WO2012013135A1

WO2012013135A1 - Dye sensitized solar cell

Info

Publication number: WO2012013135A1
Application number: PCT/CN2011/077555
Authority: WO
Inventors: 邹德春; 傅永平; 吕志彬; 简蓉
Original assignee: 北京大学
Priority date: 2010-07-30
Filing date: 2011-07-25
Publication date: 2012-02-02
Also published as: CN102347147A

Abstract

Disclosed is a dye sensitized solar cell comprising a working electrode, a counter electrode (3), an electrolyte (4), and a transparent sleeve (5). The working electrode comprises a filamentous conductor base (1) and a sensitized semi-conductor thin film (2) covering the base (1). The counter electrode (3) and the working electrode form a winding structure, constituting a cell body; the cell body is arranged within the transparent sleeve. The electrolyte (4) is disposed between the transparent sleeve (5) and the cell body. The filamentous conductor base (1) and the counter electrode (3) respectively are drawn out from one end of the transparent sleeve (5). The cell has a symmetrical and stable structure, and a short path of transmission for the charge generated within the cell. This increases the charge-collection capacity of the counter electrode (3), thereby increasing efficiency, and also greatly increases the working stability of the cell and the insensitivity thereof towards the angle of incident light rays. Meanwhile, the sleeve structure facilitates the replenishment of the electrolyte, thus extending the service life of the cell. In addition, a plurality of this type of independent, single-piece cell units can be easily assembled to form a large-surface solar cell pack.

Description

Dye sensitized solar cell

The invention belongs to the technical field of dye-sensitized solar cells, and particularly relates to a tubular dye-sensitized solar cell suitable for a liquid electrolyte system. Background technique

The dye-sensitized solar cell is mainly composed of a working electrode, an electrolyte layer and a counter electrode, wherein the electrolyte layer may be a solid or a liquid. The working electrode includes a conductive substrate, a semiconductor porous film, and a sensitizing dye. Due to the limitations of materials and processing techniques of conventional solar cells, the conductive substrate of the working electrode is usually a flat plate structure, and the working electrode, the electrolyte, and the counter electrode form a flat sandwich structure. The biggest problems with this type of structure are the problem of electrolyte filling and battery packaging, and the resulting battery instability caused by electrolyte leakage. In addition, due to the limitation of the structure and process of the flat-plate battery, the proportion of the transparent conductive substrate in the manufacturing cost of the conventional flat-type photovoltaic cell is still quite high, resulting in a high cost per unit of power generation, and it is difficult to reach the civilian level. The cost level of the commodity limits the large-scale application of dye-sensitized solar cells.

In order to facilitate the filling of electrolytes and to facilitate battery packaging, some dye-sensitized solar cell structures are designed to be tubular. However, one of the existing sleeve-like structures requires a transparent counter electrode to be plated on the inner wall of the tube, but this also brings about new problems such as complicated manufacturing process and high cost. The other is based on the thinking of the traditional flat battery. The electrode wire is kept parallel to the working electrode in the tube and kept at a certain distance. It is considered that this can ensure that the battery is not short-circuited, but the structure can not efficiently transfer the generated electric charge to the counter electrode. , or because the distance between the counter electrode and the working electrode is unstable, the output of the battery is unstable, and also because the battery structure is asymmetrical, the battery performance is easily affected by the illumination angle.

Meanwhile, in terms of a solid-state battery, the inventors of the present invention have invented a solar cell having a conductive filament-like substrate, a sensitized semiconductor film, a charge transport layer, and a counter electrode as basic structural units, wherein the sensitized semiconductor The film layer is coated on the outer surface of the conductive filament substrate, the charge transport layer covers the surface of the sensitized semiconductor film layer to form a working electrode, and the counter electrode is wound around the surface of the charge transport layer to form a battery unit (Patent No.: ZL 200610114454.7). In this structure, a layer of charge transport layer is interposed between the sensitized semiconductor thin film layer and the counter electrode. Moreover, in such a structure, it is difficult to use a liquid electrolyte excellent in charge transport performance. Because liquid electrolytes are easy to flow, evaporate and are oxidized or contaminated by air, affecting the efficiency and stability of the battery. Summary of the invention

