CN103066345A - Photoelectric chemical battery electrode and preparation method and application thereof - Google Patents
Photoelectric chemical battery electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN103066345A CN103066345A CN2011103243995A CN201110324399A CN103066345A CN 103066345 A CN103066345 A CN 103066345A CN 2011103243995 A CN2011103243995 A CN 2011103243995A CN 201110324399 A CN201110324399 A CN 201110324399A CN 103066345 A CN103066345 A CN 103066345A
- Authority
- CN
- China
- Prior art keywords
- photoelectrochemical cell
- preparation
- electrode
- cell electrode
- cuprous oxide
- 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
Images
Abstract
The invention discloses a photoelectric chemical battery electrode and a preparation method and application thereof. The photoelectric chemical battery electrode comprises a conductive substrate and a semiconductor thin film, and is characterized in that the semiconductor thin film is a nano-cuprous oxide thin film which contains metal copper micro particles. The electrode is prepared by directly growing the cuprous oxide thin film with the metal copper micro particles on the conductive substrate by an electrochemical deposition method. The conductive metal Cu micro particles are introduced into the Cu2O thin film, so that the conductivity of the electrode is improved; the transmission rate of electrons to the conductive substrate is increased; composition of current carriers is reduced; a short circuit current is increased; and the energy conversion efficiency of a battery is improved. Compared with the prior art, the photoelectric chemical battery electrode has the advantages that the performance of a photoelectric chemical battery assembled by the electrode is greatly improved, and the photoelectric conversion efficiency can be up to 3.13 percent at most.
Description
Technical field
The present invention relates to a kind of photoelectrochemical cell electrode and its preparation method and application, belong to new material technology and technical field of new energies.
Background technology
The day by day exhausted and environmental pollution of traditional energy impels people more and more to pay close attention to the development and utilization of new forms of energy.Solar energy has caused widely and has paid close attention to as a kind of regenerative resource of cleaning, has been considered to the best replacer of traditional energy.Existing solar cell mostly has complex manufacturing technology, the shortcomings such as cost costliness, and its extensive use is subject to certain restrictions.Therefore, it is inexpensive to seek advantages of nontoxic raw materials, and preparation technology is simple, low energy consumption, novel solar battery has important theory and realistic meaning cheaply.
Cuprous oxide (Cu
2O) be the p-type semiconductor that a kind of energy gap is about 2.0eV, nontoxic, preparation cost is low, visible light absorbing.Cu
2The O film is applied to solar energy photocatalytic as the light anode and solar cell all receives much concern, Cu
2O/TiO
2Composite material demonstrates than TiO
2Better photocatalysis performance (Journal ofPhysical Chemistry C., 2010,114,22181.), Cu
2The O/ZnOp-n junction battery is existing relevant report also.Wherein, Cu
2O is as absorbed layer, and photohole is from Cu
2O be transferred to electrode and be collected (AdvancedMaterials., 2010,22, E254.).Xiang, the method for the human high-temperature oxydation Copper Foils such as C.X. is prepared high-quality Cu
2O uses it for photoelectrochemical cell, has obtained 1.5% electricity conversion, and its open circuit voltage is up to 820mV, and stability test is better.But its short circuit current is lower, is 3.1mA/cm
2, and its complicated process of preparation, to the high (Energy﹠amp of equipment requirement condition; Environmental Science., 2011,4,1311.).At present, Cu
2The peak efficiency that the O based solar battery can reach is 2% (Applied PhysicsLetters., 2006,88,163502.), and is still lower, this mainly be since light induced electron and hole at Cu
2The O surface is very easily compound, has limited effective collection of photo-generated carrier.If solve the collection efficiency problem of charge carrier in this type of battery, the energy conversion efficiency of battery is improved a lot.
Summary of the invention
For the existing the problems referred to above of prior art and defective, the purpose of this invention is to provide a kind of photoelectrochemical cell electrode and its preparation method and application, for this area increases a kind of not only nontoxic inexpensive, preparation technology is simple, and can improve photoelectrochemical cell electrode and the photoelectrochemical cell of carrier collection efficient.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of photoelectrochemical cell electrode comprises conducting base and semiconductive thin film, it is characterized in that: described semiconductive thin film is nanometer cuprous oxide film, and contains the metallic copper particulate in the described nanometer cuprous oxide film.
Further, described nanometer cuprous oxide film is to be grown directly upon on the described conducting base.
Described conducting base can be electro-conductive glass, conductive plastics.
The thickness of described nanometer cuprous oxide film is recommended as 8～20 μ m, is preferably 10～15 μ m.
