CN109326790A - A kind of 1-dimention nano threadiness sodium titanate and its preparation method and application - Google Patents
A kind of 1-dimention nano threadiness sodium titanate and its preparation method and application Download PDFInfo
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- CN109326790A CN109326790A CN201811003464.2A CN201811003464A CN109326790A CN 109326790 A CN109326790 A CN 109326790A CN 201811003464 A CN201811003464 A CN 201811003464A CN 109326790 A CN109326790 A CN 109326790A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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 present invention provides a kind of 1-dimention nano threadiness sodium titanate and its preparation method and application.The preparation method of the 1-dimention nano threadiness sodium titanate includes the following steps: S1, peroxo-complex dispersion liquid of the preparation containing titanium；S2, sodium compound formation solution is slowly added into the peroxo-complex dispersion liquid containing titanium；Under S3, normal temperature and pressure conditions, alcohol is added into the solution and obtains 1-dimention nano threadiness predecessor precipitating；S4, it after drying the 1-dimention nano threadiness predecessor precipitation and separation, is reacted through low-temperature heat and obtains 1-dimention nano threadiness sodium titanate product.This method simple process, technological parameter is easy to control, is easy to heavy industrialization.
Description
Technical field
The present invention relates to Material Fields, and specifically, the present invention relates to a kind of 1-dimention nano threadiness sodium titanate and its preparations
Methods and applications.
Background technique
Sodium titanate be widely used in sodium-ion battery, lithium ion battery, kalium ion battery, etc. fields, be material
The hot spot of area research.The application performance of sodium titanate material and its appearance structure are closely related.For example, compared to nano particle and
Speech, 1-dimention nano threadiness nano material can reduce intergranular crystal boundary, be conducive to carrier transporting on long axis direction, answer
When for battery electrode material, long axis is conducive to the effective mobility of electronics, and short axle is conducive to the quick insertion of sodium, lithium or potassium ion
With embedding process out.Therefore, for nano particle, there is the sodium titanate of 1-dimention nano threadiness structure will have greatly for preparation synthesis
The big application effect for improving sodium titanate material.
The method of existing synthesizing one-dimensional nanometer linear structure sodium titanate is mainly hydro-thermal reaction, and this method generallys use nanometer
The titanium dioxide of scale is predecessor, under the conditions of 10 moles every liter of sodium hydroxide, is obtained through the hydro-thermal reaction greater than 180 DEG C
?.The water-heat process of the preparation method is related to high temperature and pressure, and risk is big；Meanwhile the reaction system is 10 moles every liter
Sodium hydroxide has very strong corrosion under the high hydrothermal temperature greater than 180 DEG C and the high Hydro-thermal pressure greater than 10 atmospheric pressure
Property.Requirement of the reaction system to hydro-thermal reaction equipment is very harsh, is difficult to search out suitable consersion unit, synthesis cost is high
It is expensive.In addition, the corrosivity alkali concentration that the preparation method uses is very high, cause subsequent sodium titanate product separating-purifying difficult,
Also serious pollution is brought to environment.Therefore, no matter the hydrothermal preparing process of 1-dimention nano threadiness structure sodium titanate is set in synthesis
Standby or synthesis process and subsequent processing etc. still face many problems, cannot achieve large-scale production.
Therefore, development technology process is simple, without high temperature or the synthesis condition of high pressure, is convenient for large-scale production 1-dimention nano
The preparation method of linear structure sodium titanate still has great challenge.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of 1-dimention nano threadiness sodium titanate.
Another object of the present invention is to provide the 1-dimention nano threadiness sodium titanates that the preparation method is prepared.
Another object of the present invention is to provide using the 1-dimention nano threadiness sodium titanate as raw material be prepared from
The electrode material of sub- battery.
It is the method that raw material prepares metatitanic acid another object of the present invention is to provide the 1-dimention nano threadiness sodium titanate.
Another object of the present invention is to provide the metatitanic acids that the method is prepared.
Another object of the present invention is to provide the applications of the metatitanic acid.
Another object of the present invention is to provide a kind of methods for preparing titanium dioxide.
Another object of the present invention is to provide the titanium dioxide that the method is prepared.
A further object of the present invention is to provide the applications of the titanium dioxide.
In order to achieve the above object, on the one hand, the present invention provides a kind of preparation method of 1-dimention nano threadiness sodium titanate,
In, described method includes following steps:
S1, peroxo-complex dispersion liquid of the preparation containing titanium；
S2, sodium compound formation solution is slowly added into the peroxo-complex dispersion liquid containing titanium；
Under S3, normal temperature and pressure conditions, alcohol is added into the solution and obtains 1-dimention nano threadiness predecessor precipitating；
S4, it after drying the 1-dimention nano threadiness predecessor precipitation and separation, is reacted through low-temperature heat and obtains 1-dimention nano
Linear sodium titanate product.
Some specific embodiments according to the present invention, wherein the peroxo-complex dispersion liquid described in step S1 containing titanium
Middle titanium peroxo-complex concentration is 0.01 mole and often rises to 1 mole every liter.
