CN109904453A - A kind of porous titanium nitride microballoon and preparation method thereof and the application in lithium-sulfur cell - Google Patents
A kind of porous titanium nitride microballoon and preparation method thereof and the application in lithium-sulfur cell Download PDFInfo
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- CN109904453A CN109904453A CN201910033135.0A CN201910033135A CN109904453A CN 109904453 A CN109904453 A CN 109904453A CN 201910033135 A CN201910033135 A CN 201910033135A CN 109904453 A CN109904453 A CN 109904453A
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Abstract
The invention discloses a kind of porous titanium nitride microballoons and preparation method thereof and the application in lithium-sulfur cell；This method is mainly using titanium dioxide as titanium source, using dicyandiamide or melamine as nitrogen source, using nano silica as pore creating material, has the porous titanium nitride microballoon of high-specific surface area, macropore volume using the preparation of spray drying process combination high-temperature heat treatment.The preparation method simple process, be easy to control, environmental pollution is small, be suitble to large-scale production, the porous titanium nitride pattern of preparation is uniform, stable structure.For being used as the fixed material of sulphur in lithium-sulfur cell, the high specific surface area of the microballoon, big pore volume can guarantee the insertion of sufficient sulphur, and good electric conductivity can enhance electrons/ions transfer efficiency in electrode；High polarity provides the crystallized ability strong to polysulfide；The porous titanium nitride/sulphur anode shows high specific capacity, outstanding cyclical stability.
Description
Technical field
The invention belongs to micro Nano material science and battery power technical field, and in particular to a kind of porous titanium nitride microballoon
And preparation method thereof with the application in lithium-sulfur cell.
Background technique
Porous material has many advantages, such as bigger serface, macropore appearance, good penetrability, in adsorbing separation, catalysis, super capacitor
The fields such as device and lithium ion battery have a wide range of applications.Wherein, porous titanium nitride (TiN) is due to its good electric conductivity, strong
Polarity, it is considered to be a kind of fixed material of ideal sulphur, in lithium-sulfur cell with good application prospect.Good electric conductivity can
To accelerate the transfer of electronics in electrode, the electrochemical reaction dynamic process of entire electrode is promoted；Porous structure not only can be with
Guarantee the insertion of sufficient activity sulphur, and the infiltration of electrolyte can be conducive to；Strong polarity can provide polysulfide strong
Chemisorption, inhibit shuttle effect, and then improve battery cyclical stability.
However the existing method for preparing porous titanium nitride, there is also some disadvantages and deficiency, preparation method generally uses water
Thermal method or solvent-thermal method, and generally require to be passed through the transformation of ammonia realization titanium dioxide to titanium nitride in preparation process, these
The method duration is long, is difficult to be mass produced, and environmental pollution is larger；And the titanium nitride specific surface area of preparation, pore volume are lower.
The application utilizes simple spray drying process, with the porous titanium nitride microballoon that double-template is prepared for bigger serface, macropore holds.It answers
For in lithium-sulfur cell, high specific surface area, big pore volume can to guarantee the insertion of sufficient sulphur；Good electric conductivity enhances
The electrons/ions transfer efficiency of electrode；High polarity provides the crystallized ability strong to polysulfide；Finally, TiN/S anode exhibition
High specific capacity, outstanding cyclical stability are shown.
Summary of the invention
In order to solve the shortcomings of the prior art, the present invention provide a kind of porous titanium nitride microballoon and preparation method thereof with
Using the porous titanium nitride that the preparation method obtains has high-specific surface area, macropore volume and good electric conductivity, can apply
In lithium-sulfur cell.
Technical scheme is as follows:
A kind of preparation method of porous titanium nitride microballoon, comprising the following steps:
Nano-titanium dioxide, aerosil are added in the aqueous solution containing surfactant by S1, ultrasound point
Dissipate 1h；Nitrogen source and carbohydrate are added, continues to stir 30min, obtains uniform solution, the nitrogen source is dicyandiamide or melamine
Amine, the carbohydrate are glucose or sucrose；
S2, the solution in S1, which is transferred to drying, the intake air temperature that spray dryer is arranged in spray dryer, is
220-300 DEG C, air outlet temperature is 90-140 DEG C；Obtain dry powder；
Powder obtained in S2 is placed in tube furnace by S3, under an argon atmosphere, is heated up with the heating rate of 5 DEG C/min
To 800-900 DEG C, 2h is kept the temperature, cooled to room temperature obtains SiO2@TiN complex microsphere；
Complex microsphere obtained in S3 is added in the sodium hydroxide solution of 20wt% by S4, stirs 6h, removes titanium dioxide
Silicon template obtains porous TiN microballoon.