In view of the problems and deficiencies of the above-mentioned solar cells of the prior art, the object of the present invention is to provide a non-flat type, without a transparent conductive substrate, which is easy to fill and replace the electrolyte, and is easy to package, especially the structural height. Symmetrical, stable, efficient, inexpensive, dye-sensitized solar cells especially suitable for liquid electrolyte systems.

The above object of the present invention is achieved by the following technical solutions:

A dye-sensitized solar cell comprising a working electrode, a counter electrode, an electrolyte and a transparent sleeve, the working electrode further comprising a conductive filament substrate and a sensitized semiconductor film coated on the outside of the conductive filament substrate; a counter electrode and a working electrode Forming a winding structure to form a battery body; the battery body is placed in the transparent sleeve, the electrolyte is filled between the transparent sleeve and the battery body; and the conductive filament substrate and the counter electrode are respectively led out from the ends of the transparent sleeve.

The conductive filament-like substrate may be a solid structure or a hollow structure, and the shape of the cut surface may be circular or other shapes such as a rectangle, an ellipse or the like. The conductive filament-shaped substrate may be a wire or a non-metallic conductive wire, such as carbon fiber, a conductive polymer fiber, an inorganic conductive compound fiber, and an organic/inorganic conductive composite fiber; or may be made of a conductive material or a non-conductive material. The outer layer of the filament core is wrapped with a conductive material; the core and the layer of skin are also included, and the core and the inner layer are made of a conductive material or a non-conductive material, and the skin is wrapped on the outer side of the core layer by layer, and the outermost layer is The skin is a conductive material. The conductive material is an organic conductive material or an inorganic conductive material or an organic/inorganic composite conductive material.

The sensitized semiconductor film is a porous semiconductor film to which sensitized dye molecules are adsorbed, and the sensitized semiconductor film is coated on the outer surface of the conductive filament substrate to constitute a working electrode. The thickness of the sensitized semiconductor film is from 1 μm to 100 μm.

Depending on the design of the battery, a layer of dense semiconductor or insulator material may be applied over the conductive filament substrate to a thickness of 0.1-0.5 microns and then coated with the sensitized semiconductor film.

The counter electrode described above may also be a solid structure or a hollow structure. Like the conductive filament-like substrate, the counter electrode may be a wire or a non-metallic conductive wire, such as a composite conductive wire mainly composed of carbon fiber or carbon fiber. The counter electrode may be a sheath of a conductive material wrapped in an outer layer of a filamentary core made of a conductive material or a non-conductive material; a core and a plurality of layers of skin may be included, and the sheath of the core and the inner layer is a conductive material or non-conductive The material is wrapped on the outer side of the core layer by layer, and the outermost layer is made of a conductive material. The conductive material is an organic conductive material or an inorganic conductive material or an organic/inorganic composite conductive material.

The working electrode and the counter electrode surface may be coated with a catalytic layer having a thickness of between 1 nm and 100 nm. The catalytic layer may be continuous or discontinuous. The typical material of the catalytic layer is metal platinum.

According to the design requirements of the battery, an additional layer of isolation layer and spacer layer may be added outside the catalytic layer of the counter electrode. The material may be a semiconductor or an insulator, and the thickness of the isolation layer is between 1 nm and 100 nm to ensure that electrons can pass through the isolation layer. The barrier layer may be a dense layer or a thin layer of a porous structure. The outer surface of the counter electrode may be a dense flat surface or a porous or uneven surface.

