CN110277549A - A kind of titania nanotube and the compound electrode material and preparation method thereof of tin oxide nano particles - Google Patents
A kind of titania nanotube and the compound electrode material and preparation method thereof of tin oxide nano particles Download PDFInfo
- Publication number
- CN110277549A CN110277549A CN201910488087.4A CN201910488087A CN110277549A CN 110277549 A CN110277549 A CN 110277549A CN 201910488087 A CN201910488087 A CN 201910488087A CN 110277549 A CN110277549 A CN 110277549A
- Authority
- CN
- China
- Prior art keywords
- nanotube
- titania nanotube
- nano particles
- tin oxide
- oxide nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
- 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
-
- 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
A kind of titania nanotube and the compound electrode material and preparation method thereof of tin oxide nano particles, belong to sodium-ion battery technical field.Titania nanotube, then one layer of the growth in situ tin oxide nano particles layer with high-specific surface area are prepared with hydro-thermal method first, successively by centrifugation, washing is dried to obtain the composite material of amorphous.Agents useful for same of the present invention is safe and harmless, and preparation flow is simple.Compared to simple titanium dioxide and stannic oxide, titania nanotube and the compound electrode material of tin oxide nano particles significantly improve the first circle efficiency and cycle performance of sodium-ion battery, restrained effectively stannic oxide caused volume change in cyclic process, it is therefore prevented that the dusting of its material with fall off.Therefore the present invention has very big potentiality to be exploited and application prospect.
Description
Technical field
The invention belongs to sodium-ion battery technical field, especially a kind of titania nanotube and stannic oxide nanometer
The compound electrode material and preparation method thereof of grain
Background technique
With increasingly exhausted and environmental problem the worsening of resource, develop green, it is safe, clean renewable
New energy it is extremely urgent.Electrochemical cell is a kind of energy storage system of efficient stable, wherein lithium ion battery
Because of operating voltage with higher, biggish energy density, longer cycle life, lesser self-discharge rate and environmentally protective
Many advantages, such as and be concerned in fields such as mancarried electronic aid, space flight and aviation and military affairs, but lithium ion battery by
Reserves of its lithium resource in the earth's crust are small, price, the disadvantages of being unevenly distributed and study it is limited so that sodium-ion battery weight again
The visual field of researchers, rich reserves, cheap, widely distributed, tin-based oxide of the sodium element in the earth's crust are newly returned to
Negative electrode material is widely studied because of the advantages that theoretical specific capacity is higher, and operating voltage is lower, but it also has many problems urgently
It needs to solve.
1) it is used as anode material of lithium-ion battery, during recycling deintercalation sodium ion, huge volume can be brought to become
Change, cubical expansivity is up to 420%, causes the dusting of material and fall off, therefore cyclic specific capacity can decay rapidly, to material
Cycle performance causes very big influence.
2) stannic oxide is the negative electrode material of a kind of alloy and conversion class, and in the two-step reaction of half-cell, the first step is anti-
It answers dynamics poor, has seriously affected first circle efficiency, Ding et al. has passed through XRD, and the means such as XPS, TEM confirm tin-based oxide
When discharging into 0.5V, stannic oxide is converted into β-Sn, and when discharging into 0.01V, XRD, XPS, TEM, which is shown, exists simultaneously Na15Sn4
With β-Sn, when being charged to 1.5V, Na15Sn4Peak disappears, and the peak SnO and faint β-Sn occurs, when being charged to 3V, the peak Sn disappears
It loses, SnO2Peak occurs.β-Sn does not participate in further alloying reaction in peak during discharge, and specific capacity is caused to reduce.
3) stannic oxide electric conductivity itself is poor, so electron transport rate is lower, therefore high rate performance is poor.
In order to solve the problems, such as three above, forefathers have done a large amount of work, and main contents are as follows: 1) synthesizing special appearance
Tin-based oxide nano material, 2) tin-based oxide and the compound nano material of carbon material of synthesis low dimensional nanostructure, 3)
Construct 3-D nano, structure.