In above-mentioned technical proposal, surfactant described in step S1 is polyvinylpyrrolidone (PVP).
Nitrogen source described in step S1 and the molar ratio of nano-titanium dioxide are preferably 1-2.
The intake air temperature of spray dryer is preferably 220 DEG C in step S2, and blower frequency is preferably 50HZ, material sample introduction
Rate is preferably 400mL/h.
Using porous titanium nitride microballoon made from the above method, specific surface area is up to 964m2g-1, pore volume is up to
2.67cm3g-1.The microballoon can be used as the fixed material of sulphur for lithium-sulphur cell positive electrode.
Compared with prior art, porous silicon carbide titanium microballoon prepared by the present invention has the advantage that
1) reduction can be directly provided during heating using dicyandiamide or melamine as nitrogen source in the present invention
Property atmosphere, is converted into titanium nitride for titanium dioxide in situ；Avoid the use of a large amount of ammonias in existing method；
2) using nanometer titanium dioxide silica aerogel, dicyandiamide or melamine as double-template, the nitrogen of preparation in the present invention
Changing titanium microballoon has the characteristics that bigger serface, macropore hold；
3) the good electric conductivity of titanium nitride produced by the present invention improves electronics in electrode, ion transfer efficiency, enhances
Performance under battery high magnification；The confinement of nano-pore and the chemisorption of polarity titanium nitride, which provide polysulfide, to be had by force
Polysulfide is effectively limited in inside microballoon by the fixed function of power, realizes the high long circulating stability of battery.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph of porous titanium nitride prepared by the embodiment of the present invention 1, (a) low power, (b) high power；
Fig. 2 is the XRD spectrum of porous titanium nitride prepared by the embodiment of the present invention 1；
Fig. 3 is nitrogen adsorption-desorption isotherm of porous titanium nitride prepared by the embodiment of the present invention 1, and built-in figure is hole
Diameter distribution map；
Fig. 4 is that difference electric current is close when porous titanium nitride prepared by the embodiment of the present invention 1 is used as lithium sulphur battery electrode material
Capacitance-voltage curves figure under degree；
Fig. 5 is the cycle performance song that porous titanium nitride prepared by the embodiment of the present invention 1 is used as lithium sulphur battery electrode material
Line chart.
Specific embodiment
The preparation of 1 porous titanium nitride microballoon of embodiment
The PVP of 4g nano-titanium dioxide, 2g aerosil, 1.62g are added to the deionized water of 400ml by S1
In, ultrasonic disperse 1h；8g dicyandiamide and 2g sucrose are added, 30min is stirred, obtains uniform solution；
Solution in S1 is transferred to drying in spray dryer by S2, and the intake air temperature that spray dryer is arranged is 220
DEG C, air outlet temperature is 100 DEG C；Obtain presoma powder；
Powder obtained in S2 is placed in tube furnace by S3, under an argon atmosphere, is heated up with the heating rate of 5 DEG C/min
To 800 DEG C, 2h is kept the temperature, cooled to room temperature obtains SiO2@TiN complex microsphere；
Composite inorganic membranes obtained in S3 are added in the sodium hydroxide solution of 20wt% by S4, stir 6h, remove dioxy
SiClx template obtains porous TiN microballoon.