A kind of preparation method of described photoelectrochemical cell electrode comprises the steps:
The pH value of a) preparation electrolyte solution, and adjusting electrolyte solution is 4.0～5.7;
B) adopt electrochemical deposition method direct growth on conducting base to contain the cuprous oxide film of metallic copper particulate;
C) take out sample, washing, drying.
Described electrolyte solution is recommended as to be mixed with the water-soluble inorganic mantoquita by the water-soluble inorganic sodium salt and forms.
Further, described electrolyte solution is the mixed solution that is formed by sodium chloride and copper chloride or sodium nitrate and copper nitrate or sodium acetate and Schweinfurt green.
Further, in the described electrolyte solution, the mol ratio of water-soluble inorganic sodium salt and water-soluble inorganic mantoquita is 5: 1～10: 1.
Step b) electrochemical deposition process in is recommended as follows: take conducting base as work electrode, platinum filament was to electrode, and saturated calomel electrode is reference electrode, adopts permanent electromotive force pattern, 20～70 ℃ of reactions 20～60 minutes.
Further, described permanent electromotive force refers to that constant potential is-245mV.
Photoelectrochemical cell electrode of the present invention can be applicable to prepare photoelectrochemical cell.
The present invention passes through at Cu
2Introduce conducting metal Cu particulate in the O film, improved the conductance of electrode, accelerated the transfer rate of electronic service guide electricity matrix, reduced the compound of charge carrier, increased short circuit current, finally improved the energy conversion efficiency of battery.Compare with titanium dioxide electrodes with pure zirconia is cuprous, short circuit current and the open circuit voltage of using the photoelectrochemical cell of photoelectrochemical cell electrode assembling of the present invention significantly rise, and electricity conversion can reach 3.13%.
Therefore, compared with prior art, the present invention has following beneficial effect:
1, with cuprous oxide as electrode, visible light is had the good effect of utilizing.
2, metallic copper has improved the conductance of electrode, has accelerated the transfer rate of electronic service guide electricity matrix, has reduced the compound of charge carrier, has increased short circuit current, has finally improved the energy conversion efficiency of battery.
3, advantages of nontoxic raw materials, cheap and easy to get, preparation technology's weak point consuming time need not special installation, is easy to accomplish scale production.
4, the electricity conversion of the photoelectrochemical cell of preparation is higher, can be up to 3.13%.
Description of drawings
Fig. 1 is embodiment 1,2 and the battery structure schematic diagram that makes of Comparative Examples 1,2, and among the figure: 1 is conducting base, and 2 is semiconductive thin film, and 3 is electrolyte, and 4 is to electrode.
Fig. 2 is the XRD spectra of the electrode sample of embodiment 1 and Comparative Examples 1 preparation, and wherein curve a is the XRD spectra of the electrode sample of embodiment 1 preparation, and curve b is the XRD spectra of the electrode sample of Comparative Examples 1 preparation;
Fig. 3 is the SEM photo of the electrode sample of embodiment 1 preparation;
Fig. 4 is the current-voltage characteristic curve figure that the photoelectrochemical cell of embodiment 1 preparation is tested under simulated solar irradiation;
Fig. 5 is the SEM photo of the electrode sample of embodiment 2 preparations;
Fig. 6 is the current-voltage characteristic curve figure that the photoelectrochemical cell of embodiment 2 preparations is tested under simulated solar irradiation;
Fig. 7 is the SEM photo of the electrode sample of Comparative Examples 1 preparation;
Fig. 8 is the current-voltage characteristic curve figure that the photoelectrochemical cell of Comparative Examples 1 preparation is tested under simulated solar irradiation;
Fig. 9 is the current-voltage characteristic curve figure that the photoelectrochemical cell of Comparative Examples 2 preparations is tested under simulated solar irradiation.
Embodiment
Below in conjunction with embodiment to the present invention do further in detail, intactly explanation.
Embodiment 1
Clean the FTO electro-conductive glass, then in deionized water, ethanol and acetone, distinguish ultrasonic 30 minutes, dry for standby;
Prepare respectively SAS and Schweinfurt green solution, with the two mixing, stir, wherein the mol ratio of sodium acetate and Schweinfurt green is 5: 1; Adding the vinegar acid for adjusting pH value is about 5.4;
The employing mentioned solution is electrolyte, electrochemical deposition contains the cuprous oxide film of metallic copper particulate on the FTO electro-conductive glass: take the FTO electro-conductive glass as work electrode, platinum filament is to electrode, saturated calomel electrode is reference electrode, adopt permanent electromotive force pattern, keep electromotive force to be-245mV, at 60 ℃ of reaction 20min;
Take out electrode sample, use deionized water or absolute ethanol washing 3 times, all volatilization is complete then to be dried to moisture or ethanol in 60 ℃, namely gets photoelectrochemical cell electrode of the present invention, and film thickness wherein is about 10 μ m.