Summary of the invention
The purpose of the present invention is to provide a kind of titania nanotube and stannic oxide with excellent electrochemical performance
The electrode material and preparation method of nano-particles reinforcement.
The electrode material of titania nanotube and tin oxide nano particles, which is characterized in that titania nanotube
As the kernel of the composite material, tin oxide nano particles a part is attached to titanium dioxide as the shell of the composite material
Nanotube surface, another part is in conjunction with the endpoint position of titania nanotube；The two of titania nanotube endpoint position
Tin oxide nanoparticles quantity or density are greater than the quantity and density on titania nanotube surface.(see Fig. 4)
A kind of preparation method of titania nanotube and the compound electrode material of tin oxide nano particles, including it is following
Step:
(1) by TiO2Powder is dissolved in sodium hydroxide solution, and ultrasound transferred the solution into polytetrafluoroethylene (PTFE) after 30 minutes
In 120 DEG C of -150 DEG C of hydro-thermal 10-15h in reaction kettle；
(2) suspension that step (1) obtains is centrifuged, for several times with the salt acid elution of concentration 0.1mol/L, then is spent
Ion water washing for several times, obtains TiO2Nanotube；
(3) powdered composite material is obtained after the solid product of step (2) being dried；
(4) TiO for taking a certain amount of step (3) to synthesize2Nanotube ultrasonic disperse deionized water in, by two water dichloros
Change the urea that tin solid powder is slowly added thereto, and is added thereto, stirs 2h, wherein TiO2Nanotube, stannous chloride are solid
Body powder, urea mass ratio be 1:(25-75): 5；It is preferred that 1:50:5；
(5) suspension that step (4) obtains is filtered, is repeatedly washed with deionized water and ethyl alcohol, form mixture；
(6) mix powder is obtained after the mixture of step (5) being dried；
Lower further preferred: the concentration of the sodium hydroxide solution in step (1) is 8mol/L, and hydrothermal temperature is 130 DEG C,
The hydro-thermal time is 12h.
Concentration of hydrochloric acid in step (2) is 0.1mol/L.
Drying temperature in step (3) is 80 DEG C.
TiO2With SnO2Dosage relation be preferably such that last SnO2Mass percentage in the product is 98%-
95%, most preferably 97%.
The titania nanotube and application of the tin dioxide composite material as negative electrode material that the present invention obtains.
The invention has the following advantages that
(1) preparation method of a kind of titania nanotube of the present invention and tin dioxide composite material is simple, item
Part is mild, easily operated.The titania nanotube composite material of the stannic oxide cladding of amorphous is obtained, reference can be made to Fig. 1
XRD。
(2) composite material for using titania nanotube and tin oxide nano particles, improves sodium-ion battery
First circle efficiency and cycle performance.Because the invention is capable of providing the method with good circulation performance and high first circle efficiency, tool
There are very big industry and commercial value.
Detailed description of the invention
Fig. 1 is 1 titania nanotube of embodiment and tin dioxide composite material and tin dioxide material, titanium dioxide titanium
The XRD curve comparison figure of material.
Fig. 2 is (A), (B), (C) in 1 gained titania nanotube of embodiment and tin dioxide composite material and titanium dioxide
The battery charging and discharging curve graph that tin material, titanic oxide material are prepared in the case where current density is 50mAh/g.Wherein A, B, C distinguish
For SnO2Battery, the TiO of material preparation2Battery, the 1 gained TiO of embodiment of nanotube preparation2-SnO2The electricity of composite material preparation
The performance in pond；
Fig. 3 is 1 gained TiO of embodiment2-SnO2, SnO2, TiO2Circulation of three kinds of materials in the case where current density is 50mAh/g
Performance map, wherein letter C represents charging, and D represents electric discharge.
Fig. 4 is the scanning electron microscope (SEM) photograph of titania nanotube and tin oxide nano particles composite material.
Specific embodiment
The present invention is further illustrated with comparative example combined with specific embodiments below, but the present invention is not limited to following
Embodiment.