The manner in which the counter electrode and the working electrode form a winding structure may be that the counter electrode is wound around the working electrode, or the working electrode is wound around the counter electrode, or the working electrode and the counter electrode are intertwined with each other; and the counter electrode may be a single electrode or a single or multiple The working electrode is wound in combination, and a working electrode may be wound with a single or a plurality of counter electrodes. Preferably, the gap between the working electrode and the counter electrode is less than 1 mm.

The distance between the battery body and the inner wall of the transparent sleeve is preferably from 0.01 to 5 mm.

The electrolyte may be a liquid electrolyte or a semi-solid electrolyte, wherein the semi-solid electrolyte comprises a solid inorganic or organic semiconductor, an ionic liquid, an inorganic or organic gel electrolyte or a solid inorganic fast ion conductor which is re-solidified after pouring.

The dye-sensitized solar cell of the present invention may constitute a solar cell including a plurality of dye-sensitized solar cells, a liquid inlet side tube, a liquid outlet side tube, a positive electrode and a negative electrode, wherein the plurality of dye-sensitized solar cells Arranged in parallel according to a certain density, one end of the transparent sleeve of each dye-sensitized solar cell unit is in communication with the inlet side tube, and the other end is in communication with the outlet side tube; the positive and negative electrodes are from the inlet side tube or the outlet side tube Leading out, or separately from the inlet side tube and the outlet side tube, wherein the positive electrode is connected to the conductive filament substrate of all the battery cells, and the negative electrode is connected to the opposite electrode of all the battery cells; the inlet side tube and the outlet The liquid side tubes are filled with electrolyte and integrated with the electrolyte in the transparent sleeve of each dye-sensitized solar cell unit.

Preferably, the above battery pack has an opening on the inlet side tube and the outlet side tube for use in electrolyte perfusion and cleaning, respectively.

Technical Applicability of the Invention: The dye-sensitized solar cell of the present invention is a sleeve structure as a whole, and the counter electrode and the working electrode are combined by winding to form a symmetrical and stable battery structure, and a charge transmission path occurring inside the battery is short, not only Improve the ability of the electrode to collect electric charge, thereby improving the efficiency of the device, and can greatly improve the working stability of the battery and the insensitivity to the angle of incident light. At the same time, the casing structure is beneficial to the replenishment of the electrolyte, and the battery is extended. Service life. In addition, this stand-alone, single-cell battery unit is easily integrated into a large-area solar module. In summary, the dye-sensitized solar cell of the present invention has the advantages of structural symmetry, stable battery operation, high efficiency, low cost, and the like, and is an inexpensive and highly efficient solar cell solution. DRAWINGS

The invention will now be described in detail in conjunction with the drawings. 1 is a schematic structural view showing an axial section of a dye-sensitized solar cell of the present invention;

2 is a schematic structural view showing a transverse section of a dye-sensitized solar cell of the present invention;

3 is a schematic structural view of a dye-sensitized solar cell body of the present invention;

Figure 4 is a schematic structural view showing an axial section of a working electrode of the present invention;

Figure 5 is a schematic structural view showing a radial section of a working electrode of the present invention;

6 is a schematic structural view showing an axial section of another working electrode of the present invention;

7 is a schematic structural view of a dye-sensitized solar cell of the present invention;

Figure 8 is a I-V graph of a class A battery in the embodiment;

Figure 9 is a I-V graph of a B-type battery in the embodiment;

Figure 10a is a I-V graph of the test immediately after the preparation of the Class C battery in the embodiment;

Figure 10b is a I-V graph of the test 10 minutes after the preparation of the Class C battery in the embodiment;

Figure 11a is a graph showing changes in short-circuit current of a battery output with time in a case where a type A battery prepared in the embodiment is subjected to light reception on one side and both sides;

Figure lib is a graph showing the change of the short-circuit current of the battery output with time in the case where the B-type battery prepared in the embodiment receives light on one side and both sides;

Figure 12 is a graph showing the relationship between the performance of a class A battery and the angle of incident light in the embodiment;

Figure 13 is a graph showing the relationship between the performance of a B-type battery and the incident light angle in the embodiment;

Figure 14 is a graph showing the relationship between the performance of a class C battery and the angle of incident light in the embodiment;

Figure 1 - Figure 7: 1 conductive filament substrate, 2_sensitized semiconductor film, 3_counter electrode, 4_electrolyte, 5-outer casing, 6-outlet side tube, 7-inlet side tube, 8 - positive electrode, 9_ negative electrode. detailed description

A specific embodiment of the present invention will now be described.