Some specific embodiments according to the present invention, wherein the peroxo-complex dispersion liquid described in step S1 containing titanium
Middle titanium peroxo-complex concentration is 0.05 mole and often rises to 0.5 mole every liter.
Some specific embodiments according to the present invention, wherein the preparation peroxo-complex containing titanium point described in step S1
The method of dispersion liquid includes dispersing titanium source in peroxide aqueous solution to form dispersion liquid；The titanium source is selected from Titanium, ethyl alcohol
Titanium, isopropyl titanate, titanium propanolate, butyl titanate, titanium ethylene glycolate, glycerine titanium, titanium sulfate, titanyl sulfate, titanium tetrachloride, tetrafluoro
Change one of titanium, ammonium titanium fluoride, titanium nitride, titanium dioxide, metatitanic acid, hydration metatitanic acid and positive metatitanic acid or several combinations；
The peroxide is selected from the combination of one or more of hydrogen peroxide, carbamide peroxide and Peracetic acid.
Some specific embodiments according to the present invention, wherein the peroxo-complex dispersion liquid containing titanium is prepared in step S1
While polymer can also be added into dispersion liquid；The polymer is selected from chitosan, guar gum, methylcellulose, ethyl
Cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyacrylamide, polyoxygenated
One of ethylene and polyvinylpyrrolidone or several combinations；The content that polymer is added in the solution is very much
One of to 10.
Some specific embodiments according to the present invention, wherein the content that polymer is added in solution described in step S1 is thousand
/ mono- to 1 percent.
Some specific embodiments according to the present invention, wherein in step S2 sodium compound be selected from sodium hydroxide, sodium oxide molybdena,
The combination of one or more of sodium peroxide and sodium superoxide.
Some specific embodiments according to the present invention, wherein in step S2 be added sodium compound formed solution in sodium from
The concentration of son is 0.5 mole and often rises to 4.0 moles every liter.
Some specific embodiments according to the present invention, wherein alcohol described in step S3 be selected from methanol, ethyl alcohol, propyl alcohol, butanol,
One of amylalcohol, ethylene glycol, propylene glycol, glycerine and polyethylene glycol or several combinations.
Some specific embodiments according to the present invention, wherein the volume ratio that alcohol additive amount described in step S3 accounts for solution is hundred
/ five to percent 50.
Some specific embodiments according to the present invention, wherein the volume ratio that alcohol additive amount described in step S3 accounts for solution is hundred
/ ten to percent 25.
Some specific embodiments according to the present invention, wherein the reaction temperature of the reaction of low-temperature heat described in step S4 is 150
Degree Celsius to 550 degrees Celsius；The reaction time of the low-temperature heat reaction is 1 hour to 24 hours.
Some specific embodiments according to the present invention, wherein the reaction temperature of the reaction of low-temperature heat described in step S4 is 150
Degree Celsius to 450 degrees Celsius.
Some specific embodiments according to the present invention, wherein the reaction temperature of the reaction of low-temperature heat described in step S4 is 200
Degree Celsius to 450 degrees Celsius.
Some specific embodiments according to the present invention, wherein step S4 low-temperature heat reaction reaction time be 5 hours extremely
24 hours.
Some specific embodiments according to the present invention, wherein the method also includes being reacted through low-temperature heat step S4
The step of sodium titanate product is surface modified is obtained, the surface modification includes that load is selected from one of following material or several
The combination of kind: carbon, carbon nanotube, graphene, black phosphorus and metal.
On the other hand, the present invention also provides the 1-dimention nanos that preparation method described in any one of the present invention is prepared
Linear sodium titanate.
On the other hand, the present invention also provides be prepared using 1-dimention nano threadiness sodium titanate of the present invention as raw material
Ion battery electrode material.
Some specific embodiments according to the present invention, wherein the ion battery is selected from lithium ion battery, sodium ion electricity
Pond, kalium ion battery or Magnesium ion battery.
On the other hand, the present invention also provides one kind prepares by raw material of 1-dimention nano threadiness sodium titanate of the present invention
The method of metatitanic acid, wherein the method includes exchanging the 1-dimention nano threadiness sodium titanate to obtain metatitanic acid product through hydrogen ion.
Some specific embodiments according to the present invention, wherein the hydrogen ion exchange process includes: by the 1-dimention nano
Linear sodium titanate, which is put into acid solution, carries out hydrogen ion exchange acquisition metatitanic acid.
Some specific embodiments according to the present invention, wherein the acid solution is in nitric acid, hydrochloric acid, sulfuric acid, acetic acid
It is one or several kinds of.
Some specific embodiments according to the present invention, wherein the concentration of acid solution is 0.001 mole and often rises to 0.1 mole
Every liter.
Some specific embodiments according to the present invention, wherein the concentration of acid solution is 0.01 mole and often rises to 0.02 mole
Every liter.
