CN110323070B - Light-assisted rechargeable battery based on dual-function compatible electrode - Google Patents
Light-assisted rechargeable battery based on dual-function compatible electrode Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005286 illumination Methods 0.000 claims abstract description 11
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002390 adhesive tape Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 239000012982 microporous membrane Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
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- 230000009977 dual effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 abstract 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
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- 239000002096 quantum dot Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a light-assisted rechargeable battery based on a bifunctional compatible electrode, which is formed by combining a solar battery and a lithium ion battery, using cuprous sulfide prepared by a hydrothermal method as a common electrode to realize the functions of energy storage and release, and directly blade-coating the cuprous sulfide on the surface of an N719 ruthenium dye-sensitized titanium dioxide photo-anode. And infiltrating the composite electrode and the lithium metal by using an electrolyte, and separating and compacting by using a diaphragm to finally form the light-assisted rechargeable battery with two electrodes. The short-circuited composite electrode fully exerts the characteristics of high catalytic activity and high capacity of the cuprous sulfide, and the compact battery structure can ensure that the electrolyte can be fully immersed into the active substance, thereby improving the performance of the rechargeable battery. Under the auxiliary condition of illumination, the charge and discharge capacity can be respectively improved, so that the performance of the battery is improved.
Description
Technical Field
The invention relates to a light-assisted rechargeable battery based on a dual-function compatible electrode, belonging to the field of photoelectrochemistry energy storage materials. The invention is realized by directly adding Cu2And S is attached to the surface of the photoanode, and the functions of converting light energy into electric energy and directly storing the electric energy are realized in one electrode.
Background
Under the situation that energy problems are increasingly tense, non-renewable energy sources such as coal and petroleum cannot meet the future requirements for energy sources, and the non-renewable energy sources cause serious environmental problems, so that the utilization of sustainable energy sources becomes an urgent field to be researched. Sunlight, which is the most common clean energy source, contains huge energy and is also considered as the final source of all energy resources on the earth. Therefore, a variety of solar cells that convert light energy into electrical energy have been developed. However, since sunlight is intermittent energy for the earth, the utilization rate of sunlight by the solar cell is reduced. The common method is to connect a solar cell and a rechargeable battery in series, store solar energy in the rechargeable battery directly, and indirectly apply the solar energy to daily life.
Because the mode of directly connecting the two in series can cause great ohmic loss, and the space is very occupied, and the use is not easy. The device which integrates the solar cell and the rechargeable cell is an effective means for directly utilizing clean energy (solar energy). When the photoelectrode is illuminated to generate an electron hole pair, the photohole can drive the ions in the photoelectrode to change, the photoelectrons can simultaneously reach the other electrode through an external circuit, the photoelectrons and the photohole pair cooperate to complete the conversion of light energy and store the light energy in the battery, and the discharge is the same as that of a common secondary battery.
Disclosure of Invention
The invention aims to provide a light-assisted rechargeable battery structure based on a dual-function compatible electrode, which can improve the performance of the battery when being irradiated by sunlight in the charging and discharging processes. During charging, light irradiation lowers the charging voltage and increases the charging capacity, while during discharging, light irradiation lengthens the discharging time. The invention utilizes the simplest device structure to effectively utilize sunlight and effectively improve the charge and discharge performance of the battery.
The invention provides a light-assisted rechargeable battery based on a dual-function compatible electrode, which comprises the following parts: from Cu2S is directly attached to the surface of a dye-sensitized titanium dioxide photo-anode, and is a difunctional compatible electrode taking FTO conductive glass as a carrier; shearing into Cu2S is a positive electrode composed of metal lithium with the same shape as the active material; dripping LiTFSI/DOL-DME organic electrolyte on two sides of the diaphragm; a diaphragm composed of a polypropylene microporous membrane; and a positive current collector composed of copper foil. The positive pole of the metal lithium is pasted on the positive pole current collector, and the dual-function compatible electrode and the positive pole of the metal lithium are soaked by electrolyte, separated by a diaphragm and then compressed.
Cu provided by the invention2S is synthesized by a hydrothermal method, and the specific synthesis method is as follows:
(1) weighing 0.01mol/L-0.1mol/L CuCl and CH4N20.05mol/L-0.15mol/L S and 0.005g/mL-0.01g/mL PVP are mixed in ethanol and glycol solution with equal volume, and the stirring time is 5min-15 min.