Fig. 1 is the SEM shape appearance figure of the porous silicon carbide titanium of preparation, and titanium nitride shows micron-sized spherical structure；
Fig. 2 is the XRD spectrum of the porous silicon carbide titanium of preparation, shows that the microballoon main component of preparation is titanium nitride, and contain
A small amount of carbon；Fig. 3 is the BET curve of the porous silicon carbide titanium of preparation, illustrates the high specific surface area (964m of titanium nitride2g-1) and
High pore volume (2.67cm3g-1)。
The preparation of 2 porous titanium nitride microballoon of embodiment
The PVP of 4g nano-titanium dioxide, 2g aerosil, 1.62g are added to the deionized water of 400ml by S1
In, ultrasonic disperse 1h；8g dicyandiamide and 2g sucrose are added, 30min is stirred, obtains uniform solution；
Solution in S1 is transferred to drying in spray dryer by S2, and the intake air temperature that spray dryer is arranged is 220
DEG C, air outlet temperature is 100 DEG C；Obtain presoma powder；
Powder obtained in S2 is placed in tube furnace by S3, under an argon atmosphere, is heated up with the heating rate of 5 DEG C/min
To 900 DEG C, 2h is kept the temperature, cooled to room temperature obtains SiO2@TiN complex microsphere；
Composite inorganic membranes obtained in S3 are added in the sodium hydroxide solution of 20wt% by S4, stir 6h, remove dioxy
SiClx template obtains porous TiN microballoon.
The preparation of 3 porous titanium nitride microballoon of embodiment
The PVP of 4g nano-titanium dioxide, 2g aerosil, 1.62g are added to the deionized water of 400ml by S1
In, ultrasonic disperse 1h；8g dicyandiamide and 2g glucose are added, 30min is stirred, obtains uniform solution；
Solution in S1 is transferred to drying in spray dryer by S2, and the intake air temperature that spray dryer is arranged is 220
DEG C, air outlet temperature is 100 DEG C；Obtain presoma powder；
Powder obtained in S2 is placed in tube furnace by S3, under an argon atmosphere, is heated up with the heating rate of 5 DEG C/min
To 800 DEG C, 2h is kept the temperature, cooled to room temperature obtains SiO2@TiN complex microsphere；
Composite inorganic membranes obtained in S3 are added in the sodium hydroxide solution of 20wt% by S4, stir 6h, remove dioxy
SiClx template obtains porous TiN microballoon.
The preparation of 4 porous titanium nitride microballoon of embodiment
The PVP of 4g nano-titanium dioxide, 2g aerosil, 1.62g are added to the deionized water of 400ml by S1
In, ultrasonic disperse 1h；6g melamine and 1g sucrose are added, heating stirring 30min at 60 DEG C obtains uniform solution；
Solution in S1 is transferred to drying in spray dryer by S2, and the intake air temperature that spray dryer is arranged is 220
DEG C, air outlet temperature is 100 DEG C；Obtain presoma powder；
Powder obtained in S2 is placed in tube furnace by S3, under an argon atmosphere, is heated up with the heating rate of 5 DEG C/min
To 800 DEG C, 2h is kept the temperature, cooled to room temperature obtains SiO2@TiN complex microsphere；
Composite inorganic membranes obtained in S3 are added in the sodium hydroxide solution of 20wt% by S4, stir 6h, remove dioxy
SiClx template obtains porous TiN microballoon.
The preparation of 5 porous titanium nitride microballoon of embodiment
The PVP of 4g nano-titanium dioxide, 2g aerosil, 1.62g are added to the deionized water of 400ml by S1
In, ultrasonic disperse 1h；6g melamine and 1g glucose are added, heating stirring 30min at 60 DEG C obtains uniform solution；
Solution in S1 is transferred to drying in spray dryer by S2, and the intake air temperature that spray dryer is arranged is 220
DEG C, air outlet temperature is 100 DEG C；Obtain presoma powder；
Powder obtained in S2 is placed in tube furnace by S3, under an argon atmosphere, is heated up with the heating rate of 5 DEG C/min
To 800 DEG C, 2h is kept the temperature, cooled to room temperature obtains SiO2@TiN complex microsphere；
Composite inorganic membranes obtained in S3 are added in the sodium hydroxide solution of 20wt% by S4, stir 6h, remove dioxy
SiClx template obtains porous TiN microballoon.
