 percent, the mass ratio of the adhesive of 4 percent and the loading capacity of the electrode sheet surface of 10mg/cm2Compacted density of 2.4g/cm3The test condition is normal temperature test.
FIG. 1 is a TiNb prepared in example 12O7X-ray diffraction pattern of @ C. It can be seen from the figure that TiNb is present in the sample2O7Characteristic peak of @ C.
FIG. 2 is a TiNb prepared in example 12O7The thermogravimetric analysis Test (TGA) profile of @ C, from which it can be seen that the sample contains about 2.5 wt% carbon.
FIG. 3 is a TiNb prepared in example 12O7The Scanning Electron Microscope (SEM) image of @ C, from which it can be seen that the sample particle size range is uniform from 1 to 3 microns.
FIG. 4 is a TiNb prepared in example 12O7@ C first charge-discharge capacity performance plot at 2C rate. The mass ratio of active substances in the pole piece is 91%, the mass ratio of the conductive agent is 5%, the mass ratio of the binder is 4%, and the loading capacity of the pole piece surface is 10mg/cm2The compacted density is 2.4g/cm3. From the figure, TiNb can be seen2O7@ C is up to 205.1mAh/g under the condition of 2C current density within the voltage range of 1.0-3.0, the initial coulombic efficiency is up to 96.2%, and the discharge platform is about 1.49V, which indicates that the TiNb is constructed according to the invention2O7@ C is effective in releasing its capacity with minimal polarization.
FIG. 5 is a TiNb prepared in example 12O7@ C is the cycle performance graph for button cell tests prepared with active material. The mass ratio of active substances in the pole piece is 91%, the mass ratio of the conductive agent is 5%, the mass ratio of the binder is 4%, and the loading capacity of the pole piece surface is 10mg/cm2The compacted density is 2.4g/cm3. It can be seen from the figure that when TiNb is used2O7@ C is supplied when it is circulated with 2C charging and discharging currentGood discharge capacity and little fading. After the material is circulated for 100 circles at 2C current density, the discharge capacity is still as high as 203.2mAh/g, the capacity retention rate is as high as 99.07%, and the coulombic efficiency is close to 100%, which shows that TiNb is2O7@ C has good rate capability and cycle life.
FIG. 6 is a TiNb prepared in example 12O7@ C is a rate performance graph of button cell tests prepared by active substances. The mass ratio of active substances in the pole piece is 91%, the mass ratio of the conductive agent is 5%, the mass ratio of the binder is 4%, and the loading capacity of the pole piece surface is 10mg/cm2The compacted density is 2.5g/cm3. It can be seen from the figure that when TiNb is used2O7@ C provides a discharge capacity of 260mAh/g when charged and discharged at 0.2C. Even if the material is charged and discharged at the current density of 3C, the discharge capacity of the material is still as high as 180mAh/g, and the coulombic efficiency is close to 100 percent, which shows that the TiNb is2O7@ C has good rate capability.
FIG. 7 is a TiNb prepared in example 22O7@ C is a cycle performance plot for button cell testing prepared with active material. The mass ratio of active substances in the pole piece is 91%, the mass ratio of the conductive agent is 5%, the mass ratio of the binder is 4%, and the loading capacity of the pole piece surface is 10mg/cm2The compacted density is 2.7g/cm3. It can be seen from the figure that when TiNb is used2O7@ C provides good discharge capacity with little decay when cycled with 2C charge-discharge current. After the material is circulated for 100 circles at 2C current density, the discharge capacity is still as high as 214mAh/g, the capacity retention rate is as high as 98.6 percent, and the coulombic efficiency is close to 100 percent, which shows that TiNb is2O7@ C has good rate capability and cycle life.
