CN107302106B - A kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device and preparation method thereof - Google Patents
A kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device and preparation method thereof Download PDFInfo
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- CN107302106B CN107302106B CN201710559671.5A CN201710559671A CN107302106B CN 107302106 B CN107302106 B CN 107302106B CN 201710559671 A CN201710559671 A CN 201710559671A CN 107302106 B CN107302106 B CN 107302106B
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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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- 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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- 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
- H01M10/058—Construction or manufacture
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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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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device and preparation method thereof, it is related to a kind of integrated device and preparation method thereof.The invention aims to solve the problems, such as that existing glass door and the great and blocky titanic oxide material of ratio of the window loss total building energy consumption of Zhan have lower optical parameter regulated value and lower energy storage performance.A kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device is made of the electrically-conductive backing plate, sticky rectangle frame and electrolyte of two panels surface growth mesoporous titanium dioxide nano-tube array.Method: one, the electrically-conductive backing plate for containing nanometic zinc oxide rod array in surface is prepared；Two, the electrically-conductive backing plate of preparation surface growth amorphous titanium dioxide nano-tube array；Three, the electrically-conductive backing plate of preparation surface growth mesoporous titanium dioxide nano-tube array；Four, it assembles.The present invention is suitable for preparing lithium battery/smart window integration device.
Description
Technical field
The invention belongs to multi-functional electrochemical device technical fields, and in particular to a kind of integration device and its preparation side
Method.
Background technique
Currently, with the continuous development of China's economy the rapid growth of propulsion with Urbanization Construction, economy and population makes
It is increasing to obtain the national pressure faced in terms of energy supply and environmental protection.In particular with domestic fast-developing room
Real estate construction, the specific gravity that building energy consumption accounts for China's whole energy consumption are higher and higher.In view of passing through glass door and window in building energy consumption
The energy consumption of family loss accounts for the 40%-50% of total building energy consumption, it is therefore seen that, use the electricity with intelligent, energy-saving function
There is mutagens color smart window important environmental protection and economy to be worth.Since inorganic, metal oxide is in resistance to environment, long circulating, discoloration shape
The advantage of state stabilization etc., it is considered to be the ideal composition material of electrochromic intelligent window device.Metal oxide electricity
It causes metachromatism to be derived from the Dual Implantations process of ion-electron, is that the one kind for improving its performance has very much by oxide structure nanosizing
The means of effect.In nanostructure, the reduction of size greatly reduces the diffusion length of ion and shortens the response time, and
High-specific surface area increases electro-chemical activity number of sites amount and improves electrochromic material discoloration contrast.Meanwhile it aoxidizing
The lithium ion storge quality of object is also the Dual Implantations process of lithium ion electronics, therefore the metal oxide with high electrochromic property
Excellent energy-storage property can also be symbolized during lithium ion electronics deintercalation.
Titanium dioxide is in human eye sensitivity region (colourless to blue), discoloration contrast height, crystalline substance with its color change state range
Body structural stability is good, environment compatibility is relatively strong and the factors such as cheap, becomes a kind of ideal electrochromism and energy storage material
Material.But due to diffusion coefficient of the lithium ion in titanium dioxide relatively low (2 × 10-17cm2/ s), delay lithium ion to exist
Deintercalation speed in titanium dioxide crystal structure, so that block shape titanic oxide material shows lower optical parameter regulated value
(less than 20%) and lower energy storage performance (about 75mAh/g).
Summary of the invention
It is great and blocky two the invention aims to solve the ratio of existing glass door and the window loss total building energy consumption of Zhan
Titania meterial has the problem of lower optical parameter regulated value and lower energy storage performance, and provides a kind of based on two
The lithium battery of medium pore of titania nano-tube array/smart window integration device and preparation method thereof.
A kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device is grown by two panels surface
The electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array, sticky rectangle frame and electrolyte composition；The sticky rectangle frame upper end
Face and lower end surface are respectively arranged with the electrically-conductive backing plate of surface growth mesoporous titanium dioxide nano-tube array, form confined space；Institute
Electrolyte is equipped in the confined space stated, and on the electrically-conductive backing plate of two piece of one side surface growth mesoporous titanium dioxide nano-tube array
Mesoporous titanium dioxide nano-tube array shifted to install in confined space；
Growth has mesoporous titanium dioxide nano-tube array on the half surface area of the electrically-conductive backing plate, and titanium dioxide is situated between
Hole nano-tube array is grown close to one end of electrically-conductive backing plate.