Some specific embodiments according to the present invention, wherein the hydrogen ion exchange process includes:
The 1-dimention nano threadiness sodium titanate is separated into drying；
1-dimention nano threadiness sodium titanate of the separation after dry is repeatedly washed into separation；
1-dimention nano threadiness sodium titanate after the washing separation is put into acid solution and carries out hydrogen ion exchange acquisition titanium
Acid；
The metatitanic acid of the acquisition is carried out washing to be separated and dried to obtain metatitanic acid product.
On the other hand, the present invention also provides the metatitanic acids that method described in any one of the present invention is prepared.
On the other hand, it adsorbs and prepares in ion battery in pollutant the present invention also provides metatitanic acid of the present invention
Using.
Some specific embodiments according to the present invention, wherein the ion battery is selected from lithium ion battery, sodium ion electricity
Pond, kalium ion battery or Magnesium ion battery.
On the other hand, the present invention also provides a kind of sides that titanium dioxide is prepared using metatitanic acid of the present invention as raw material
Method, wherein the method includes by the metatitanic acid through one of hydro-thermal reaction, high annealing or combined heat treatment mode
Obtain titanium dioxide product.
Some specific embodiments according to the present invention, wherein the temperature of the hydro-thermal reaction is 100 degrees Celsius to 200 and takes the photograph
Family name's degree.
Some specific embodiments according to the present invention, wherein the temperature of the hydro-thermal reaction is 150 degrees Celsius to 190 and takes the photograph
Family name's degree.
Some specific embodiments according to the present invention, wherein the temperature of the hydro-thermal reaction is 160 degrees Celsius to 180 and takes the photograph
Family name's degree.
Some specific embodiments according to the present invention, wherein the hydro-thermal reaction time is 1 hour to 24 hours.
Some specific embodiments according to the present invention, wherein the hydro-thermal reaction time is 12 hours to 24 hours.
Some specific embodiments according to the present invention, wherein the temperature of the high annealing is 300 degrees Celsius to 700 and takes the photograph
Family name's degree.
Some specific embodiments according to the present invention, wherein the temperature of the high annealing is 400 degrees Celsius to 700 and takes the photograph
Family name's degree.
Some specific embodiments according to the present invention, wherein the time of the high temperature anneal is 1 hour to 24 small
When.
Some specific embodiments according to the present invention, wherein the time of the high temperature anneal is 3 hours to 6 hours.
Some specific embodiments according to the present invention, wherein the method also includes to obtained titanium dioxide product into
The step of row surface modification；The surface modification includes combination of the load selected from one or more of following material: carbon, carbon are received
Mitron, graphene, carbonitride, black phosphorus, metal and semiconductor.
On the other hand, the present invention also provides a kind of titanium dioxide being prepared in method of the present invention.
In another aspect, the present invention also provides titanium dioxide of the present invention in photocatalysis degradation organic contaminant, light
Catalytic decomposition water hydrogen manufacturing, gas sensing, field of biomedicine, prepare catalytic hydrogenation material, preparation dye-sensitized solar cells,
Perovskite solar battery is prepared, ion battery electrode materials are prepared or prepares the application in hydrophobe material.
In conclusion the present invention provides a kind of sodium titanates and its preparation method and application.Method of the invention has such as
Lower advantage:
(1) this method provides that a kind of preparation process is simple, and technological parameter is easy to control, is easy to the system of large-scale industrial production
Standby sodium titanate, the method for metatitanic acid and titanium dioxide.
(2) raw material is easy to get, lower production costs.
Detailed description of the invention
Fig. 1 is preparation technology flow chart of the present invention；
Fig. 2 is the SEM figure of the 1-dimention nano threadiness predecessor precipitated product of embodiment 1；
Fig. 3 is the SEM figure of the 1-dimention nano threadiness sodium titanate product of embodiment 1；
Fig. 4 is the cathode that the 1-dimention nano threadiness sodium titanate that embodiment 1 obtains is applied to sodium-ion battery, in different charge and discharges
The discharge capacity figure of sodium-ion battery under electric rate；
Fig. 5 is the SEM figure of the metatitanic acid product of embodiment 10；
Fig. 6 is the rate diagram of the photocatalytic degradation rhodamine B for the anatase phase titanium dioxide that embodiment 13 obtains.
Specific embodiment
Below by way of the beneficial effect of the specific embodiment implementation process that the present invention will be described in detail and generation, it is intended to which help is read
Reader more fully understands essence and feature of the invention, does not limit the scope of the present invention.