(2) Pouring the mixed solution into a high-pressure reaction kettle for high-temperature and high-pressure treatment, wherein the heating temperature is 120-180 ℃, the pressurizing pressure is 0-70 Mpa, and the reaction time is 6-18 h.
(3) Carrying out ultrasonic centrifugal cleaning on the solution, wherein the centrifugal rotating speed is 1000rad/min-8000rad/min, cleaning the ethanol and the water in sequence until the ethanol and the water are uniformly dispersed, the cleaning frequency is 3-5 times, then drying the solution at the temperature of 60-80 ℃, and storing the solution in an environment with the water content of less than 0.1ppm and the oxygen content of less than 0.1 ppm.
The preparation method of the N719 dye sensitized titanium dioxide photo-anode provided by the invention comprises the following steps:
(1) uniformly dispersing the N719 dye in an ethanol solution, wherein the concentration is 3.6mmol L-1And at an illumination intensity of 0W/m2-0.2W/m2Is stored in the environment of (1).
(2) The conductive glass is cleaned for 20min to 40min by an ultrasonic cleaning method in the sequence of deionized water, ethanol, acetone, ethanol and deionized water, and then the conductive glass is dried at the drying temperature of 60 ℃ to 80 ℃.
(3) The TiO is mixed by a spin coater2The slurry is spin-coated on conductive glass at a rotation speed of 3000rad/min-7000rad/min for 1-3 times to obtain TiO with a thickness of 5-20 μm2And drying the electrode after each spin coating at the drying temperature of 60-80 ℃, then sintering the electrode in an air atmosphere at the temperature of 450-500 ℃ for 30 minutes, and cooling the electrode to room temperature.
(4) In dark environment, TiO is added2The photoanode is soaked in 3.6mmol L-1The N719 dye is evenly dispersed in the ethanol solution, soaked for 12-24 h, then cleaned by ethanol and dried by blowing, and then stored in a dark environment.
The preparation method of the bifunctional compatible electrode provided by the invention comprises the following steps:
(1) mixing Cu by mass ratio280-90% of S, 10-15% of PVDF and 0-5% of conductive acetylene black are added dropwise with N-methyl pyrrolidone and ground for 30min to form uniformly dispersed slurry.
(2) Mixing Cu2S slurry is placed in a place with the illumination intensity of 0W/m2-0.2W/m2In the environment of (1), the dye-sensitized TiO is coated by a blade coating mode of 45-90 DEG2Coating the surface of the photo-anode with a thickness of 8-20 μm to obtain Cu2And the slurry is completely and uniformly covered.
(3) Drying the electrode in dark vacuum environment at-0.08-0.1 MPa and illumination intensity of 0W/m2-0.2W/m2The temperature is 60-80 ℃, and the time is 6-12 h.
The invention provides an assembling method of a light-assisted rechargeable battery, which comprises the following steps:
(1) extending copper wires out of the surface of the carrier (conductive glass) of the dual-function compatible electrode, fixing the copper wires by using adhesive tapes, and doping SnO with fluorine2The transparent film is a current collector, and the battery is assembled in an environment filled with high-purity Ar, wherein the purity of the Ar is>99.99%, water content<0.1ppm, oxygen content<0.1ppm。
(2) Shearing metallic lithium into Cu2The S film was of the same shape, and was attached to a copper foil (current collector) and fixed with an adhesive tape.
(3) Firstly, dripping LiTFSI/DOL-DME electrolyte in Cu2Adhering a polypropylene microporous membrane on the surface of S, dripping LiTFSI/DOL-DME electrolyte on the surface of the metal lithium, wherein the volume of the dripped electrolyte is 5-15 muL, and then jointing and compacting the two electrodes at the pressure of 0kg/cm2-50kg/cm2。
(4) Standing the assembled battery for 5-12 h, wherein the purity of Ar is>99.99%, water content<0.1ppm, oxygen content<0.1ppm, light intensity of 0W/m2-0.2W/m2So that the electrolyte is sufficiently impregnated with the active material.