One, the electrically-conductive backing plate of nanometic zinc oxide rod array is contained on electrodeposition process preparation surface:
1., successively using acetone, methanol and ultrapure water 10min~20min is cleaned by ultrasonic to electrically-conductive backing plate respectively, obtain clear
Electrically-conductive backing plate after washing；
Step 1 1. described in electrically-conductive backing plate be FTO electro-conductive glass；
2., electrolyte is added in electrolytic cell, then electrolyte is heated to 80 DEG C~100 DEG C, with the conduction after cleaning
Substrate is as working electrode, and platinized platinum is to electrode, and Ag/AgCl electrode is reference electrode, starts electrochemical workstation, in deposition temperature
Degree is 90 DEG C and depositing current density is 0.2mA/cm2~0.7mA/cm2Lower deposition 1200s~2400s, then electrically-conductive backing plate is taken
Out, electrically-conductive backing plate is cleaned 3 times~5 times using deionization, then electrically-conductive backing plate is dried at room temperature for 1h~3h, place into temperature
To be heat-treated 1h~4h in 350 DEG C of Muffle furnaces, the electrically-conductive backing plate that nanometic zinc oxide rod array is contained on surface is obtained；
Step 1 2. described in electrolyte be zinc nitrate, ammonium acetate, methenamine and water mixed liquor；The electrolysis
Nitric acid zinc concentration is 0.02mol/L~0.2mol/L in liquid, and the concentration of ammonium acetate is 0.02mol/L~0.2mol/L, crow
The concentration of Lip river tropine is 0.02mol/L~0.2mol/L；
Two, by step 1 2. obtained in the surface electrically-conductive backing plate that contains nanometic zinc oxide rod array be placed in ammonium hexa-fluorotitanate
With 1h~3h is impregnated in the deionized water solution of boric acid, then electrically-conductive backing plate taken out, obtains surface and contain amorphous titanium dioxide
The electrically-conductive backing plate of meso-porous nano pipe array；Amorphous titanium dioxide meso-porous nano pipe array is contained to surface using deionized water
Electrically-conductive backing plate cleans 3 times~5 times, obtains the electrically-conductive backing plate of surface growth amorphous titanium dioxide meso-porous nano pipe array；
The concentration of ammonium hexa-fluorotitanate is in the deionized water solution of ammonium hexa-fluorotitanate described in step 2 and boric acid
0.02mol/L~0.1mol/L, the concentration of boric acid are 0.04mol/L~0.2mol/L；
Surface described in step 2 grows the amorphous on the electrically-conductive backing plate of amorphous titanium dioxide meso-porous nano pipe array
The area of state mesoporous titanium dioxide nano-tube array is 3.5cm2~5.5cm2, and grown close to one end of electrically-conductive backing plate；
Three, by surface growth amorphous titanium dioxide meso-porous nano pipe array electrically-conductive backing plate be placed in temperature be 380 DEG C~
It is heat-treated 1h~3h in 450 DEG C of Muffle furnace, obtains the electrically-conductive backing plate of surface growth mesoporous titanium dioxide nano-tube array；
Four, it assembles: by the conductive base board group of sticky rectangle frame and two panels surface growth mesoporous titanium dioxide nano-tube array
At confined space, electrolyte is injected into confined space, is reused epoxy resin sealing and is injected the hole left, obtains based on two
The lithium battery of medium pore of titania nano-tube array/smart window integration device；
Two pieces of surface growths described in step 4 have the dioxy on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Change titanium meso-porous nano pipe array to shift to install in confined space.
Surface obtained in step 3 of the present invention grows the dioxy on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Change the mesoporous titanium dioxide nano-tube array that titanium meso-porous nano pipe array is crystalline state.