(I) Structure and preparation method of a dye-sensitized solar cell of the present invention

As shown in Figs. 1 and 2, the dye-sensitized solar cell comprises a conductive filament substrate 1, a sensitized semiconductor film (i.e., a functional layer) 2, a counter electrode 3, an electrolyte 4, and an outer sleeve 5. The sensitized semiconductor film 2 is a porous film structure in which sensitized dye molecules are adsorbed, and the sensitized semiconductor film 2 is attached to the outer surface of the conductive filament substrate 1. The counter electrode 3 is wound around the outer surface of the sensitized semiconductor film 2. The conductive filament substrate 1, the functional layer 2 and the counter electrode 3 together constitute a battery body. After the battery body is inserted into the outer sleeve 5, the electrolyte 4 is refilled in the outer sleeve 5 to form a complete dye-sensitized solar cell unit. The sensitized semiconductor film in the working electrode of the dye-sensitized solar cell is prepared by: coating and sintering the semiconductor material on the conductive filament substrate a plurality of times, or performing anodization using a corresponding metal (such as Ti), or Electrochemical deposition or growth produces a porous semiconductor layer, and a conductive filament-like substrate with a sintered or anodized semiconductor material is sensitized in a dye.

The semiconductor material is any semiconductor material suitable for the working electrode of the dye-sensitized solar cell, and the most representative one is nano-scale Ti0 ₂ , ZnO, and the like. The size and distribution of the nanoparticles are the same as those for the conventional dye-sensitized solar cells. The coating method can also be extended by conventional methods such as spraying, printing, soaking, pulling, and doctoring. The wire for preparing the semiconductor layer by anodization may be a pure titanium wire, or a composite fiber in which the core is another conductive material and the outer layer is titanium. Semiconductor nanostructures can also be deposited or grown on a conductive filament substrate by electrochemical methods.

All dyes suitable for conventional dye-sensitized solar cells are also suitable for sensitization of the semiconductor material of the working electrode, and the same sensitization method can be used.

The thickness of the sensitized semiconductor film 2 attached to the conductive filament-like substrate 1 is 1 to 100 μm.

While ensuring sufficient mechanical strength and electrical conductivity, in order to ensure good flexibility, the diameter of the conductive filament-like substrate 1 does not exceed lmm in principle, and its apparent resistivity is <100 ohm cm.

The conductive filament-like substrate 1 may be a wire, such as a filament structure made of stainless steel wire, alloy wire, or the like, or a non-metallic conductive wire such as carbon fiber, conductive polymer fiber, inorganic conductive compound fiber, and organic/inorganic conductive composite. Fiber, etc. The conductive material skin may also be wrapped on the outer layer of the filamentary core made of a conductive material or a non-conductive material, or the conductive filament substrate 1 may be made of a conductive material wrapped around a gaseous medium or a vacuum medium.

The cross-sectional shape of the conductive filament-like substrate 1 may be circular or any other shape such as a rectangular shape (as shown in Fig. 6) and an elliptical shape.

Referring to Figures 1 and 2, a conductive filament substrate 1 having a titanium wire having a diameter of about 250 μm as a working electrode was used; and a Pt wire having a diameter of about 40 μm was used as the counter electrode 3, and the prepared battery had an effective length of 10 cm ² .