The invention has the following beneficial effects:
the invention adopts a hydrothermal method to prepare Cu2The S nano particles can be assembled into flower shapes by the nano sheets under the conditions of high temperature and high pressure, so that the battery has good stability. Based on Cu2S energy storage material, which is directly attached to a photo-anode with a photoelectric conversion function to form dual-functional compatible electricityThe two functions of photoelectric conversion and energy storage are realized in a single electrode. After the structure is assembled into a complete two-electrode device structure, lithium ions can be effectively embedded into Cu under the auxiliary condition of illumination2In S, the energy storage of the battery is improved, so that the charge and discharge performance of the secondary battery is improved. In summary, the electrode structure in which the counter electrode with the energy storage function is directly attached to the photo-anode to form a short circuit is an effective way to develop the integrated device of photoelectric conversion and energy storage.
Drawings
Fig. 1 is an SEM image of the surface of the composite electrode.
FIG. 2 is an SEM image of a cross section of a composite electrode.
Fig. 3 is a structural diagram of a two-electrode photo-assisted rechargeable battery.
FIG. 4 is a photo-responsive test chart of an open circuit.
Fig. 5 is a light-dark alternating constant current charge-discharge curve.
FIG. 6 is a cyclic voltammogram.
FIG. 7 is a constant current charge and discharge curve under dark conditions.
Detailed Description
The technical scheme of the invention is described in detail in the following with reference to the attached drawings and embodiments:
the difficulty with integrated devices is finding a compatible electrode that combines both functions to integrate a solar cell with a rechargeable cell. Cu2S is widely used as a counter electrode of a quantum dot sensitized solar cell due to its extremely high catalytic activity, while it is also used as a negative electrode material in a lithium ion battery due to its good conductivity and high theoretical capacity. Thus, Cu2S may act as a dual function electrode.
Since the open circuit voltage of a general solar cell cannot satisfy the charging voltage of a rechargeable battery, sunlight is used as auxiliary energy to construct a light-assisted rechargeable battery, and it is an effective way to improve the performance of the light-assisted rechargeable battery in the charging and discharging processes.
Integrating four or three electrodes into two electrodes requires each electrode to assume more functions, but since there is no influence of different charging and discharging paths, the complicated circuit structure is simplified, and the energy loss is reduced to the maximum extent.
Example 1:
a light-assisted rechargeable battery based on a dual-function compatible electrode is composed of the following parts: from Cu2S is directly attached to the surface of a dye-sensitized titanium dioxide photo-anode, and is a difunctional compatible electrode taking FTO conductive glass as a carrier; shearing into Cu2S is a positive electrode composed of metal lithium with the same shape as the active material; dripping LiTFSI/DOL-DME organic electrolyte on two sides of the diaphragm; a diaphragm composed of a polypropylene microporous membrane; and a positive current collector composed of copper foil. The positive pole of the metal lithium is pasted on the positive pole current collector, and the dual-function compatible electrode and the positive pole of the metal lithium are soaked by electrolyte, separated by a diaphragm and then compressed.
Cu2S is synthesized by a hydrothermal method, and the specific synthesis method is as follows:
(1) weighing 0.01mol/L-0.1mol/L CuCl and CH4N20.05mol/L-0.15mol/L S and 0.005g/mL-0.01g/mL PVP are mixed in ethanol and glycol solution with equal volume, and the stirring time is 5min-15 min.
(2) Pouring the mixed solution into a high-pressure reaction kettle for high-temperature and high-pressure treatment, wherein the heating temperature is 120-180 ℃, the pressurizing pressure is 0-70 Mpa, and the reaction time is 6-18 h.
(3) Carrying out ultrasonic centrifugal cleaning on the solution, wherein the centrifugal rotating speed is 1000rad/min-8000rad/min, cleaning the ethanol and the water in sequence until the ethanol and the water are uniformly dispersed, the cleaning frequency is 3-5 times, then drying the solution at the temperature of 60-80 ℃, and storing the solution in an environment with the water content of less than 0.1ppm and the oxygen content of less than 0.1 ppm.
The preparation method of the N719 dye sensitized titanium dioxide photo-anode comprises the following steps:
(1) uniformly dispersing the N719 dye in an ethanol solution, wherein the concentration is 3.6mmol L-1And at an illumination intensity of 0W/m2-0.2W/m2Is stored in the environment of (1).
(2) The conductive glass is cleaned for 20min to 40min by an ultrasonic cleaning method in the sequence of deionized water, ethanol, acetone, ethanol and deionized water, and then the conductive glass is dried at the drying temperature of 60 ℃ to 80 ℃.