The principle of the present invention and advantage:
One, the present invention promotes Hydrolyze method using template is sacrificed, and titanium dioxide is prepared in situ in electrically conducting transparent matrix surface and is situated between
Hole nano-tube array, the surface fake capacitance effect by the infiltration of good electrolyte, shorter ion diffusion length and enhancing are real
Existing electrode film quick response, Gao Bianse contrast and high-lithium ion store high rate performance；With the mesoporous titanium dioxide nanotube
Array assembling obtains lithium battery/smart window integration device, which shows high energy storage, obvious in charge and discharge process
Color contrast and transmitance regulation performance；The above electrochemical energy storage and optical parameter regulation performance make the device in smart window
It is with a wide range of applications with fields such as displays；
Two, mesoporous titanium dioxide nanotube prepared by the present invention is nanostructure；Mesoporous titanium dioxide nanotube is by 10
Nanometer little particle below is constituted, and is the titanium dioxide of Detitanium-ore-type；
Three, mesoporous titanium dioxide nano-tube array prepared by the present invention sweeps the oxidation of the cyclic voltammetry curve under speed in difference
Reduction peak can be good at keeping, and illustrate that the array has good high rate performance；
Four, mesoporous titanium dioxide nano-pipe array thin film prepared by the present invention is under 15C current density, in 144s~152s
It is interior i.e. complete 96mAh/g~100mAh/g discharge capacity, while the transmitance regulated value at 700nm wavelength be 32.0%~
35.0%；
Five, the lithium battery prepared by the present invention based on mesoporous titanium dioxide nano-tube array/smart window integration device can
To show high-lithium ion storage high rate performance and transmitance regulation performance under quick charging and discharging currents density；1A/g's
Under current density, realizes the process of charge or discharge within 232 seconds and the specific capacity discharged is 60mAh/g~65mAh/g, simultaneously
The device shows transmitance regulated value in charge and discharge process, and transmitance regulated value is 30.0%~33.0% at 700nm.
The present invention is suitable for preparing lithium battery/smart window integration device.
Detailed description of the invention
Fig. 1 is the lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device prepared by embodiment one
The structural schematic diagram of part, 1 is FTO electro-conductive glass in Fig. 1, and 2 be mesoporous titanium dioxide nano-tube array, and 3 be electrolyte, and 4 be viscous
Property rectangle frame；
Fig. 2 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The surface scan electromicroscopic photograph of mesoporous titanium dioxide nano-tube array；
Fig. 3 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The cross-sectional scans electromicroscopic photograph of mesoporous titanium dioxide nano-tube array；
Fig. 4 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Transmission electron microscope photo under the low magnification of mesoporous titanium dioxide nano-tube array；
Fig. 5 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Transmission electron microscope photo under the high-amplification-factor of mesoporous titanium dioxide nano-tube array；
Fig. 6 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The selective electron diffraction photo of mesoporous titanium dioxide nano-tube array；
Fig. 7 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The high-resolution-ration transmission electric-lens photo of mesoporous titanium dioxide nano-tube array；
Fig. 8 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Cyclic voltammetry curve of the mesoporous titanium dioxide nano-tube array under different scanning rates；
Fig. 9 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Charging and discharging curve of the mesoporous titanium dioxide nano-tube array under 15C current density；
Figure 10 is the electrically-conductive backing plate that surface obtained in one step 3 of embodiment grows mesoporous titanium dioxide nano-tube array
Transmitance adjustment curve of the upper mesoporous titanium dioxide nano-tube array at 700nm wavelength under the conditions of 15C charge and discharge；
Figure 11 is lithium battery/smart window one based on mesoporous titanium dioxide nano-tube array of one step 4 of embodiment preparation
Charging and discharging curve of the body device under different charging and discharging currents density；
Figure 12 is lithium battery/smart window one based on mesoporous titanium dioxide nano-tube array of one step 4 of embodiment preparation
Color contrast photo of the body device in charge and discharge process.