In order to improve the conductivity, activity and stability of the working electrode, and the charge transfer characteristics, interfacial adhesion characteristics, etc. from the semiconductor to the conductive filament substrate, physical or chemical treatment of the surface of the filamentous structure of the conductive filament substrate 1 may be considered. Modifications, such as surface treatment, surface coating, etc. For example, in order to improve battery performance, a dense layer made of a semiconductor or an insulating material (Ti0 ₂ dense layer as described above) may be coated on the surface of the conductive filament substrate 1 to prevent the electrolyte 4 from directly contacting the conductive filament substrate 1. contact. The methods for preparing the dense layer include a sputtering method, a vacuum thermal evaporation method, a spray coating method, an electrochemical method, and a direct sintering method.

In addition, the counter electrode 3 may be a solid structure or a hollow structure made of a conductive material, or may be a core. And a plurality of layers of skin, the core and the inner layer of the skin may be made of a conductive material or a non-conductive material, and the outer layer of the skin is made of a conductive material. The conductive material used in the counter electrode 3 may be an organic conductive material, an inorganic conductive material (metal-containing material) or an organic/inorganic composite conductive material, or may be carbon fiber.

In order to improve the electrochemical activity of the counter electrode 3 and reduce the cost of the counter electrode, a highly efficient catalytic layer may be added to the surface of the counter electrode 3, for example, Pt is plated on the surface of the working electrode and the counter electrode.

(II) Comparison of preparation and performance of three different types of sensitized dye solar cells

1, the preparation of three types of batteries

The specific preparation process of the battery body is as follows:

Fifteen prepared 12 cm long titanium wires were ultrasonically cleaned with acetone for 5 minutes, and then ultrasonically cleaned with a substrate cleaning agent for 5 minutes. After being calcined at a temperature of 400 ° C to 500 ° C for 15 minutes, naturally cooled to room temperature and taken out; under the baking of an infrared lamp, spraying tetraethyl titanate / acetylacetone ethanol on the burned titanium wire The solution was further sintered at 500 ° C for 30 minutes and allowed to cool naturally, so that a Ti _{2 2} dense layer of a semiconductor material having a thickness of about 0.9 μm was obtained on the titanium wire. Spraying the TiO ₂ emulsion of the semiconductor material commonly used in the dye-sensitized solar cell on the Ti0 ₂ dense layer, and then sintering at 500 ° C for 30 minutes, repeating the above Ti0 ₂ emulsion spraying and sintering process twice, and coating the titanium wire The total thickness of the TiO ₂ layer on the semiconductor material is 6-9 microns. The sintered conductive wire substrate with the Ti0 ₂ semiconductor material layer was sensitized in a N719 dye/ethanol solution having a concentration of 5×10 ⁴ mol/L for more than 12 hours, and air-dried at room temperature to obtain 15 sensitized work. Electrode (see Figures 4 and 5). 15 sensitized working electrodes were randomly divided into 3 groups of 5 each. The three sets of working electrodes are respectively used for preparing a battery of a conventional parallel bushing structure, a battery without a casing winding structure, and a battery of the present invention, and analyzing and comparing battery performance of different battery packs.

First, a weight of 2 grams was hung on one end of a 40 micron diameter platinum wire and suspended. The other end of the platinum wire is adhered to one end of the working electrode by a PMMA (polymethyl methacrylate) solution, and is fixed after the solvent of the PMMA solution is volatilized. Then, the working electrode is kept at an angle of 45 ° between the working electrode and the suspended platinum wire, so that the platinum wire is tightly wound around the working electrode. When the platinum wire is wound 1.5 cm from the other end of the working electrode, the platinum wire is also fixed to the working electrode by a PMMA solution to form a battery body (see Fig. 3). The battery body was inserted into a glass outer sleeve having an inner diameter of 0.5 mm and an outer diameter of 0.82 mm, and the standard electrolyte of a liquid dye-sensitized solar cell was poured into the tube (preparation method: 0.1274 g of iodine, 0.6754 g of lithium iodide, and 0.15 mL of 4- The dye-sensitized solar cell of the present invention, which is referred to as a class A battery, was prepared by dissolving tert-butylpyridine in 5 mL of acetonitrile and 5 mL of a propylene carbonate mixed solvent throughout the entire tube.