FIG. 8 is a view showing TiNb prepared in comparative example 1 without secondary heat treatment2O7@ C is the cycle performance graph for button cell tests prepared with active material. The mass ratio of active substances in the pole piece is 91%, the mass ratio of the conductive agent is 5%, the mass ratio of the binder is 4%, and the loading capacity of the pole piece surface is 10mg/cm2The compacted density is 2.5g/cm3. From the figure, it can be seen that TiNb when not subjected to secondary heat treatment2O7@ C is a rapid decay in discharge capacity when cycled with a 2C charge-discharge current. The discharge capacity of the material is only kept at 82.3mAh/g after the material is circulated for 100 circles at 2C current density, which shows that TiNb is not subjected to secondary heat treatment2O7@ C does not have good rate capability and cycle life.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. A preparation method of an in-situ carbon-coated titanium niobate composite material is characterized by comprising the following steps:
(1) dissolving a niobium source, sequentially adding a titanium source and a carbon source, and uniformly stirring to obtain a mixed solution;
(2) drying the mixed solution, and removing the solvent to obtain a powder mixture;
(3) carrying out primary heat treatment on the powder mixture to obtain a primary product; wherein the treatment temperature of the first heat treatment is 500-1300 ℃, the treatment time is 2-80 hours, the heating rate is 1-10 ℃/min, and the atmosphere is inert atmosphere;
(4) carrying out secondary heat treatment on the primary product in an oxygen-containing atmosphere to obtain an in-situ carbon-coated titanium niobate composite material; wherein, the second heat treatment adjusts the carbon content and the porosity of the in-situ carbon-coated titanium niobate composite material by controlling the treatment temperature, the treatment time and the oxygen concentration of the oxygen-containing atmosphere; the treatment temperature of the second heat treatment is 250-500 ℃, the treatment time is 0.2-20 hours, the heating rate is 0.5-20 ℃ per minute, and the atmosphere is oxygen-containing atmosphere.
2. The preparation method according to claim 1, wherein the niobium source is dissolved in a solvent added in the step (1), the concentration of niobium ions is 0.001-20mol/L, and the solvent is one or more of water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, n-propanol, isobutanol and n-butanol.
3. The preparation method according to claim 2, wherein the niobium source is one or more of niobium pentachloride, ammonium niobium oxalate, niobium ethoxide, niobium hydroxide, niobium pentoxide, niobium dioxide, niobium fluoride and niobium iodide; the titanium source is one or more of isopropyl titanate, titanium sulfate, titanium tetrachloride, titanium trichloride, titanyl sulfate, titanium tetraisopropoxide, butyl titanate, titanium tetrafluoride, titanium potassium oxalate and titanium dioxide, and the carbon source is one or more of ascorbic acid, citric acid, glucose, sucrose and polyvinylpyrrolidone.
4. The method according to claim 3, wherein the titanium/niobium atomic ratio in the step (1) is 0.417 to 1; the mass ratio of the carbon source to the niobium source is 0.02-0.1.
5. The method of claim 1, wherein the drying of step (2) is one of forced air drying, vacuum drying, freeze drying, and spray drying.
6. An in-situ carbon-coated titanium niobate composite material prepared by the preparation method according to any one of claims 1 to 5.
7. The application of the in-situ carbon-coated titanium niobate composite material as claimed in claim 6 as a negative electrode plate of a lithium ion battery.
CN202011561540.9A 2020-12-25 2020-12-25 In-situ carbon-coated titanium niobate composite material and preparation method and application thereof Active CN112701260B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011561540.9A CN112701260B (en) 2020-12-25 2020-12-25 In-situ carbon-coated titanium niobate composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011561540.9A CN112701260B (en) 2020-12-25 2020-12-25 In-situ carbon-coated titanium niobate composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112701260A CN112701260A (en) 2021-04-23
CN112701260B true CN112701260B (en) 2022-05-20