The assembling and test of 6 lithium-sulfur cell of embodiment
The titanium nitride prepared in example 1 and sulphur powder 3:7 in mass ratio are carried out ground and mixed by S1, are sealed in a glass tube,
It is put into drying box, handles 12h at 155 DEG C, obtain TiN/S compound；
The TiN/S prepared in S1, carbon black, PVDF 8:1:1 in mass ratio are added in NMP by S2, and stirring prepares slurry,
Coated on aluminium foil, 60 DEG C of vacuum drying 12h obtain positive plate；
Anode, cathode (lithium piece), lithium-sulfur cell electrolyte and the diaphragm between positive and negative anodes are assembled into button by S3
Battery, carries out charge-discharge test and cycle performance is surveyed；
Fig. 4 illustrates the capacitance-voltage curves under different current densities, 0.05C (1C=1675mA h g–1) under electric discharge
Specific capacity is up to 1348mA h g–1, show the utilization rate of high sulphur；
Fig. 5 illustrates the cycle performance curve under 1C, and the initial discharge specific capacity under 1C is 989mA h g–1；700 circles follow
After ring, specific capacity residue 689mA h g–1, the capacity attenuation rate of every circle is only 0.043%, shows excellent stable circulation
Property.
Method and process of the invention is simple, be easy to control, environmental pollution is small, is suitble to large-scale production, the porous nitrogen of preparation
It is uniform to change titanium microballoon pattern, stable structure.It is the high specific surface area of the microballoon, big for being used as the fixed material of sulphur in lithium-sulfur cell
Pore volume can guarantee the insertion of sufficient sulphur, good electric conductivity can enhance electrons/ions transfer efficiency in electrode；High pole
Property provides the crystallized ability strong to polysulfide；The porous titanium nitride/sulphur anode shows high specific capacity, outstanding circulation
Stability.
Claims (7)
1. a kind of preparation method of porous titanium nitride microballoon, which is characterized in that comprise the steps of:
Nano-titanium dioxide, aerosil are added in the aqueous solution containing surfactant, ultrasonic disperse by S1
1h；Nitrogen source and carbohydrate are added, continues to stir 30min, obtains uniform solution, the nitrogen source is dicyandiamide or melamine
Amine, the carbohydrate are glucose or sucrose；
Solution in S1 is transferred to drying in spray dryer by S2, and the intake air temperature that spray dryer is arranged is 220-300
DEG C, air outlet temperature is 90-140 DEG C；Obtain dry powder；
Powder obtained in S2 is placed in tube furnace by S3, under an argon atmosphere, is warming up to the heating rate of 5 DEG C/min
800-900 DEG C, 2h is kept the temperature, cooled to room temperature obtains SiO2@TiN complex microsphere；
Complex microsphere obtained in S3 is added in the sodium hydroxide solution of 20wt% by S4, stirs 6h, removes silica mould
Plate obtains porous TiN microballoon.
2. the preparation method of porous titanium nitride microballoon according to claim 1, which is characterized in that surface described in S1 is living
Property agent be polyvinylpyrrolidone (PVP).
3. the preparation method of porous titanium nitride microballoon according to claim 1, which is characterized in that the nitrogen source and nanometer
The molar ratio of titanium dioxide is 1-2.
4. the preparation method of porous titanium nitride microballoon according to claim 1, which is characterized in that spray dryer in S2
Intake air temperature is 220 DEG C, and blower frequency is 50HZ, and material sample rate is 400mL/h.
5. a kind of porous titanium nitride microballoon that method according to any of claims 1-4 prepares.
6. a kind of application of porous titanium nitride microballoon as claimed in claim 5 in lithium-sulfur cell, which is characterized in that described
Porous titanium nitride microballoon is used for lithium-sulphur cell positive electrode as the fixed material of sulphur.