Embodiment 1
It prepares the process of 1-dimention nano threadiness sodium titanate according to Fig. 1, under stirring condition, disperses 50 for 2 grams of isopropyl titanates
In milliliter water, the rear hydrogen peroxide that 5 milliliters of concentration are added and are 30%, stirring forms the peroxo-complex suspension containing titanium.It connects
, 6 grams of sodium hydroxides are added into above-mentioned peroxo-complex suspension, stirring forms shallow yellow transparent solution.Then, in room temperature
Under the conditions of 25 milliliters of ethyl alcohol is slowly added into above-mentioned clear solution, 1-dimention nano threadiness predecessor precipitating is obtained after stirring,
Its SEM figure is as shown in Figure 2.Then, predecessor precipitation and separation is dry, after in 250 degrees Celsius lower low-temperature heat 24 hours, obtain
1-dimention nano threadiness sodium titanate product, SEM figure are as shown in Figure 3.Fig. 4 is the 1-dimention nano threadiness sodium titanate that the present embodiment obtains
Applied to the cathode of sodium-ion battery, the discharge capacity figure of the sodium-ion battery under different charge-discharge velocities.Sodium-ion battery
The preparation of electrode uses knife coating procedure, first, in accordance with sodium titanate hierarchical structure microballoon: super P: Kynoar (PVDF)=
7:2:1 mass ratio is that solvent blendes together slurry, then slurry is uniformly coated in doctor knife coater with N-Methyl pyrrolidone (NMP)
On copper foil, after done with lithium metal to electrode in glove box, electrolyte uses 1mol/L NaClO4It is dissolved in EC/DMC (volume
Than for 1:1) and being added to FEC that volume fraction is 2% as additive, Glass Fiber is assembled into model as diaphragm
Electro-chemical test is carried out for the button cell of CR2032.Fig. 4 can be seen that since material particle size is small, have one-dimensional linear structure,
The sodium-ion battery the performance test results of material are excellent, and battery still there is very high electric discharge to hold under powerful charge-discharge velocity
Amount.
Embodiment 2
It prepares the process of 1-dimention nano threadiness sodium titanate according to Fig. 1, under stirring condition, disperses 50 for 2 grams of isopropyl titanates
In milliliter water, 2 grams of carbamide peroxides are added afterwards, stirring forms the peroxo-complex suspension containing titanium.Then, toward above-mentioned peroxide
3 grams of sodium hydroxides are added in complex compound suspension, stirring forms shallow yellow transparent solution.Then, at room temperature toward above-mentioned
It is slowly added 10 milliliters of isopropanol in clear solution, predecessor precipitating is obtained after stirring, SEM figure is substantially with shown in Fig. 2 one
It causes.Then, predecessor precipitation and separation is dry, after in 350 degrees Celsius lower low-temperature heat 6 hours, obtain 1-dimention nano threadiness titanium
Sour sodium product, SEM figure substantially with it is consistent shown in Fig. 3.
Embodiment 3
It prepares the process of 1-dimention nano threadiness sodium titanate according to Fig. 1, under stirring condition, disperses 2 grams of butyl titanates in
In 50 milliliters of water, the rear hydrogen peroxide that 5 milliliters of concentration are added and are 30%, stirring forms the peroxo-complex suspension containing titanium.
Then, 3 grams of sodium oxide molybdenas are added into above-mentioned peroxo-complex suspension, stirring forms shallow yellow transparent solution.Then, in room temperature
Under the conditions of 15 milliliters of methanol is slowly added into above-mentioned clear solution, obtain predecessor precipitating after stirring, SEM figure substantially with
It is consistent shown in Fig. 2.Then, predecessor precipitation and separation is dry, after in 300 degrees Celsius lower low-temperature heat 8 hours, obtain a wiener
Rice noodles shape sodium titanate product, SEM figure substantially with it is consistent shown in Fig. 3.
Embodiment 4
It prepares the process of 1-dimention nano threadiness sodium titanate according to Fig. 1, under stirring condition, 2 grams of titanium sulfates is dissolved in 50 millis
It rises in water, the rear hydrogen peroxide that 5 milliliters of concentration are added and are 30%, stirring forms the peroxo-complex solution containing titanium.Then, past
3 grams of sodium peroxides are added in above-mentioned peroxo-complex solution, stirring forms shallow yellow transparent solution.Then, at room temperature
20 milliliters of propyl alcohol is slowly added into above-mentioned clear solution, after stirring obtain predecessor precipitating, SEM figure substantially with Fig. 2 institute
Show consistent.Then, predecessor precipitation and separation is dry, after in 400 degrees Celsius lower low-temperature heat 5 hours, obtain one-dimensional nano line
Shape sodium titanate product, SEM figure substantially with it is consistent shown in Fig. 3.
Embodiment 5
The process of 1-dimention nano threadiness sodium titanate is prepared according to Fig. 1, under stirring condition, by 2 grams of metatitanic acid ultrasonic disperses in 50
In milliliter water, the rear hydrogen peroxide that 4 milliliters of concentration are added and are 30%, stirring forms the peroxo-complex suspension containing titanium.It connects
, 2 grams of sodium hydroxides are added into above-mentioned peroxo-complex solution, stirring forms shallow yellow transparent solution.Then, in room temperature item
50 milliliters of butanol is slowly added under part into above-mentioned clear solution, after stirring obtain predecessor precipitating, SEM figure substantially with figure
It is consistent shown in 2.Then, predecessor precipitation and separation is dry, after in 200 degrees Celsius lower low-temperature heat 24 hours, obtain a wiener
Rice noodles shape sodium titanate product, SEM figure substantially with it is consistent shown in Fig. 3.