Specific embodiment
Present embodiment be a kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device by
Two panels surface grows the electrically-conductive backing plate, sticky rectangle frame and electrolyte composition of mesoporous titanium dioxide nano-tube array；Described is viscous
Property rectangle frame upper surface and lower end surface be respectively arranged with surface growth mesoporous titanium dioxide nano-tube array electrically-conductive backing plate, composition
Confined space；Electrolyte is equipped in the confined space, and two piece of one side surface grows mesoporous titanium dioxide nano-tube array
Electrically-conductive backing plate on mesoporous titanium dioxide nano-tube array shifted to install in confined space；
Growth has mesoporous titanium dioxide nano-tube array on the half surface area of the electrically-conductive backing plate, and titanium dioxide is situated between
Hole nano-tube array is grown close to one end of electrically-conductive backing plate.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: the electrically-conductive backing plate is
FTO.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: the viscosity
The material of rectangle frame is the polymethyl acrylate adhesive tape of biadhesive.Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: the electrolysis
Liquid is the mixed liquor of lithium perchlorate and propene carbonate；The concentration of lithium perchlorate is 1mol/L in the electrolyte.Other steps
Suddenly identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: the viscosity
The height of rectangle frame is 0.5mm~1.5mm.Other steps are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: the surface
The area for growing the mesoporous titanium dioxide nano-tube array on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array is 3.5cm2
~5.5cm2.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: present embodiment is a kind of lithium battery/intelligence based on mesoporous titanium dioxide nano-tube array
What the preparation method of energy window integration device was specifically realized by the following steps:
One, the electrically-conductive backing plate of nanometic zinc oxide rod array is contained on electrodeposition process preparation surface:
1., successively using acetone, methanol and ultrapure water 10min~20min is cleaned by ultrasonic to electrically-conductive backing plate respectively, obtain clear
Electrically-conductive backing plate after washing；
Step 1 1. described in electrically-conductive backing plate be FTO electro-conductive glass；
2., electrolyte is added in electrolytic cell, then electrolyte is heated to 80 DEG C~100 DEG C, with the conduction after cleaning
Substrate is as working electrode, and platinized platinum is to electrode, and Ag/AgCl electrode is reference electrode, starts electrochemical workstation, in deposition temperature
Degree is 90 DEG C and depositing current density is 0.2mA/cm2~0.7mA/cm2Lower deposition 1200s~2400s, then electrically-conductive backing plate is taken
Out, electrically-conductive backing plate is cleaned 3 times~5 times using deionization, then electrically-conductive backing plate is dried at room temperature for 1h~3h, place into temperature
To be heat-treated 1h~4h in 350 DEG C of Muffle furnaces, the electrically-conductive backing plate that nanometic zinc oxide rod array is contained on surface is obtained；
Step 1 2. described in electrolyte be zinc nitrate, ammonium acetate, methenamine and water mixed liquor；The electrolysis
Nitric acid zinc concentration is 0.02mol/L~0.2mol/L in liquid, and the concentration of ammonium acetate is 0.02mol/L~0.2mol/L, crow
The concentration of Lip river tropine is 0.02mol/L~0.2mol/L；
Two, by step 1 2. obtained in the surface electrically-conductive backing plate that contains nanometic zinc oxide rod array be placed in ammonium hexa-fluorotitanate
With 1h~3h is impregnated in the deionized water solution of boric acid, then electrically-conductive backing plate taken out, obtains surface and contain amorphous titanium dioxide
The electrically-conductive backing plate of meso-porous nano pipe array；Amorphous titanium dioxide meso-porous nano pipe array is contained to surface using deionized water
Electrically-conductive backing plate cleans 3 times~5 times, obtains the electrically-conductive backing plate of surface growth amorphous titanium dioxide meso-porous nano pipe array；
The concentration of ammonium hexa-fluorotitanate is in the deionized water solution of ammonium hexa-fluorotitanate described in step 2 and boric acid
0.02mol/L~0.1mol/L, the concentration of boric acid are 0.04mol/L~0.2mol/L；
Surface described in step 2 grows the amorphous on the electrically-conductive backing plate of amorphous titanium dioxide meso-porous nano pipe array
The area of state mesoporous titanium dioxide nano-tube array is 3.5cm2~5.5cm2, and grown close to one end of electrically-conductive backing plate；
Three, by surface growth amorphous titanium dioxide meso-porous nano pipe array electrically-conductive backing plate be placed in temperature be 380 DEG C~
It is heat-treated 1h~3h in 450 DEG C of Muffle furnace, obtains the electrically-conductive backing plate of surface growth mesoporous titanium dioxide nano-tube array；
Four, it assembles: by the conductive base board group of sticky rectangle frame and two panels surface growth mesoporous titanium dioxide nano-tube array
At confined space, electrolyte is injected into confined space, is reused epoxy resin sealing and is injected the hole left, obtains based on two
The lithium battery of medium pore of titania nano-tube array/smart window integration device；
Two pieces of surface growths described in step 4 have the dioxy on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Change titanium meso-porous nano pipe array to shift to install in confined space.