(3) The TiO is mixed by a spin coater2The slurry is spin-coated on conductive glass at a rotation speed of 3000rad/min-7000rad/min for 1-3 times to obtain TiO with a thickness of 5-20 μm2And drying the electrode after each spin coating at the drying temperature of 60-80 ℃, then sintering the electrode in an air atmosphere at the temperature of 450-500 ℃ for 30 minutes, and cooling the electrode to room temperature.
(4) In dark environment, TiO is added2The photoanode is soaked in 3.6mmol L-1The N719 dye is evenly dispersed in the ethanol solution, soaked for 12-24 h, then cleaned by ethanol and dried by blowing, and then stored in a dark environment.
The preparation method of the bifunctional compatible electrode comprises the following steps:
(1) mixing Cu by mass ratio280-90% of S, 10-15% of PVDF and 0-5% of conductive acetylene black are added dropwise with N-methyl pyrrolidone and ground for 30min to form uniformly dispersed slurry.
(2) Mixing Cu2S slurry is placed in a place with the illumination intensity of 0W/m2-0.2W/m2In the environment of (1), the dye-sensitized TiO is coated by a blade coating mode of 45-90 DEG2Coating the surface of the photo-anode with a thickness of 8-20 μm to obtain Cu2And the slurry is completely and uniformly covered.
(3) Drying the electrode in dark vacuum environment at-0.08-0.1 MPa and illumination intensity of 0W/m2-0.2W/m2The temperature is 60-80 ℃, and the time is 6-12 h.
(4) Through SEM tests, the surface and cross-sectional views of the composite electrode can be seen, as in fig. 1 and 2.
The method for assembling the light-assisted rechargeable battery comprises the following steps:
(1) extending copper wires out of the surface of the carrier (conductive glass) of the dual-function compatible electrode, fixing the copper wires by using adhesive tapes, and doping SnO with fluorine2The transparent film is a current collector, and the battery is assembled in an environment filled with high-purity Ar, wherein the purity of the Ar is>99.99%, water content<0.1ppm, oxygen content<0.1ppm。
(2) Shearing metallic lithium into Cu2S thin film is the sameAnd then the copper foil (current collector) was bonded thereto and fixed with an adhesive tape.
(3) Firstly, dripping LiTFSI/DOL-DME electrolyte in Cu2Adhering a polypropylene microporous membrane on the surface of S, dripping LiTFSI/DOL-DME electrolyte on the surface of the metal lithium, wherein the volume of the dripped electrolyte is 5-15 muL, and then jointing and compacting the two electrodes at the pressure of 0kg/cm2-50kg/cm2。
(4) Standing the assembled battery for 5-12 h, wherein the purity of Ar is>99.99%, water content<0.1ppm, oxygen content<0.1ppm, light intensity of 0W/m2-0.2W/m2So that the electrolyte is sufficiently impregnated with the active material. The complete device structure is shown in fig. 3.
(5) The device was placed in an environment of alternating light and dark, with a light source intensity of 150W, and tested for changes in open circuit voltage, with the time of light and dark being 50s, respectively. The resulting open circuit voltage photoresponse test is shown in fig. 4. The device was placed in an environment of alternating light and dark to obtain a constant current charge-discharge curve, as shown in fig. 5.
Example 2:
material preparation and device assembly were the same as in example 1.
The test method comprises the following steps: the device was subjected to cyclic voltammetry testing at a rate of 0.5mV/s under dark conditions with a start-stop voltage of 1.5-3.4V, as shown in FIG. 6. The charging and discharging tests were carried out at a current of 50mA/g, with a charging and discharging voltage range of 1.5V to 3.4V, as shown in FIG. 7.
Claims (5)
1. A light-assisted rechargeable battery based on a bifunctional compatible electrode is characterized by comprising the bifunctional compatible electrode, a diaphragm, a metal lithium anode and an anode current collector, wherein the metal lithium anode is pasted on the anode current collector, and the bifunctional compatible electrode and the metal lithium anode are soaked by electrolyte and are compressed after being separated by the diaphragm; the dual-function compatible electrode takes conductive glass as a carrier and is made of Cu2S is directly attached to the surface of the dye-sensitized titanium dioxide photo-anode;
the Cu2S is synthesized by a hydrothermal method, and the specific synthesis method comprises the following steps:
(1) balanceTaking CuCl 0.01mol/L-0.1mol/L, CH4N2S0.05 mol/L-0.15mol/L and PVP 0.005g/mL-0.01g/mL, mixing in ethanol and glycol solution with equal volume, and stirring for 5min-15 min;
(2) pouring the mixed solution into a high-pressure reaction kettle for high-temperature and high-pressure treatment, wherein the heating temperature is 120-180 ℃, the pressurizing pressure is 0-70 Mpa, and the reaction time is 6-18 h;
(3) and (2) carrying out ultrasonic centrifugal cleaning on the mixed solution after high-temperature and high-pressure treatment, wherein the centrifugal rotating speed is 1000rad/min-8000rad/min, sequentially cleaning ethanol and water until the mixed solution is uniformly dispersed, and the cleaning frequency is 3-5 times, then drying at 60-80 ℃, and storing in an environment with the water content of less than 0.1ppm and the oxygen content of less than 0.1 ppm.