Embodiment 6
The process of 1-dimention nano threadiness sodium titanate is prepared according to Fig. 1, under stirring condition, by 2 grams of titanyl sulfate ultrasonic disperses
In 50 milliliters of water, the rear hydrogen peroxide that 4 milliliters of concentration are added and are 30%, stirring forms the peroxo-complex solution containing titanium.
Then, 8 grams of sodium superoxides are added into above-mentioned peroxo-complex solution, stirring forms shallow yellow transparent solution.Then, in room temperature
Under the conditions of 5 milliliters of ethylene glycol is slowly added into above-mentioned clear solution, predecessor precipitating is obtained after stirring, SEM figure is basic
With it is consistent shown in Fig. 2.Then, predecessor precipitation and separation is dry, after in 500 degrees Celsius lower low-temperature heat 2 hours, obtain one-dimensional
The linear sodium titanate product of nanometer, SEM figure substantially with it is consistent shown in Fig. 3.
Embodiment 7
The process of 1-dimention nano threadiness sodium titanate is prepared according to Fig. 1, under stirring condition, by 2 grams of titanium tetrachloride ultrasonic disperses
In 50 milliliters of water, the rear hydrogen peroxide that 6 milliliters of concentration are added and are 30%, stirring forms the peroxo-complex solution containing titanium.
Then, 8 grams of sodium hydroxides are added into above-mentioned peroxo-complex solution, stirring forms shallow yellow transparent solution.Then, in room temperature
Under the conditions of 5 milliliters of propylene glycol is slowly added into above-mentioned clear solution, predecessor precipitating is obtained after stirring, SEM figure is basic
With it is consistent shown in Fig. 2.Then, predecessor precipitation and separation is dry, after in 350 degrees Celsius lower low-temperature heat 4 hours, obtain one-dimensional
The linear sodium titanate product of nanometer, SEM figure substantially with it is consistent shown in Fig. 3.
Embodiment 8
The process of 1-dimention nano threadiness sodium titanate is prepared according to Fig. 1, under stirring condition, by 2 grams of titanium tetrafluoride ultrasonic disperses
In 50 milliliters of water, the hydrogen peroxide and concentration that 6 milliliters of concentration of addition are 30% afterwards are millesimal hydroxypropyl methyl fiber
Element, stirring form the peroxo-complex solution containing titanium.Then, 8 grams of sodium hydroxides are added into above-mentioned peroxo-complex solution,
Stirring forms shallow yellow transparent solution.Then, the third the two of 10 milliliters are slowly added into above-mentioned clear solution at room temperature
Alcohol, obtains predecessor precipitating after stirring, SEM figure substantially with it is consistent shown in Fig. 2.Then, predecessor precipitation and separation is dry, after
In 400 degrees Celsius lower low-temperature heat 3 hours, obtain 1-dimention nano threadiness sodium titanate product, SEM figure is substantially with shown in Fig. 3 one
It causes.
Embodiment 9
The process of 1-dimention nano threadiness sodium titanate is prepared according to Fig. 1, under stirring condition, by 2 grams of titanium ethanolate titanium ultrasonic disperses
In 50 milliliters of water, the hydrogen peroxide and concentration that 8 milliliters of concentration of addition are 30% afterwards are centesimal polyvinyl alcohol, stir shape
At the peroxo-complex suspension containing titanium.Then, 8 grams of sodium hydrides are added into above-mentioned peroxo-complex solution, stirring is formed
Shallow yellow transparent solution.Then, 10 milliliters of isopropanol is slowly added into above-mentioned clear solution at room temperature, after stirring
Obtain predecessor precipitating, SEM figure substantially with it is consistent shown in Fig. 2.Then, predecessor precipitation and separation is dry, after it is Celsius in 400
Spend lower low-temperature heat 3 hours, obtain 1-dimention nano threadiness sodium titanate product, SEM figure substantially with it is consistent shown in Fig. 3.
Embodiment 10
According to the process for preparing metatitanic acid shown in Fig. 1, the 1-dimention nano threadiness sodium titanate product that embodiment 1 is prepared is used
Deionized water is repeatedly washed to neutrality, and progress hydrogen ion exchange, hydrogen ion in the nitric acid solution of 0.01mol/L are scattered in after separation
It is repeatedly washed after exchange with deionized water, until the close neutrality of cleaning solution pH, separates drying afterwards, obtain metatitanic acid product, SEM figure
As shown in Figure 5.
Embodiment 11
According to the process for preparing metatitanic acid shown in Fig. 1, the 1-dimention nano threadiness sodium titanate product that embodiment 1 is prepared is used
Deionized water is repeatedly washed to neutrality, is scattered in the hydrochloric acid solution of 0.001mol/L progress hydrogen ion exchange after separation, hydrogen from
It is repeatedly washed after son exchange with deionized water, until the close neutrality of cleaning solution pH, separates drying afterwards, obtain metatitanic acid product.
Embodiment 12
According to the process for preparing metatitanic acid shown in Fig. 1, the 1-dimention nano threadiness sodium titanate product that embodiment 1 is prepared is used
Deionized water is repeatedly washed to neutrality, and progress hydrogen ion exchange, hydrogen ion in the acetum of 0.1mol/L are scattered in after separation
It is repeatedly washed after exchange with deionized water, until the close neutrality of cleaning solution pH, separates drying afterwards, obtain metatitanic acid product.