Insert a platinum wire with a length of 15 cm and a diameter of 100 μm into the inside of the working electrode prepared at the same time. The glass outer sleeve has a diameter of 0.5 mm, and the platinum wire and the working electrode are kept substantially parallel with a pitch of 30 μm. The standard electrolyte of the usual liquid dye-sensitized solar cell (same composition as the electrolyte used for the class A battery) is filled into the tube to fill the entire tube, and a battery of a conventional parallel sleeve structure is obtained, which is referred to herein as a type B battery.

Another set of battery bodies was made in exactly the same way as a Class A battery. Put the battery body into the standard electrolyte for 3 seconds, take it out, clip the two ends of the battery with a clip and hang it horizontally, then slowly drop 3 drops of standard electrolyte on the horizontally placed battery, gently turn the battery to make the electrolysis The liquid is evenly hung on the entire battery to form another type of battery, referred to herein as a Class C battery. Class C batteries were tested immediately after preparation.

2, the performance comparison of three types of batteries

In AMI.5 (ASTM E892), the performance of A, B, and C batteries was tested under double solar intensity. The following are the average test results for various types of batteries.

Class A battery: The measured results are as follows: When single-sided light is received (light is incident from one side of the battery, the incident angle is perpendicular to the surface of the sleeve), the battery open circuit voltage is 700mV, the short-circuit current density is 1 lmA/cm ² , and the total photoelectric energy conversion The efficiency is 6.0%. When the double-sided light is received (that is, on the other side of the battery, a diffuse reflection plate is added perpendicular to the incident direction of the light). The battery open circuit voltage is 720mV, the short-circuit current density is 21mA/cm ² , and the total photoelectric energy conversion efficiency is 11 %, the IV curve of the test is shown in Figure 8.

Class B battery: The test result is: When single-sided light is received (light is incident from the opposite side of the battery, the incident angle is perpendicular to the surface of the sleeve) Battery open circuit voltage is 730mV, short-circuit current density is 8.6mA/cm ² , total photoelectric energy conversion The efficiency is 4.2%, and when the double-sided light is received (that is, on the working electrode side of the battery, a diffuse reflection plate is added perpendicular to the incident direction of the light), the IV curve has been tested due to structural defects (described below). Not a normal IV curve, as shown in Figure 9.

Class C battery: The test result is: When single-sided light is received (light is incident from one side of the battery, the incident angle is perpendicular to the surface of the working electrode). The open circuit voltage of the battery is 770mV, the short-circuit current density is 1.6mA/cm ² , and the total photoelectric energy conversion efficiency is 1.0%, since the battery electrolyte temporarily adheres to the battery by capillary action, the electrolyte is opened in the air, and after a while, the battery is completely degraded, as shown in Fig. 10a and Fig. 10b. Figure 10a shows the results of the test immediately after the battery is prepared, and Figure 10b shows the results of the test after 10 minutes.

Comparison of the working stability of the three types of batteries A, B and C:

As mentioned above, the defect of the B-type battery structure means that since the two electrodes are parallel, the average diffusion distance of the iodine is far, and the battery cannot continuously maintain a stable output current during actual operation. For Class C batteries, since the electrolyte is easily volatilized, it is basically impossible to compare the actual application. There is no need to compare the stability here. Figure 11a and lib are the short-circuit currents of the battery output with time when the Class A battery and the Class B battery are exposed on one side and both sides, respectively. The change.

It can be seen from Fig. 1b that the B-type battery only has an output current that is always stable when the angle of the incident light is 0 degrees (that is, when the light is incident from the opposite side of the battery), and the actual output efficiency is also It meets the test efficiency, and when the incident light angle is 180 degrees (that is, the light is incident from the working electrode side of the battery), the output current is sharply attenuated with time. In actual use, it is impossible to ensure that the angle of the incident light is always 0 degrees. Therefore, the output current of the B-type battery will be greatly attenuated, and the actual output efficiency will be far lower than the test efficiency. However, Class A batteries do not have this problem. From Figure 11a, it can be seen that the output current does not change with time, whether it is single-sided or double-sided, and the Class A battery can be simply combined with a white plate. The efficiency doubles, which is beyond the reach of Class B batteries.