2. The photo-assisted rechargeable battery with bifunctional compatible electrode as claimed in claim 1, wherein the separator is polypropylene microporous membrane; the electrolyte is LiTFSI/DOL-DME electrolyte; the positive current collector is copper foil.
3. The photo-assisted rechargeable battery based on the bifunctional compatible electrode as claimed in claim 1, wherein the preparation method of the dye-sensitized titanium dioxide photo-anode comprises:
(1) uniformly dispersing the N719 dye in an ethanol solution, wherein the concentration is 3.6mmol L-1And at an illumination intensity of 0W/m2～0.2W/m2Is stored in the environment of (1);
(2) cleaning the conductive glass by an ultrasonic cleaning method in sequence of deionized water, ethanol, acetone, ethanol and deionized water, wherein each step is respectively cleaned for 20-40 min; then drying the conductive glass at the temperature of 60-80 ℃;
(3) the TiO is mixed by a spin coater2The slurry is spin-coated on the conductive glass at a rotating speed of 3000rad/min-7000rad/min for 1-3 times to obtain TiO with a thickness of 5-20 μm2An electrode; drying after each spin coating, wherein the drying temperature is 60-80 ℃, then sintering for 30 minutes in an air atmosphere at 450-500 ℃, and cooling to room temperature;
(4) in dark environment, TiO is added2The photoanode is soaked in 3.6mmol L-1The N719 dye is evenly dispersed in the ethanol solution, soaked for 12-24 h, cleaned by ethanol, dried by blowing and stored in a dark environment.
4. The photo-assisted rechargeable battery based on the dual-function compatible electrode as claimed in claim 1, wherein the method for preparing the dual-function compatible electrode comprises:
(1) mixing Cu by mass ratio2S80% -90%, PVDF 10% -15%, conductive acetylene black 0% -5%, dripping N-methyl pyrrolidone, and grinding for 30min to obtain uniformly dispersed slurry;
(2) mixing Cu2S slurry is placed in a place with the illumination intensity of 0W/m2～0.2W/m2In the environment of (1), the surface of a dye-sensitized titanium dioxide photo-anode is coated with a blade coating mode of 45-90 degrees, the blade coating thickness is 8-20 mu m, so that Cu is coated2S, completely and uniformly covering the slurry;
(3) drying the electrode in a dark vacuum environment at a pressure of-0.08 to-0.1 MPa and an illumination intensity of 0W/m2～0.2W/m2The temperature is 60-80 ℃ and the time is 6-12 h.
5. The photo-assisted rechargeable battery based on dual function compatible electrodes as claimed in claim 1, wherein the assembling method is as follows:
(1) extending copper wires out of the surface of the carrier of the dual-function compatible electrode, and fixing the copper wires by using adhesive tapes to prepare SnO doped with fluorine2The transparent film is a current collector, and the battery is assembled in an environment filled with high-purity Ar, wherein the purity of the Ar is>99.99%, water content<0.1ppm, oxygen content<0.1ppm；
(2) Shearing metallic lithium into Cu2The S film is in the same shape and is attached to the positive current collector and fixed by an adhesive tape;
(3) firstly, the electrolyte is dripped into Cu2S surface, pasting a diaphragm, dripping electrolyte on the surface of the metal lithium, wherein the volume of the dripped electrolyte is5-15 mu L, then attaching the dual-function compatible electrode and the lithium metal anode, compacting, and the pressure is 0kg/cm2～50kg/cm2；
(4) Standing the assembled battery for 5-12 h, wherein the purity of Ar is>99.99%, water content<0.1ppm, oxygen content<0.1ppm, light intensity of 0W/m2～0.2W/m2So that the electrolyte is sufficiently impregnated with the active material.
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