Embodiment 13
According to the process for preparing titanium dioxide shown in Fig. 1, the 1-dimention nano threadiness metatitanic acid that embodiment 10 is prepared is produced
Object is put into Muffle furnace, and anneal 4h at 350 DEG C, obtains anatase phase titanium dioxide product.Fig. 6 is the sharp of the present embodiment acquisition
The rate diagram of the photocatalytic degradation rhodamine B of titanium ore phase titanic oxide.Test condition is to take 50mg dioxy manufactured in the present embodiment
Change titanium products to be scattered in the rhodamine B solution of 10mg/L, using the photocatalytic degradation Luo Dan under the ultraviolet light irradiation of 3 watts of LED
The rate diagram of bright B；Under the same test conditions, using P25 substance as a comparison.Fig. 6 can be seen that the decomposition of this material light catalysis
The performance of organic matter is higher than existing commercialization P25 product, about the 1.8 of P25 product rate times, has preferable organic contamination
The application prospect of object light catalytic decomposition.
Embodiment 14
According to the process for preparing titanium dioxide shown in Fig. 1, the metatitanic acid product that embodiment 10 is prepared is put into Muffle furnace
In, anneal 1h at 700 DEG C, obtains red schorl phase titanium dioxide product.
Embodiment 15
According to the process for preparing titanium dioxide shown in Fig. 1, the metatitanic acid product that embodiment 10 is prepared is put into Muffle furnace
In, it anneals at 300 DEG C for 24 hours, obtains anatase phase titanium dioxide product.
Embodiment 16
According to the process for preparing titanium dioxide shown in Fig. 1,100 millis are dispersed by the metatitanic acid product that embodiment 10 is prepared
It rises in pure water, hydro-thermal reaction 12h, obtains titanium dioxide product at 150 DEG C.
Embodiment 17
According to the process for preparing titanium dioxide shown in Fig. 1,100 millis are dispersed by the metatitanic acid product that embodiment 10 is prepared
It rises in pure water, hydro-thermal reaction for 24 hours, obtains titanium dioxide product at 100 DEG C.
Embodiment 18
According to the process for preparing titanium dioxide shown in Fig. 1,100 millis are dispersed by the metatitanic acid product that embodiment 10 is prepared
It rises in pure water, hydro-thermal reaction 2h, obtains titanium dioxide product at 200 DEG C.
Embodiment 19
According to the process for preparing titanium dioxide shown in Fig. 1,100 millis are dispersed by the metatitanic acid product that embodiment 10 is prepared
It rises in the nitric acid solution that concentration is 0.01mol/L, hydro-thermal reaction 12h, obtains titanium dioxide product at 160 DEG C.
Embodiment 20
According to the process for preparing titanium dioxide shown in Fig. 1,100 millis are dispersed by the metatitanic acid product that embodiment 10 is prepared
It rises in pure water, the hydro-thermal reaction 8h at 120 DEG C；It will be put into Muffle furnace after the separation drying of above-mentioned hydrothermal product, moved back at 400 DEG C
Fiery 2h obtains anatase phase titanium dioxide product.
Embodiment 21
According to the process for preparing titanium dioxide shown in Fig. 1, the metatitanic acid product that embodiment 10 is prepared is put into Muffle furnace
In, anneal 3h at 300 DEG C；It disperses product after above-mentioned annealing in 100 milliliters of pure water, hydro-thermal reaction 15h is obtained at 140 DEG C
To anatase phase titanium dioxide product.
Claims (20)
1. a kind of preparation method of 1-dimention nano threadiness sodium titanate, wherein described method includes following steps:
S1, peroxo-complex dispersion liquid of the preparation containing titanium；
S2, sodium compound formation solution is slowly added into the peroxo-complex dispersion liquid containing titanium；
Under S3, normal temperature and pressure conditions, alcohol is added into the solution and obtains 1-dimention nano threadiness predecessor precipitating；
S4, will the 1-dimention nano threadiness predecessor precipitation and separation it is dry after, react that obtain 1-dimention nano linear through low-temperature heat
Sodium titanate product.
2. preparation method according to claim 1, wherein in the peroxo-complex dispersion liquid described in step S1 containing titanium
Titanium peroxo-complex concentration be 0.01 mole often rise to 1 mole every liter (preferred concentration be 0.05 mole often rise to 0.5 mole it is every
It rises).
3. preparation method according to claim 1, wherein peroxo-complex dispersion of the preparation described in step S1 containing titanium
The method of liquid includes dispersing titanium source in peroxide aqueous solution to form dispersion liquid；The titanium source be selected from Titanium, titanium ethanolate,
Isopropyl titanate, titanium propanolate, butyl titanate, titanium ethylene glycolate, glycerine titanium, titanium sulfate, titanyl sulfate, titanium tetrachloride, tetrafluoride
One of titanium, ammonium titanium fluoride, titanium nitride, titanium dioxide, metatitanic acid and metatitanic acid or several combinations；The peroxide
Combination selected from one or more of hydrogen peroxide, carbamide peroxide and Peracetic acid.