Inject I
-/ I
3 -Solution is electrolyte, adopt the sealed membrane of 120 micron thickness as the intermediate isolating layer, the electro-conductive glass sheet of platinum plating is as to electrode, and the photoelectrochemical cell electrode that makes take present embodiment is as work electrode, be assembled into photoelectrochemical cell, its structural representation as shown in Figure 1.
Curve a among Fig. 2 is the XRD spectra of the electrode sample that makes of present embodiment, and as seen from Figure 1: this photoelectric chemical electrode is by Cu, Cu
2O and FTO form, that is, prepared electrode is comprised of conducting base FTO glass and the cuprous oxide film that contains the metallic copper particulate that is grown in its surface.
Fig. 3 is the SEM photo of the electrode sample that makes of present embodiment, and as seen from Figure 3: film surface is with particulate.
Fig. 4 is that the photoelectrochemical cell of present embodiment assembling is 100mV/cm in intensity
2The AM1.5G simulated solar irradiation under the current-voltage characteristic curve figure that tests, when test, determine that with the pertusate shadow shield in center the effective area of battery is 0.12cm
2, as seen from Figure 4: the short circuit current of the photoelectrochemical cell of present embodiment assembling reaches 11.30mA/cm
2, open circuit voltage is 0.56V, electricity conversion is 3.13%.
The difference of present embodiment and embodiment 1 only is: the time of electro-deposition replaces with 60min by 20min, and all the other contents are with identical described in the embodiment 1.
The film thickness of the prepared photoelectrochemical cell electrode of present embodiment is about 15 μ m.
Fig. 5 is the SEM photo of the electrode sample that makes of present embodiment, as seen from Figure 5: and the increase of sedimentation time, the thickness of film is increased, and the metal particle that film surface adheres to also increases.
Fig. 6 is that the photoelectrochemical cell of present embodiment assembling is 100mV/cm in intensity
2The AM1.5G simulated solar irradiation under the current-voltage characteristic curve figure that tests, when test, determine that with the pertusate shadow shield in center the effective area of battery is 0.12cm
2, as seen from Figure 6: the short circuit current of the photoelectrochemical cell of present embodiment assembling reaches 10.77mA/cm
2, open circuit voltage is 0.56V, electricity conversion is 2.61%.In addition, present embodiment also illustrates: the increase of electrochemical deposition time, can cause the reduction of cell photoelectric stream and electricity conversion, and this is because too much copper can affect electrode pair Optical Absorption ability.
Comparative Examples 1
The cuprous based photoelectrochemicalcell cell of preparation pure zirconia: the preparation method is with embodiment 1, and difference only is: with acetic acid the pH value of electrolyte solution is transferred to 5.7～6.5.
Curve b among Fig. 2 is the XRD spectra of the prepared electrode sample of this Comparative Examples, and as seen from Figure 2: the prepared electrode of this Comparative Examples is by Cu
2O and FTO form, and do not contain metallic copper.
Fig. 7 is the SEM photo of the prepared electrode sample of this Comparative Examples, and as seen from Figure 7: film surface does not have particulate to adhere to.
Fig. 8 is the current-voltage characteristic curve figure that the photoelectrochemical cell of this Comparative Examples assembling is tested under simulated solar irradiation, and as seen from Figure 8: the short circuit current of the photoelectrochemical cell of this Comparative Examples assembling only is 0.50mA/cm
2, open circuit voltage only has 0.10V, and its photoelectric conversion efficiency also only has 0.013%.
Comparative Examples 2
Preparation pure titinium dioxide based photoelectrochemicalcell cell: clean the FTO electro-conductive glass, then in deionized water, ethanol and acetone, distinguish ultrasonic 30 minutes, dry for standby; The P25 powder is dispersed in the ethanol, adds an amount of terpinol and ethyl cellulose, electromagnetic agitation 12h; The rotary sample that obtains is evaporated ethanol, make the P25 slurry; With knife coating P25 slurry blade coating is calcined 30min on the FTO electro-conductive glass and at 450 ℃; The sample that obtains is put into titanium tetrachloride solution, in 60 ℃ of baking ovens, take out drying behind the placement 1h, then at 450 ℃ of calcining 30min.
Be assembled into battery with reference to the method among the embodiment 1.