Embodiment 1:
By TiO2Powder is dissolved in sodium hydroxide solution, and ultrasound transferred the solution into 100ml polytetrafluoroethyl-ne after 30 minutes
In 130 DEG C of hydro-thermal 12h in alkene reaction kettle, centrifugation for several times with the salt acid elution of 0.1mol/L, then is washed with deionized for several times,
In 80 DEG C of drying overnight, TiO is obtained2Nanotube.The TiO for taking 10mg to synthesize2Deionized water of the nanotube ultrasonic disperse in 40ml
In, the stannous chloride solid powder (being convertible into using two water stannous chloride) of 0.5g is slowly added thereto, and adds thereto
Enter the urea of 0.05g, stirs 2h, obtained suspension is filtered, is repeatedly washed with deionized water and ethyl alcohol, is obtained yellowish
The product of color, 60 DEG C of vacuum dryings.The dosage relation of two water stannous chloride and titania nanotube is so that last titanium dioxide
Mass percentage of the tin in titania nanotube and tin oxide nano particles composite material is 97%.
Embodiment 2:
Remaining is constant, and the quality for changing stannous chloride solid particle is 0.25g.
Embodiment 3:
Remaining is constant, and the quality for changing two water stannous chloride solid particles is 0.75g.
It is conductive agent for binder, acetylene black that composite material made of embodiment 1, which is used, as negative electrode material, PVDF, is pressed
Certain ratio (active material: conductive agent: mass ratio=6:2:2 of binder) weighs a certain amount of negative electrode material and acetylene black
After be poured into mortar grind uniformly, be added a certain amount of 10% PVDF continue grinding obtains uniform thick dark slurry,
It is uniformly coated on copper foil paper and prepares electrode slice.80 DEG C of drying, it is small that the vacuum drying oven for having claimed quality to be placed in 120 DEG C dries 12
When, then sodium-ion battery is assembled in vacuum glove box, according to negative electrode casing, sodium piece, diaphragm, anode, steel disc, spring leaf, anode
The sequence of shell is assembled (drips 5-6 drop electrolyte, electrolyte is 1mol/L NaClO before putting anode pole piece4/EC:PC (1:
), 1, Vol) contain 5%FEC.Original titania nanotube is used again, tin dioxide material and composite material are negative electrode material,
Remaining operation is same as Example 1, respectively carry out sodium-ion battery assembling, respectively under the conditions of 25 DEG C of room temperature, 50mAh/g into
Row discharge test.
Fig. 1 is titania nanotube, the stannic oxide of synthesis and the composite material XRD curve graph of the two of synthesis.
As shown in Figure 1, the titania nanotube of Detitanium-ore-type has been synthesized, the stannic oxide of cassiterite structure, and the composite material of the two
But there is apparent broad peak, illustrate the composite material for foring amorphous.The composite material of amorphous is for tin dioxide material
Stability plays certain supporting role.
Fig. 2 (A), (B), (C) are shown: in charge and discharge process, comparing titanium dioxide, stannic oxide, titanium dioxide of the present invention
Titanium nanotube and tin oxide nano particles composite material sodium-ion battery first circle efficiency with higher, this illustrates the present invention two
Titanium oxide nanotubes have preferable chemical property in sodium-ion battery field with tin oxide nano particles composite material.And
And titania nanotube and tin oxide nano particles composite material can preferably control tin dioxide material in cyclic process
Middle bring volume change, improves the chemical property of material.
Fig. 3 is SnO2、TiO2、TiO2-SnO2The cycle performance figure in the case where current density is 50mAh/g of three kinds of materials,
From the graph, it is apparent that the cycle performance of composite material is best.
Table 1 is the first circle of titanium dioxide, stannic oxide, titania nanotube and tin oxide nano particles composite material
Electric discharge, first circle charge specific capacity and first circle efficiency table, the first circle efficiency highest of composite material, illustrates composite wood as seen from the table
The first circle efficiency of single material can be improved in material.
1 three kinds of material electrochemical performance comparison sheets of table
Claims (7)
1. the electrode material of titania nanotube and tin oxide nano particles, which is characterized in that titania nanotube is made
For the kernel of the composite material, tin oxide nano particles a part is attached to titanium dioxide as the shell of the composite material and receives
Nanotube surface, another part is in conjunction with the endpoint position of titania nanotube；The dioxy at titania nanotube endpoint position
Change tin nanoparticles quantity or density is greater than the quantity and density on titania nanotube surface.