Surface obtained in present embodiment step 3 is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Mesoporous titanium dioxide nano-tube array is the mesoporous titanium dioxide nano-tube array of crystalline state.
The principle and advantage of present embodiment:
One, present embodiment promotes Hydrolyze method using template is sacrificed, and titanium dioxide is prepared in situ in electrically conducting transparent matrix surface
Titanium meso-porous nano pipe array is imitated by the surface fake capacitance of the infiltration of good electrolyte, shorter ion diffusion length and enhancing
It should realize electrode film quick response, Gao Bianse contrast and high-lithium ion storage high rate performance；It is received with the mesoporous titanium dioxide
Mitron array assembling obtain lithium battery/smart window integration device, the device shown in charge and discharge process high energy storage,
Apparent color contrast and transmitance regulation performance；The above electrochemical energy storage and optical parameter regulation performance make the device in intelligence
The fields such as energy window and display are with a wide range of applications；
Two, the mesoporous titanium dioxide nanotube of present embodiment preparation is nanostructure；Mesoporous titanium dioxide nanotube is
It is made of 10 nanometers of little particles below, is the titanium dioxide of Detitanium-ore-type；
Three, the mesoporous titanium dioxide nano-tube array of present embodiment preparation sweeps the cyclic voltammetry curve under speed in difference
Redox peaks can be good at keeping, and illustrate that the array has good high rate performance；
Four, present embodiment preparation mesoporous titanium dioxide nano-pipe array thin film under 15C current density, 144s~
The discharge capacity of 96mAh/g~100mAh/g is completed in 152s, while the transmitance regulated value at 700nm wavelength is
32.0%~35.0%；
Five, the lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device of present embodiment preparation
Part can show high-lithium ion storage high rate performance and transmitance regulation performance under quick charging and discharging currents density；?
Under the current density of 1A/g, realizes the process of charge or discharge within 232 seconds and the specific capacity discharged is 60mAh/g~65mAh/
G, while the device shows transmitance regulated value in charge and discharge process, at 700nm transmitance regulated value be 30.0%~
33.0%.
Present embodiment is suitable for preparing lithium battery/smart window integration device.
Specific embodiment 8: the difference of present embodiment and specific embodiment seven is: step 1 1. described in
Electrically-conductive backing plate is FTO electro-conductive glass.It is other identical as specific embodiment seven.
Specific embodiment 9: the difference of present embodiment and specific embodiment seven or eight is: described in step 4
Sticky rectangle frame material be biadhesive polymethyl acrylate adhesive tape, the height of sticky rectangle frame be 0.5mm~
1.5mm.It is other identical as specific embodiment seven or eight.
Specific embodiment 10: the difference of present embodiment and specific embodiment seven to nine is: described in step 4
Electrolyte be lithium perchlorate and propene carbonate mixed liquor；The concentration of lithium perchlorate is 1mol/L in the electrolyte.
It is other identical as specific embodiment seven to nine.
Beneficial effects of the present invention are verified using following embodiment:
A kind of embodiment one: system of the lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device
Preparation Method is specifically realized by the following steps:
One, the electrically-conductive backing plate of nanometic zinc oxide rod array is contained on electrodeposition process preparation surface:
1., successively using acetone, methanol and ultrapure water respectively to electrically-conductive backing plate be cleaned by ultrasonic 10min, after being cleaned
Electrically-conductive backing plate；
Step 1 1. described in electrically-conductive backing plate be FTO electro-conductive glass；
2., electrolyte is added in electrolytic cell, then electrolyte is heated to 90 DEG C, using the electrically-conductive backing plate after cleaning as
Working electrode, platinized platinum are to electrode, and Ag/AgCl electrode is reference electrode, start electrochemical workstation, are 90 DEG C in depositing temperature
It is 0.5mA/cm with depositing current density2Lower deposition 1800s, then electrically-conductive backing plate is taken out, it is clear to electrically-conductive backing plate using deionization
It washes 5 times, then electrically-conductive backing plate is dried at room temperature for 1h, place into the Muffle furnace that temperature is 350 DEG C and be heat-treated 2h, obtain surface