Fig. 9 is the current-voltage characteristic curve figure that the photoelectrochemical cell of this Comparative Examples assembling is tested under simulated solar irradiation, and as seen from Figure 9: the short circuit current of the photoelectrochemical cell of this Comparative Examples assembling only is 0.10mA/cm
2, its photoelectric conversion efficiency also only has 0.019%.
In sum as seen: the present invention passes through at Cu
2Introduce conducting metal Cu particulate in the O film, improved the conductance of electrode, accelerated the transfer rate of electronic service guide electricity matrix, reduced the compound of charge carrier, increased short circuit current, finally improved the energy conversion efficiency of battery; But the meeting of electrochemical deposition overlong time affects sample to Optical Absorption so that Cu content is too much, reduces on the contrary the electricity conversion of battery; Battery with the cuprous base of pure zirconia and titania-based electrode assembling is compared, and the performance of using the photoelectrochemical cell of photoelectrochemical cell electrode assembling of the present invention improves greatly, and electricity conversion reaches as high as 3.13%.
Be necessary to be pointed out that at this: above embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (11)
1. a photoelectrochemical cell electrode comprises conducting base and semiconductive thin film, it is characterized in that: described semiconductive thin film is nanometer cuprous oxide film, and contains the metallic copper particulate in the described nanometer cuprous oxide film.
2. photoelectrochemical cell electrode according to claim 1, it is characterized in that: described nanometer cuprous oxide film is to be grown directly upon on the described conducting base.
3. photoelectrochemical cell electrode according to claim 1, it is characterized in that: described conducting base is electro-conductive glass, conductive plastics.
4. photoelectrochemical cell electrode according to claim 1, it is characterized in that: the thickness of described nanometer cuprous oxide film is 8～20 μ m.
5. the preparation method of a photoelectrochemical cell electrode claimed in claim 1 is characterized in that, comprises the steps:
The pH value of a) preparation electrolyte solution, and adjusting electrolyte solution is 4.0～5.7;
B) adopt electrochemical deposition method direct growth on conducting base to contain the cuprous oxide film of metallic copper particulate;
C) take out sample, washing, drying.
6. the preparation method of photoelectrochemical cell electrode according to claim 5, it is characterized in that: described electrolyte solution is to be mixed with the water-soluble inorganic mantoquita by the water-soluble inorganic sodium salt to form.
7. the preparation method of photoelectrochemical cell electrode according to claim 6 is characterized in that: described electrolyte solution is the mixed solution that is formed by sodium chloride and copper chloride or sodium nitrate and copper nitrate or sodium acetate and Schweinfurt green.
8. the preparation method of photoelectrochemical cell electrode according to claim 6, it is characterized in that: in the described electrolyte solution, the mol ratio of water-soluble inorganic sodium salt and water-soluble inorganic mantoquita is 5: 1～10: 1.
9. the preparation method of photoelectrochemical cell electrode according to claim 5, it is characterized in that: the electrochemical deposition process step b) is as follows: take conducting base as work electrode, platinum filament is to electrode, saturated calomel electrode is reference electrode, adopt permanent electromotive force pattern, 20～70 ℃ of reactions 20～60 minutes.
10. the preparation method of photoelectrochemical cell electrode according to claim 9, it is characterized in that: described permanent electromotive force refers to that constant potential is-245mV.
11. an application rights requires the photoelectrochemical cell of each described photoelectrochemical cell electrode preparation in 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103243995A CN103066345A (en) | 2011-10-21 | 2011-10-21 | Photoelectric chemical battery electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103243995A CN103066345A (en) | 2011-10-21 | 2011-10-21 | Photoelectric chemical battery electrode and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103066345A true CN103066345A (en) | 2013-04-24 |
Family
ID=48108870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103243995A Pending CN103066345A (en) | 2011-10-21 | 2011-10-21 | Photoelectric chemical battery electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103066345A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244408A (en) * | 2014-06-13 | 2016-01-13 | 山东建筑大学 | Method for preparing cuprous oxide photoelectric film by copper chloride |
| CN107204284A (en) * | 2017-05-09 | 2017-09-26 | 西北大学 | The method that cuprous oxide semiconductor conductivity types are controlled based on deposition potential |