7. a kind of lithium ion battery, which is characterized in that the anode pole piece of the lithium ion battery contains as claimed in claim 5 more
Hole titanium nitride microballoon and sulphur powder.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244416A (en) * | 2020-01-16 | 2020-06-05 | 中南大学 | Active quantum dot @ porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111900371A (en) * | 2020-07-28 | 2020-11-06 | 肇庆市华师大光电产业研究院 | Titanium nitride/sulfur composite material for lithium-sulfur battery anode and preparation method thereof |
| CN112820887A (en) * | 2021-01-18 | 2021-05-18 | 南京大学 | Fuel cell cathode oxygen reduction catalyst and preparation method and application thereof |
| CN113292052A (en) * | 2021-04-29 | 2021-08-24 | 上海师范大学 | Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof |
| CN113745543A (en) * | 2021-09-26 | 2021-12-03 | 重庆科技学院 | Preparation method of hollow titanium nitride-carbon, catalyst and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103021672A (en) * | 2012-12-12 | 2013-04-03 | 常州大学 | Spherical metal nitride material and preparation method and application thereof |
| WO2015027147A1 (en) * | 2013-08-22 | 2015-02-26 | Oregon State University | Hydrolysis deposition |
| CN105152146A (en) * | 2015-08-11 | 2015-12-16 | 上海应用技术学院 | Preparation method of TiN nano-material |
| CN105655139A (en) * | 2016-01-21 | 2016-06-08 | 东南大学 | Molybdenum oxide/carbon-coated titanium nitride nanotube array composite material and preparation method and application thereof |
-
2019
- 2019-01-14 CN CN201910033135.0A patent/CN109904453A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103021672A (en) * | 2012-12-12 | 2013-04-03 | 常州大学 | Spherical metal nitride material and preparation method and application thereof |
| WO2015027147A1 (en) * | 2013-08-22 | 2015-02-26 | Oregon State University | Hydrolysis deposition |
| CN105152146A (en) * | 2015-08-11 | 2015-12-16 | 上海应用技术学院 | Preparation method of TiN nano-material |
| CN105655139A (en) * | 2016-01-21 | 2016-06-08 | 东南大学 | Molybdenum oxide/carbon-coated titanium nitride nanotube array composite material and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| EASWARAMOORTHI RAMASAMY等: "Soft-Template Simple Synthesis of Ordered Mesoporous Titanium Nitride-Carbon Nanocomposite for High Performance Dye-Sensitized Solar Cell Counter Electrodes", 《CHEMISTRY OF MATERIALS》 * |
| HANGJUN YING等: "Ultrasmall Sn nanodots embedded inside N-doped carbon microcages as high-performance lithium and sodium ion battery anodes", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| HAN-SHENG HSUEH等: "Formation of Titanium Nitride Nanoparticles within Mesoporous Silica SBA-15", 《JOURNAL OF PHYSICAL CHEMISTRY B》 * |
| JIN HO BANG 和 KENNETH S. SUSLICK: "Dual Templating Synthesis of Mesoporous Titanium Nitride Microspheres", 《ADVANCED MATERIALS》 * |
| NEGAR MOSAVATI等: "Nanostructured titanium nitride as a novel cathode for high performance lithium/dissolved polysulfide batteries", 《JOURNAL OF POWER SOURCES》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244416A (en) * | 2020-01-16 | 2020-06-05 | 中南大学 | Active quantum dot @ porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111244416B (en) * | 2020-01-16 | 2021-04-09 | 中南大学 | Active quantum dot @ porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111900371A (en) * | 2020-07-28 | 2020-11-06 | 肇庆市华师大光电产业研究院 | Titanium nitride/sulfur composite material for lithium-sulfur battery anode and preparation method thereof |
| CN112820887A (en) * | 2021-01-18 | 2021-05-18 | 南京大学 | Fuel cell cathode oxygen reduction catalyst and preparation method and application thereof |
| CN112820887B (en) * | 2021-01-18 | 2022-03-18 | 南京大学 | Fuel cell cathode oxygen reduction catalyst and preparation method and application thereof |
| CN113292052A (en) * | 2021-04-29 | 2021-08-24 | 上海师范大学 | Hollow metal nitride/carbon microsphere composite material and preparation method and application thereof |
| CN113745543A (en) * | 2021-09-26 | 2021-12-03 | 重庆科技学院 | Preparation method of hollow titanium nitride-carbon, catalyst and application |
| CN113745543B (en) * | 2021-09-26 | 2022-12-27 | 重庆科技学院 | Preparation method of hollow titanium nitride-carbon, catalyst and application |
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