We further compare the illumination angle dependence of the three types of batteries A, B, and C:

The dependence of the A, B, and C batteries on the illumination angle is shown in Figure 12, Figure 13, and Figure 14, respectively. It can be seen that when the angle of the incident light changes, the output efficiency of the A and C batteries is basically unchanged, which ensures that the battery has a stable power output when the solar elevation angle changes from morning to evening in practical applications. However, the front of the C-type battery has basically failed to talk about practical applications. For Class B batteries, when the angle of incident light changes, the output efficiency changes greatly. When the angle of the incident light is 180 degrees, the output efficiency is the largest, but in fact, this is only the apparent test efficiency. From Fig. lib, the output current actually has a large attenuation with time.

From the above comparison of the output efficiency of the battery, the stability of the battery, the dependence of the output efficiency on the angle of incidence of sunlight, it can also be clearly seen that the class A battery of the present invention has a very significant advantage in various aspects.

(3) Preparation and performance testing of solar cells

Referring to FIG. 7, the dye-sensitized solar cells shown in FIG. 1 are arranged in parallel at a certain density to form a solar battery group. One end of the outer sleeve 5 of each dye-sensitized solar cell is connected to the liquid inlet side tube 7 and the other end is connected. The liquid side tube 6 is connected. The positive electrode 8 and the negative electrode 9 are respectively connected to the counter electrode of all the cells and the conductive filament substrate in the side tube. Both the inlet side tube 7 and the outlet side tube 6 are filled with electrolyte and integrated with the electrolyte in the outer sleeve 5 of each dye-sensitized solar cell. An opening is provided in each of the inlet side tube 7 and the outlet side tube 6 for electrolyte perfusion and cleaning.

The specific manufacturing process of the battery pack is as follows: Use a glass tube with an inner diameter of 3 mm and a length of 10 cm 7

(One end is sealed, the other end is opened as a liquid inlet), and a row of holes having a diameter of about 0.85 mm is drilled on one side of the wall, and the distance between the holes is 1 mm. Inserting a single A-type battery without an electrolyte into a round hole to form a battery row composed of a plurality of battery cells, and then using a low-temperature glass having a melting point of 360 degrees Celsius The glass powder will seal into the gap at the interface. Thereafter, the positive and negative electrodes of each battery were respectively connected to two gold wires having a diameter of 0.2 mm and a length of 15 cm at the other end of the battery row. Use a glass tube 6 with an inner diameter of 4 mm and a length of 10 cm (--end seal, the other port is open), and cut a width of 0.85 mm with a precision grinding wheel on one side of the wall, and the length is parallel to the glass tube 6 and A side groove is formed through the opening of the entire glass tube 6. The other end of the battery row that has been connected to the positive and negative electrodes of the output is embedded in the side groove of the glass tube 6, and the gap between the side groove of the glass tube 6 and the battery row is also sealed with the low temperature glass powder, and the positive and negative electrodes are open. After the port is taken out, the port is sealed with low-temperature glass powder to form a battery pack consisting of 54 unit cells. Use a tee with a continuity selector valve. One end of the three-way structure hose is connected to the open end of the glass side tube 7, one end is connected to the electrolyte outlet tube, and the other end is connected to the vacuum pump. First, the directional valve of the tee is rotated, so that the vacuum pump is connected to the opening of the side tube 7, the battery pack is evacuated, and the directional valve of the tee is rotated for 5 minutes, so that the output tube of the electrolyte is connected to the opening of the side tube 7. The electrolyte is poured into the battery pack. After filling the electrolyte, the opening of the side tube 7 is sealed with a low temperature curing resin to form a complete working battery module. The performance of the battery module was tested in exactly the same way as a single battery. The result was an open circuit voltage of 700 mV without a reflector, a short-circuit photocurrent of 400 mA, and a photoelectric conversion efficiency of the battery module of 5.5%. The efficiency of a layer of reflector is 8%.