| CN107576704A (en) * | 2017-07-26 | 2018-01-12 | 上海师范大学 | Microcysin LR molecular engram optical electro-chemistry sensor and its preparation and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101620935A (en) * | 2009-07-21 | 2010-01-06 | 华中师范大学 | TiO2-based composite film material with functions of solar energy storage and release |
| JP2010177109A (en) * | 2009-01-30 | 2010-08-12 | Toyota Central R&D Labs Inc | Composition for forming underlayer, method of manufacturing underlayer, method of manufacturing photoelectrode, method of manufacturing solar cell, and solar cell module |
-
2011
- 2011-10-21 CN CN2011103243995A patent/CN103066345A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010177109A (en) * | 2009-01-30 | 2010-08-12 | Toyota Central R&D Labs Inc | Composition for forming underlayer, method of manufacturing underlayer, method of manufacturing photoelectrode, method of manufacturing solar cell, and solar cell module |
| CN101620935A (en) * | 2009-07-21 | 2010-01-06 | 华中师范大学 | TiO2-based composite film material with functions of solar energy storage and release |
Non-Patent Citations (2)
| Title |
|---|
| R.P. WIJESUNDERA等: "Growth and characterisation of potentiostatically electrodeposited Cu2O and Cu thin films", 《THIN SOLID FILMS》 * |
| YIWEN TANG等: "Electrodeposition and characterization of nanocrystalline cuprous oxide thin films on TiO films", 《MATERIALS LETTERS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244408A (en) * | 2014-06-13 | 2016-01-13 | 山东建筑大学 | Method for preparing cuprous oxide photoelectric film by copper chloride |
| CN105244408B (en) * | 2014-06-13 | 2017-05-03 | 山东建筑大学 | Method for preparing cuprous oxide photoelectric film by copper chloride |
| CN107204284A (en) * | 2017-05-09 | 2017-09-26 | 西北大学 | The method that cuprous oxide semiconductor conductivity types are controlled based on deposition potential |
| CN107576704A (en) * | 2017-07-26 | 2018-01-12 | 上海师范大学 | Microcysin LR molecular engram optical electro-chemistry sensor and its preparation and application |
| CN107576704B (en) * | 2017-07-26 | 2020-03-17 | 上海师范大学 | microcystin-LR molecular imprinting photoelectric chemical sensor and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104157788B (en) | It is a kind of to be based on SnO2Perovskite thin film photovoltaic cell and preparation method thereof | |
| CN102347143B (en) | A kind of graphene composite porous counter electrode, preparation method and applications | |
| CN101901693A (en) | Graphene composite dye-sensitized solar cell light anode and preparation method thereof | |
| CN105869893B (en) | One step hydrothermal synthesis graphene-SnS2The method of combined counter electrode material | |
| Wei et al. | Investigation on interfacial charge transfer process in CdSexTe1-x alloyed quantum dot sensitized solar cells | |
| CN103560013B (en) | A kind of sulfide is to DSSC of electrode and preparation method thereof | |
| CN103560014B (en) | Dye-sensitized cell is with to electrode, its preparation method and dye-sensitized cell | |
| CN105047826A (en) | Perovskite solar cell with cadmium sulfide-doped perovskite layer and preparation method of perovskite solar cell | |
| CN108579765A (en) | The preparation of copper sulfide/pucherite bilayer film composite material and the application as photo cathode | |
| CN106128772B (en) | A kind of preparation method of vulcanized lead quantum dot photovoltaic battery | |
| CN101567268B (en) | Method for preparing ternary two-layer titanium dioxide film | |
| CN102220615A (en) | Method for preparing CdS/ZnO nanotube array photoelectrode | |
| CN103400878A (en) | Zinc oxide nanopencil array electrode and preparation method and application thereof | |
| CN103117173A (en) | Double-side light entering quantum dot sensitization solar cell and preparation method thereof | |
| CN104377036A (en) | Method for preparing AgInS2 quantum dot sensitized TiO2 photoelectrode with In2S3 used as buffer layer | |
| CN103594249B (en) | A kind of graphene oxide-nano-graphite flour complexes is to the preparations and applicatio of electrode | |
| CN108172401A (en) | Dye-sensitized cell combined counter electrode and its preparation method and application | |
| CN103887071A (en) | Flexible nano paper-base compound photo-anode for dye-sensitized solar cell and preparation method thereof | |
| CN102280256B (en) | Dye-sensitized solar cell quasi solid electrolyte and method for preparing solar cell by using same | |
| CN103066345A (en) | Photoelectric chemical battery electrode and preparation method and application thereof | |
| CN101872685B (en) | Solid dye-sensitized nanocrystal/microcrystal silicon composite film solar cell and preparation method thereof | |
| CN108376613A (en) | It is a kind of to be used for zno-based composite material and preparation method of the dye-sensitized solar cells to electrode | |
| CN107342364A (en) | A kind of UV photodetector of zinc oxide polyaniline sandwich structure and preparation method thereof | |
| CN108922654B (en) | Low-temperature screen-printable carbon paste and high-conductivity carbon electrode | |
| CN110085428A (en) | A kind of compound light anode of titanium dioxide/graphene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130424 |