4. preparation method according to claim 1, wherein prepare the peroxo-complex dispersion liquid containing titanium in step S1
Polymer can also be added into dispersion liquid simultaneously；It is fine that the polymer is selected from chitosan, guar gum, methylcellulose, ethyl
Tie up element, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyacrylamide, polyoxyethylene
One of alkene and polyvinylpyrrolidone or several combinations；The content that polymer is added in the solution is a ten thousandth
To 10 (adding the content of polymer preferably in solution as one thousandth to 1 percent).
5. preparation method according to claim 1, wherein sodium compound is selected from sodium hydroxide, sodium oxide molybdena, mistake in step S2
The combination of one or more of sodium oxide molybdena and sodium superoxide.
6. preparation method according to claim 1, wherein the sodium ion in liquor that sodium compound is formed is added in step S2
Concentration be 0.5 mole often rise to 4.0 moles every liter.
7. preparation method according to claim 1, wherein alcohol described in step S3 is selected from methanol, ethyl alcohol, propyl alcohol, butanol, penta
One of alcohol, ethylene glycol, propylene glycol, glycerine and polyethylene glycol or several combinations.
8. preparation method according to claim 1, wherein the volume ratio that alcohol additive amount described in step S3 accounts for solution is percentage
Five to percent 50 (preferred volume ratios be 10 to percent 25).
9. preparation method according to claim 1, wherein the reaction temperature of the reaction of low-temperature heat described in step S4 is 150
Degree Celsius to 550 degrees Celsius (preferably low-temperature heat reaction temperature be 200 degrees Celsius to 450 degrees Celsius)；The low-temperature heat
The reaction time of reaction is 1 hour to 24 hours.
10. preparation method described in any one according to claim 1~9, wherein the method also includes to step S4 through low
Temperature heating reaction obtains the step of 1-dimention nano threadiness sodium titanate product is surface modified, and the surface modification includes load choosing
From the combination of one or more of following material: carbon, carbon nanotube, graphene, black phosphorus and metal.
11. the 1-dimention nano threadiness sodium titanate that preparation method described in claim 1~10 any one is prepared.
12. using the electrode material for the ion battery that the 1-dimention nano threadiness sodium titanate described in claim 11 is prepared as raw material
(the preferably described ion battery is selected from lithium ion battery, sodium-ion battery, kalium ion battery or Magnesium ion battery).
13. a kind of method that the 1-dimention nano threadiness sodium titanate using described in claim 11 prepares metatitanic acid as raw material, wherein described
Method includes exchanging the 1-dimention nano threadiness sodium titanate to obtain metatitanic acid product through hydrogen ion.
14. according to the method for claim 13, wherein the hydrogen ion exchange process includes: by the one-dimensional nano line
Shape sodium titanate be put into acid solution carry out hydrogen ion exchange obtain metatitanic acid (the preferably described acid solution be selected from nitric acid, hydrochloric acid, sulfuric acid,
One of acetic acid is several) (preferably the concentration of acid solution often rises to 0.1 mole every liter for 0.001 mole).
15. according to the method for claim 14, wherein the hydrogen ion exchange process includes:
The 1-dimention nano threadiness sodium titanate is separated into drying；
1-dimention nano threadiness sodium titanate of the separation after dry is repeatedly washed into separation；
1-dimention nano threadiness sodium titanate after the washing separation is put into acid solution and carries out hydrogen ion exchange acquisition metatitanic acid；
The metatitanic acid of the acquisition is carried out washing to be separated and dried to obtain metatitanic acid product.
16. the metatitanic acid that method described in claim 13~15 any one is prepared.
17. metatitanic acid described in claim 16 adsorbs and prepares application (the preferably described ion-conductance in ion battery in pollutant
Pond is selected from lithium ion battery, sodium-ion battery, kalium ion battery or Magnesium ion battery).
18. a kind of method that the metatitanic acid using described in claim 16 prepares titanium dioxide as raw material, wherein the method includes will
The metatitanic acid is through hydro-thermal reaction (temperature of the preferably described hydro-thermal reaction is 100 degrees Celsius to 200 degrees Celsius) (the preferably described hydro-thermal
Reaction time is 1 hour to 24 hours), (temperature of the preferably described high annealing is 300 degrees Celsius to 700 Celsius to high annealing
Degree) one of (time of the preferably described the high temperature anneal be 1 hour to 24 hours) or combined heat treatment mode obtain
To titanium dioxide product, (preferably the method also includes being surface modified obtained titanium dioxide product；It is described
Surface modification includes combination of the load selected from one or more of following material: carbon, carbon nanotube, graphene, carbonitride, black
Phosphorus, metal and semiconductor).
19. the titanium dioxide that method of claim 18 is prepared.