Electrically-conductive backing plate containing nanometic zinc oxide rod array；
Step 1 2. described in electrolyte be zinc nitrate, ammonium acetate, methenamine and water mixed liquor；The electrolysis
Nitric acid zinc concentration is 0.05mol/L in liquid, and the concentration of ammonium acetate is 0.05mol/L, and the concentration of methenamine is
0.05mol/L；
Two, by step 1 2. obtained in the surface electrically-conductive backing plate that contains nanometic zinc oxide rod array be placed in ammonium hexa-fluorotitanate
With 2h is impregnated in the deionized water solution of boric acid, then electrically-conductive backing plate taken out, obtaining surface, to contain amorphous titanium dioxide mesoporous
The electrically-conductive backing plate of nano-tube array；Contain the conduction of amorphous titanium dioxide meso-porous nano pipe array to surface using deionized water
Base-plate cleaning 4 times, obtain the electrically-conductive backing plate of surface growth amorphous titanium dioxide meso-porous nano pipe array；
The concentration of ammonium hexa-fluorotitanate is in the deionized water solution of ammonium hexa-fluorotitanate described in step 2 and boric acid
0.05mol/L, the concentration of boric acid are 0.1mol/L；
Surface described in step 2 grows the amorphous on the electrically-conductive backing plate of amorphous titanium dioxide meso-porous nano pipe array
The area of state mesoporous titanium dioxide nano-tube array is 4.5cm2, and grown close to one end of electrically-conductive backing plate；
Three, the electrically-conductive backing plate of surface growth amorphous titanium dioxide meso-porous nano pipe array is placed in temperature is 420 DEG C
It is heat-treated 2h in Muffle furnace, obtains the electrically-conductive backing plate of surface growth mesoporous titanium dioxide nano-tube array；
Four, it assembles: by the conductive base board group of sticky rectangle frame and two panels surface growth mesoporous titanium dioxide nano-tube array
At confined space, electrolyte is injected into confined space, is reused epoxy resin sealing and is injected the hole left, obtains based on two
The lithium battery of medium pore of titania nano-tube array/smart window integration device；
The material of sticky rectangle frame described in step 4 is the polymethyl acrylate adhesive tape of biadhesive, is highly 1mm；
Electrolyte described in step 4 is the mixed liquor of lithium perchlorate and propene carbonate；High chlorine in the electrolyte
The concentration of sour lithium is 1mol/L；
Two pieces of surface growths described in step 4 have the dioxy on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Change titanium meso-porous nano pipe array to shift to install in confined space.
Surface obtained in one step 3 of embodiment grows two on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Medium pore of titania nano-tube array is the mesoporous titanium dioxide nano-tube array of crystalline state.
Fig. 1 is the lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device prepared by embodiment one
The structural schematic diagram of part, 1 is FTO electro-conductive glass in Fig. 1, and 2 be mesoporous titanium dioxide nano-tube array, and 3 be electrolyte, and 4 be viscous
Property rectangle frame；
Fig. 2 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The surface scan electromicroscopic photograph of mesoporous titanium dioxide nano-tube array；
Fig. 3 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The cross-sectional scans electromicroscopic photograph of mesoporous titanium dioxide nano-tube array；
It can be seen that mesoporous titanium dioxide nano-tube array vertical-growth is in electrically conducting transparent substrate surface from Fig. 2 and Fig. 3,
It is can be confirmed from nanotube bottom notch as nano tube structure.
Fig. 4 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Transmission electron microscope photo under the low magnification of mesoporous titanium dioxide nano-tube array；
Fig. 5 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Transmission electron microscope photo under the high-amplification-factor of mesoporous titanium dioxide nano-tube array；
Fig. 6 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The selective electron diffraction photo of mesoporous titanium dioxide nano-tube array；
Fig. 7 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
The high-resolution-ration transmission electric-lens photo of mesoporous titanium dioxide nano-tube array；
It can further confirm that mesoporous titanium dioxide nanotube is nano tube structure from Fig. 4~Fig. 7, and nanotube is by 10
Nanometer little particle below is constituted, it can be seen that nanometer from high-resolution-ration transmission electric-lens picture and selective electron diffraction picture
Grain is the titanium dioxide of Detitanium-ore-type.