2. a kind of preparation method of the electrode material of titania nanotube and tin oxide nano particles, which is characterized in that packet
Include following steps:
(1) by TiO2Powder is dissolved in sodium hydroxide solution, and ultrasound transferred the solution into ptfe autoclave after 30 minutes
It is interior in 120 DEG C of -150 DEG C of hydro-thermal 10-15h；
(2) suspension that step (1) obtains is centrifuged, for several times with the salt acid elution of concentration 0.1mol/L, then uses deionization
Water washing for several times, obtains TiO2Nanotube；
(3) powdered composite material is obtained after the solid product of step (2) being dried；
(4) TiO for taking a certain amount of step (3) to synthesize2Nanotube ultrasonic disperse deionized water in, by two water stannous chloride
Solid powder is slowly added thereto, and the urea being added thereto, stirs 2h, wherein TiO2Nanotube, stannous chloride solid powder
Last, urea mass ratio is 1:(25-75): 5；It is preferred that 1:50:5；
(5) suspension that step (4) obtains is filtered, is repeatedly washed with deionized water and ethyl alcohol, form mixture；
(6) composite powder is obtained after the mixture of step (5) being dried.
3. according to the method for claim 2, which is characterized in that wherein TiO2Nanotube, stannous chloride solid powder, urea
Mass ratio be 1:50:5.
4. according to the method for claim 2, which is characterized in that the concentration of the sodium hydroxide solution in step (1) is 8mol/
L, hydrothermal temperature are 130 DEG C, and the hydro-thermal time is 12h.
5. according to the method for claim 2, which is characterized in that the drying temperature in step (3) is 80 DEG C.
6. according to the method for claim 2, which is characterized in that TiO2With SnO2Dosage relation be preferably such that it is last
SnO2Mass percentage in the product is 98% -95%, most preferably 97%.
7. the application of the electrode material of titania nanotube described in claim 1 and tin oxide nano particles, as negative
The application of pole material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910488087.4A CN110277549A (en) | 2019-06-05 | 2019-06-05 | A kind of titania nanotube and the compound electrode material and preparation method thereof of tin oxide nano particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910488087.4A CN110277549A (en) | 2019-06-05 | 2019-06-05 | A kind of titania nanotube and the compound electrode material and preparation method thereof of tin oxide nano particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110277549A true CN110277549A (en) | 2019-09-24 |
Family
ID=67961936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910488087.4A Pending CN110277549A (en) | 2019-06-05 | 2019-06-05 | A kind of titania nanotube and the compound electrode material and preparation method thereof of tin oxide nano particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110277549A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112531152A (en) * | 2020-11-11 | 2021-03-19 | 张叶芳 | Electrode material for lithium battery and preparation method thereof |
| CN114242981A (en) * | 2021-12-17 | 2022-03-25 | 太原理工大学 | TiO 22-SnO2Composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949990A (en) * | 2011-08-16 | 2013-03-06 | 同济大学 | Macroporous tin dioxide-titanium dioxide nanotube composite electrode and its preparation method |
| CN105161678A (en) * | 2015-06-16 | 2015-12-16 | 中国石油大学(华东) | Multi-layer composite titanium dioxide nanotube material for lithium battery electrode |
| CN106299294A (en) * | 2016-09-13 | 2017-01-04 | 天津大学 | A kind of preparation method of tin dioxide nanocrystal/titania nanotube composite |
-
2019
- 2019-06-05 CN CN201910488087.4A patent/CN110277549A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949990A (en) * | 2011-08-16 | 2013-03-06 | 同济大学 | Macroporous tin dioxide-titanium dioxide nanotube composite electrode and its preparation method |
| CN105161678A (en) * | 2015-06-16 | 2015-12-16 | 中国石油大学(华东) | Multi-layer composite titanium dioxide nanotube material for lithium battery electrode |
| CN106299294A (en) * | 2016-09-13 | 2017-01-04 | 天津大学 | A kind of preparation method of tin dioxide nanocrystal/titania nanotube composite |