Alternatively, the positive and negative electrodes of each battery may be taken out from the liquid discharge side pipe and the liquid inlet side pipe, respectively. Specifically, in the process of winding the platinum wire around the working electrode, one end of the platinum wire carries a heavy object, and the other one is connected to the working electrode through the PMMA, and a longer length of platinum wire can be reserved as an electrode. It is possible to divide the positive and negative electrodes of the battery on both sides, and then assemble them according to the above method. In summary, the present invention discloses a working electrode of a dye-sensitized solar cell and a dye-sensitized solar cell structure based on the working electrode. The above described application scenarios and embodiments are not intended to limit the present invention, and various modifications and refinements can be made by those skilled in the art without departing from the spirit and scope of the present invention. As defined by the scope of the claims.

Claims

Claim

A dye-sensitized solar cell comprising a working electrode, a counter electrode, an electrolyte and a transparent sleeve, the working electrode further comprising a conductive filament-like substrate and a sensitized semiconductor film coated on the outside of the conductive filament-like substrate; The electrode forms a winding structure to form a battery body; the battery body is placed in the transparent sleeve, the electrolyte is filled between the transparent sleeve and the battery body; and the conductive filament substrate and the counter electrode are respectively led out from the ends of the transparent sleeve.

The dye-sensitized solar cell according to claim 1, wherein the sensitized semiconductor film is a porous semiconductor film having sensitized dye molecules adsorbed thereto, and has a thickness of from 1 to 100 μm.

The dye-sensitized solar cell according to claim 1, wherein a layer of a dense semiconductor or insulator material is coated on said conductive filament substrate.

The dye-sensitized solar cell according to claim 1, wherein the working electrode and/or the counter electrode surface is coated with a catalytic layer having a thickness of 1-1000 nm.

The dye-sensitized solar cell according to claim 4, wherein the catalyst layer of the counter electrode is coated with a separator of a semiconductor or an insulator material, and the separator has a thickness of 1-100 nm.

The dye-sensitized solar cell according to claim 1, wherein: the counter electrode and the working electrode form a winding structure by winding the working electrode on the electrode, or winding the working electrode around the counter electrode, or the working electrode and The counter electrodes are intertwined.

The dye-sensitized solar cell according to claim 1, wherein: a pair of electrodes forms a winding structure with one or more working electrodes, or a working electrode is wound with one or more counter electrodes structure. The dye-sensitized solar cell according to claim 1, wherein the distance between the battery main body and the inner wall of the transparent sleeve is 0.01 to 5 mm.

The dye-sensitized solar cell according to claim 1, wherein the electrolyte is a liquid electrolyte or a semi-solid electrolyte.

A dye-sensitized solar cell comprising a plurality of dye-sensitized solar cells according to any one of claims 1 to 9, and a liquid inlet side tube, a liquid outlet side tube, a positive electrode and a negative electrode, wherein: A plurality of dye-sensitized solar cells are arranged in parallel at a certain density, and one end of each transparent smear of the dye-sensitized solar cell is connected to the liquid inlet side tube, and the other end is connected to the liquid discharge side tube; the positive and negative electrodes are from the liquid inlet side The tube or the outlet side tube is taken out or taken out from the inlet side tube and the outlet side tube, respectively, wherein the positive electrode is connected to the conductive filament-like substrate of all the dye-sensitized solar cells, and the negative electrode and all the dye-sensitized solar energy The counter electrode connection of the battery; the inlet side tube and the outlet side tube are filled with electrolyte and integrated with the electrolyte in the transparent sleeve of each dye-sensitized solar cell.