Fig. 8 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Cyclic voltammetry curve of the mesoporous titanium dioxide nano-tube array under different scanning rates；
There are apparent redox peaks in Fig. 8, illustrates that mesoporous titanium dioxide nano-tube array energy storage is derived from lithium ion
Deintercalation process, and with speed is swept from 0.2mV/s to 1mV/s, redox peaks can be good at keeping, and illustrate that the array has
Good high rate performance, the lithium ion deintercalation reaction being directed to can be carried out quickly.
Fig. 9 is that surface obtained in one step 3 of embodiment is grown on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Charging and discharging curve of the mesoporous titanium dioxide nano-tube array under 15C current density；
Figure 10 is the electrically-conductive backing plate that surface obtained in one step 3 of embodiment grows mesoporous titanium dioxide nano-tube array
Transmitance adjustment curve of the upper mesoporous titanium dioxide nano-tube array at 700nm wavelength under the conditions of 15C charge and discharge；
From Fig. 9 and Figure 10 it is found that mesoporous titanium dioxide nano-pipe array thin film is under 15C current density, 144s~
The discharge capacity of 98mAh/g is completed in 152s, while the transmitance regulated value at 700nm wavelength is 33.5%；Titanium dioxide
The short time releases high capacity and high transmittance regulated value to titanium meso-porous nano pipe array at higher current densities, this illustrates the array
Film has good lithium ion deintercalation invertibity, is ideal lithium ion battery and electrochromic device thin-film electrode material.
Figure 11 is lithium battery/smart window one based on mesoporous titanium dioxide nano-tube array of one step 4 of embodiment preparation
Charging and discharging curve of the body device under different charging and discharging currents density；
As can be seen from Figure 11, the lithium battery prepared by the present invention based on mesoporous titanium dioxide nano-tube array/smart window one
High-lithium ion storage high rate performance and transmitance regulation performance can be shown under quick charging and discharging currents density by changing device；
Under the current density of 1A/g, realizes the process of charge or discharge within 232 seconds and the specific capacity discharged is 60mAh/g, simultaneously
The device shows transmitance regulated value in charge and discharge process, and transmitance regulated value is 30.4% at 700nm.
Figure 12 is lithium battery/smart window one based on mesoporous titanium dioxide nano-tube array of one step 4 of embodiment preparation
Color contrast photo of the body device in charge and discharge process.
As can be seen from Figure 12, lithium battery/intelligence based on mesoporous titanium dioxide nano-tube array of one step 4 of embodiment preparation
Color contrast of the energy window integration device in charge and discharge process, good color contrast illustrate that the integration device is being shown
Field also has certain practicability.
Claims (10)
1. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device, it is characterised in that a kind of
Lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device grows mesoporous titanium dioxide by two panels surface
The electrically-conductive backing plate of nano-tube array, sticky rectangle frame and electrolyte composition；The sticky rectangle frame upper surface and lower end surface point
It is not provided with the electrically-conductive backing plate of surface growth mesoporous titanium dioxide nano-tube array, forms confined space；The confined space
It is interior to be equipped with electrolyte, and the titanium dioxide on the electrically-conductive backing plate of two piece of one side surface growth mesoporous titanium dioxide nano-tube array is situated between
Hole nano-tube array shifts to install in confined space；
Growth has mesoporous titanium dioxide nano-tube array on the half surface area of the electrically-conductive backing plate, and mesoporous titanium dioxide is received
Mitron array is grown close to one end of electrically-conductive backing plate.
2. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 1/smart window integration
Device, it is characterised in that the electrically-conductive backing plate is FTO.
3. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 1/smart window integration
Device, it is characterised in that the material of the sticky rectangle frame is the polymethyl acrylate adhesive tape of biadhesive.
4. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 1/smart window integration
Device, it is characterised in that the electrolyte is the mixed liquor of lithium perchlorate and propene carbonate；High chlorine in the electrolyte
The concentration of sour lithium is 1mol/L.
5. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 1/smart window integration
Device, it is characterised in that the height of the sticky rectangle frame is 0.5mm~1.5mm.
6. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 1/smart window integration
Device, it is characterised in that the mesoporous titanium dioxide on the electrically-conductive backing plate of the surface growth mesoporous titanium dioxide nano-tube array
The area of nano-tube array is 3.5cm2~5.5cm2。
7. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device as described in claim 1
A kind of part, it is characterised in that preparation side of the lithium battery based on mesoporous titanium dioxide nano-tube array/smart window integration device
What method was specifically realized by the following steps:
One, the electrically-conductive backing plate of nanometic zinc oxide rod array is contained on electrodeposition process preparation surface:
1., successively using acetone, methanol and ultrapure water respectively to electrically-conductive backing plate be cleaned by ultrasonic 10min~20min, after obtaining cleaning
Electrically-conductive backing plate；
Step 1 1. described in electrically-conductive backing plate be FTO electro-conductive glass；
2., electrolyte is added in electrolytic cell, then electrolyte is heated to 80 DEG C~100 DEG C, with the electrically-conductive backing plate after cleaning
As working electrode, platinized platinum is to electrode, and Ag/AgCl electrode is reference electrode, starts electrochemical workstation, is in depositing temperature
90 DEG C are 0.2mA/cm with depositing current density2~0.7mA/cm2Lower deposition 1200s~2400s, then electrically-conductive backing plate is taken out, make
It spends ion pair electrically-conductive backing plate to clean 3 times~5 times, then electrically-conductive backing plate is dried at room temperature for 1h~3h, placing into temperature is 350
DEG C Muffle furnace in be heat-treated 1h~4h, obtain the electrically-conductive backing plate that nanometic zinc oxide rod array is contained on surface；
Step 1 2. described in electrolyte be zinc nitrate, ammonium acetate, methenamine and water mixed liquor；In the electrolyte
Nitric acid zinc concentration is 0.02mol/L~0.2mol/L, and the concentration of ammonium acetate is 0.02mol/L~0.2mol/L, methenamine
Concentration be 0.02mol/L~0.2mol/L；
Two, by step 1 2. obtained in the surface electrically-conductive backing plate that contains nanometic zinc oxide rod array be placed in ammonium hexa-fluorotitanate and boron
1h~3h is impregnated in the deionized water solution of acid, then electrically-conductive backing plate is taken out, and obtaining surface, to contain amorphous titanium dioxide mesoporous
The electrically-conductive backing plate of nano-tube array；Contain the conduction of amorphous titanium dioxide meso-porous nano pipe array to surface using deionized water
Base-plate cleaning 3 times~5 times, obtain the electrically-conductive backing plate of surface growth amorphous titanium dioxide meso-porous nano pipe array；
The concentration of ammonium hexa-fluorotitanate is 0.02mol/L in the deionized water solution of ammonium hexa-fluorotitanate described in step 2 and boric acid
~0.1mol/L, the concentration of boric acid are 0.04mol/L~0.2mol/L；
Surface described in step 2 grows the amorphous state two on the electrically-conductive backing plate of amorphous titanium dioxide meso-porous nano pipe array
The area of medium pore of titania nano-tube array is 3.5cm2~5.5cm2, and grown close to one end of electrically-conductive backing plate；
Three, the electrically-conductive backing plate of surface growth amorphous titanium dioxide meso-porous nano pipe array is placed in temperature is 380 DEG C~450 DEG C
Muffle furnace in be heat-treated 1h~3h, obtain surface growth mesoporous titanium dioxide nano-tube array electrically-conductive backing plate；
Four, it assembles: the electrically-conductive backing plate composition of sticky rectangle frame and two panels surface growth mesoporous titanium dioxide nano-tube array is close
Space is closed, electrolyte is injected into confined space, epoxy resin sealing is reused and injects the hole left, obtain based on titanium dioxide
The lithium battery of titanium meso-porous nano pipe array/smart window integration device；
Two pieces of surface growths described in step 4 have the titanium dioxide on the electrically-conductive backing plate of mesoporous titanium dioxide nano-tube array
Meso-porous nano pipe array shifts to install in confined space.
8. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 7/smart window integration
Device, it is characterised in that step 1 1. described in electrically-conductive backing plate be FTO electro-conductive glass.
9. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 7/smart window integration
Device, it is characterised in that the material of sticky rectangle frame described in step 4 is the polymethyl acrylate adhesive tape of biadhesive, is glued
Property rectangle frame height be 0.5mm~1.5mm.
10. a kind of lithium battery based on mesoporous titanium dioxide nano-tube array according to claim 7/smart window integration
Device, it is characterised in that electrolyte described in step 4 is the mixed liquor of lithium perchlorate and propene carbonate；The electrolysis
The concentration of lithium perchlorate is 1mol/L in liquid.
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