Non-Patent Citations (1)
| Title |
|---|
| XIAOMENG WUA等: "Coaxial SnO2@TiO2 Nanotube Hybrids: From Robust Assembly Strategies to Potential Application in Li+ Storage", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112531152A (en) * | 2020-11-11 | 2021-03-19 | 张叶芳 | Electrode material for lithium battery and preparation method thereof |
| CN112531152B (en) * | 2020-11-11 | 2022-12-27 | 山东兴丰新能源科技有限公司 | Electrode material for lithium battery and preparation method thereof |
| CN114242981A (en) * | 2021-12-17 | 2022-03-25 | 太原理工大学 | TiO 22-SnO2Composite material and preparation method and application thereof |
| CN114242981B (en) * | 2021-12-17 | 2024-04-09 | 太原理工大学 | TiO (titanium dioxide) 2 -SnO 2 Composite material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Interface engineering of Co 3 O 4 nanowire arrays with ultrafine NiO nanowires for high-performance rechargeable alkaline batteries | |
| Lan et al. | Hierarchically porous TiO 2 microspheres as a high performance anode for lithium-ion batteries | |
| Jiang et al. | Co 3 O 4 nanocage derived from metal-organic frameworks: An excellent cathode catalyst for rechargeable Li-O 2 battery | |
| EP3062372A1 (en) | Tungsten-based material super battery and supercapacitor | |
| Meng et al. | Spent alkaline battery-derived manganese oxides as efficient oxygen electrocatalysts for Zn–air batteries | |
| Ghiyasiyan-Arani et al. | Comparative study on electrochemical hydrogen storage of nanocomposites based on S or N doped graphene quantum dots and nanostructured titanium niobate | |
| CN107275606A (en) | A kind of carbon coating spinel lithium manganate nano composite material and preparation method and application | |
| CN106602047A (en) | Preparation method for carbon and lithium titanate compound material | |
| CN110265649A (en) | A kind of preparation method of the chargeable water system Zinc ion battery positive electrode of manganese dioxide of metal oxide cladding | |
| CN109473663A (en) | A kind of anode material of lithium-ion battery and preparation method thereof of redox graphene load antimony | |
| Chen et al. | Hierarchical flower-like cobalt phosphosulfide derived from Prussian blue analogue as an efficient polysulfides adsorbent for long-life lithium-sulfur batteries | |
| CN103247787A (en) | Composite negative pole material for lithium-ion battery and manufacturing method of negative pole material | |
| CN110364732A (en) | With the compound zinc load and preparation method and application of inorganic functional decorative layer in a kind of water system battery | |
| CN110277549A (en) | A kind of titania nanotube and the compound electrode material and preparation method thereof of tin oxide nano particles | |
| CN108807945A (en) | Redox graphene/stannate anode material of lithium-ion battery and its preparation method and application | |
| CN109390579A (en) | A kind of preparation method of the nickelic tertiary cathode material of dry and wet carbon coating | |
| CN104300133A (en) | Carbon nanotube coated lithium titanate material and its preparation method | |
| CN105470492B (en) | Recycling method of waste alkaline manganese battery positive electrode material, trimanganese tetroxide composite slurry and application thereof | |
| CN110289407A (en) | A kind of carbon coating cobalt-doping zinc oxide nano material for lithium ion battery | |
| CN109786769A (en) | A kind of carbon supported noble metal oxide bifunctional catalyst and its preparation method and application | |
| CN109167034A (en) | Using ternary material as lithium-sulfur battery composite cathode material of carrier and preparation method thereof | |
| CN110518212B (en) | Preparation method of positive plate for lithium-sulfur battery | |
| CN106784750A (en) | A kind of TiO/C negative materials and its preparation method and application | |
| CN107256963A (en) | Negative material and preparation method, negative pole and the full battery of lithium ion and preparation method | |
| CN108470901B (en) | Carbon nanotube lithium manganate nanocomposite 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190924 |