20. titanium dioxide described in claim 19 is passed in photocatalysis degradation organic contaminant, photocatalytic hydrogen production by water decomposition, gas
Sense, field of biomedicine, prepare catalytic hydrogenation material, prepare dye-sensitized solar cells, prepare perovskite solar battery,
It prepares ion battery electrode materials or prepares the application in hydrophobe material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110304652A (en) * | 2019-07-16 | 2019-10-08 | 福建师范大学 | A kind of synthetic method of magnesium ion electrode material |
| EP3617149A1 (en) * | 2018-08-30 | 2020-03-04 | Petrochina Company Limited | Nanostructured titanic acid salts and preparation process and use thereof |
| CN113611853A (en) * | 2021-05-17 | 2021-11-05 | 中国电子产品可靠性与环境试验研究所（（工业和信息化部电子第五研究所）（中国赛宝实验室）） | Two-dimensional titanium-based nano material, preparation method thereof and application thereof in magnesium storage |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915835A (en) * | 2006-07-27 | 2007-02-21 | 北京先讯东泰科技有限公司 | Method for preparing Nano line of titania, and application of the prepared Nano line of titania |
| CN1974405A (en) * | 2006-12-25 | 2007-06-06 | 华东师范大学 | Prepn process of periodic nanometer titania line |
| KR20140092483A (en) * | 2012-12-28 | 2014-07-24 | 재단법인 포항산업과학연구원 | Conversion method of crystal shape to control titanium dioxide |
| CN104201364A (en) * | 2014-09-15 | 2014-12-10 | 李建明 | Method for preparing spinel lithium titanate |
| CN106816599A (en) * | 2017-01-11 | 2017-06-09 | 杭州电子科技大学 | A kind of composite of one-dimensional bronze crystal form titanium dioxide nano wire/Ag and preparation method thereof |
| CN107081150A (en) * | 2017-06-12 | 2017-08-22 | 青岛科技大学 | One kind carries platinum sodium titanate mixed crystal nano wire assembly and preparation method thereof |
| CN107256961A (en) * | 2017-06-14 | 2017-10-17 | 北京大学 | A kind of preparation method and applications of lithium titanate hierarchy microballoon |
| WO2018125640A1 (en) * | 2016-12-27 | 2018-07-05 | Nanotek Instruments, Inc. | Flexible and shape-conformal cable-shape alkali metal-sulfur batteries |
-
2018
- 2018-08-30 CN CN201811003464.2A patent/CN109326790B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915835A (en) * | 2006-07-27 | 2007-02-21 | 北京先讯东泰科技有限公司 | Method for preparing Nano line of titania, and application of the prepared Nano line of titania |
| CN1974405A (en) * | 2006-12-25 | 2007-06-06 | 华东师范大学 | Prepn process of periodic nanometer titania line |
| KR20140092483A (en) * | 2012-12-28 | 2014-07-24 | 재단법인 포항산업과학연구원 | Conversion method of crystal shape to control titanium dioxide |
| CN104201364A (en) * | 2014-09-15 | 2014-12-10 | 李建明 | Method for preparing spinel lithium titanate |
| WO2018125640A1 (en) * | 2016-12-27 | 2018-07-05 | Nanotek Instruments, Inc. | Flexible and shape-conformal cable-shape alkali metal-sulfur batteries |
| CN106816599A (en) * | 2017-01-11 | 2017-06-09 | 杭州电子科技大学 | A kind of composite of one-dimensional bronze crystal form titanium dioxide nano wire/Ag and preparation method thereof |
| CN107081150A (en) * | 2017-06-12 | 2017-08-22 | 青岛科技大学 | One kind carries platinum sodium titanate mixed crystal nano wire assembly and preparation method thereof |
| CN107256961A (en) * | 2017-06-14 | 2017-10-17 | 北京大学 | A kind of preparation method and applications of lithium titanate hierarchy microballoon |
Non-Patent Citations (1)
| Title |
|---|
| ZHIHONG LI ETAL: "Free-Standing Sandwich-Structured Flexible Film Electrode Composed of Na2Ti3O7 Nanowires@CNT and Reduced Graphene Oxide for Advanced Sodium-Ion Batteries", 《ACS OMEGA》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3617149A1 (en) * | 2018-08-30 | 2020-03-04 | Petrochina Company Limited | Nanostructured titanic acid salts and preparation process and use thereof |
| US11554966B2 (en) * | 2018-08-30 | 2023-01-17 | Petrochina Company Limited | Nanostructured titanic acid salts and preparation process and use thereof |
| CN110304652A (en) * | 2019-07-16 | 2019-10-08 | 福建师范大学 | A kind of synthetic method of magnesium ion electrode material |
| CN110304652B (en) * | 2019-07-16 | 2022-05-31 | 福建师范大学 | Synthesis method of magnesium ion electrode material |
| CN113611853A (en) * | 2021-05-17 | 2021-11-05 | 中国电子产品可靠性与环境试验研究所（（工业和信息化部电子第五研究所）（中国赛宝实验室）） | Two-dimensional titanium-based nano material, preparation method thereof and application thereof in magnesium storage |
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