Family

ID=75510536

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011561540.9A Active CN112701260B (en) 2020-12-25 2020-12-25 In-situ carbon-coated titanium niobate composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112701260B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114551784B (en) * 2021-10-22 2024-01-05 万向一二三股份公司 Negative plate capable of being charged rapidly at low temperature, preparation method thereof and battery cell
CN114477284B (en) * 2022-03-16 2023-12-05 中物院成都科学技术发展中心 Method for preparing titanium niobium oxide
CN114665084A (en) * 2022-04-08 2022-06-24 合肥学院 Carbon-coated TiNb2O7Preparation method of porous nanosheet negative electrode material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493408A (en) * 2018-03-09 2018-09-04 成都新柯力化工科技有限公司 A kind of compound porous titanium niobate lithium cell cathode material of modified clay and preparation method

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105304887A (en) * 2015-12-09 2016-02-03 南阳师范学院 Mesoporous microspherical titanium niobate/carbon composite material and preparation method thereof
CN105502499A (en) * 2015-12-30 2016-04-20 哈尔滨工业大学 Method for preparing spherical titanium oxide niobate anode material in large scale by utilizing spray drying method and application thereof to lithium ion battery
CN105552346A (en) * 2016-02-26 2016-05-04 南阳师范学院 Titanium niobate/carbon composite electrode material and preparation method thereof
CN108097242A (en) * 2017-12-29 2018-06-01 中国矿业大学(北京) A kind of preparation method of high-specific surface area hexa-aluminate class catalyst
CN109473641A (en) * 2018-10-10 2019-03-15 河南工程学院 A kind of preparation method of coated modified carbon high magnification titanium niobium oxide material
CN109888245B (en) * 2019-03-21 2021-01-15 浙江大学 Titanium niobium oxygen/carbon composite material with oxygen vacancy and carbon coating adjustment and preparation method and application thereof
CN110137481A (en) * 2019-06-12 2019-08-16 湖北锂诺新能源科技有限公司 Carbon coating oxygen defect titanium niobate negative electrode material and preparation method thereof and lithium battery
CN111874947B (en) * 2020-07-09 2023-04-21 江苏理工学院 Tin-carbon co-doped titanium niobate material and preparation method and application thereof
CN112103493A (en) * 2020-08-13 2020-12-18 华北电力大学 Preparation method of lithium battery negative electrode material titanium-niobium composite oxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493408A (en) * 2018-03-09 2018-09-04 成都新柯力化工科技有限公司 A kind of compound porous titanium niobate lithium cell cathode material of modified clay and preparation method

Also Published As

Publication number Publication date
CN112701260A (en) 2021-04-23

Similar Documents

Publication Publication Date Title
CN112701260B (en) In-situ carbon-coated titanium niobate composite material and preparation method and application thereof
JP2010528410A (en) Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery
US10431817B2 (en) Electrode material for lithium-ion secondary battery and method for manufacturing the same, electrode for lithium-ion secondary battery, and lithium-ion secondary battery
US20140356716A1 (en) Electrode material, electrode and method of manufacturing electrode material
US9281521B2 (en) Graphite negative material for lithium-ion battery, method for preparing the same and lithium-ion battery
US9722250B2 (en) Electrode material and method for manufacturing same
JP2012185979A (en) Method for manufacturing electrode active material
CN111769272A (en) Bi @ C hollow nanosphere composite material and preparation method and application thereof
JP2003017053A (en) Electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP4868677B2 (en) Electrode composition containing doped tungsten oxide and method for producing the same
CN115020685B (en) Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof
CN115504524B (en) Single-crystal high-nickel material, and preparation method and application thereof
CN111646459A (en) Preparation method and application of boron-doped graphene material
CN114204002B (en) Composite coating method of high-compaction high-nickel layered positive electrode material for solid-state battery
CN113321244B (en) Preparation method and application of surface-modified layered oxide positive electrode material
CN113066980B (en) Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material
KR20180018884A (en) Surface-modified cathode active materials for aqueous lithium secondary battery
JP4522682B2 (en) Method for producing electrode material powder, electrode material powder and electrode, and lithium battery
KR101858933B1 (en) Heterogeneous metal nanowire electrode and preparing method thereof
CN113526552B (en) Composite positive electrode active material of lithium ion battery and preparation method thereof
CN113991104B (en) Vanadium-based material and preparation method and application thereof
CN113716609B (en) Nano-block quick-charging electrode material and preparation method and application thereof
CN115172639A (en) Self-supporting potassium ion pre-embedded manganese-based positive electrode and preparation method and application thereof
CN114094073A (en) Tin dioxide @ carbon foam self-supporting composite material and preparation method and application thereof
CN114361433A (en) Lithium battery negative electrode material MXene and preparation method 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
GR01 Patent grant
GR01 Patent grant