CN116399924A - Photoelectrochemical working electrode, preparation method thereof and photoelectrochemical device - Google Patents
Photoelectrochemical working electrode, preparation method thereof and photoelectrochemical device Download PDFInfo
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- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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Abstract
The invention provides a photoelectrochemical working electrode and a preparation method thereof, and a photoelectrochemical device. The photoelectrochemical working electrode includes: a conductive substrate; a double-sided conductive adhesive tape which is in a two-dimensional shape, and a first side of the double-sided conductive adhesive tape is stuck on the conductive substrate; and the nano semiconductor material is adhered to the second surface of the double-sided conductive adhesive tape. The double-sided conductive adhesive tape is used as a conductive bridge, and is electrically connected with the conductive substrate and the nano semiconductor material, so that an increased current signal is obtained, the problems of large design difficulty, long time consumption, uncontrollable preparation process, small photocurrent density, large dark current and the like of a photoelectrochemical working electrode in the traditional preparation method are solved, the charge carrier transmission capacity at a polycrystalline nano semiconductor interface is improved, the performance of a photoelectrochemical detector is improved, and the photoelectrochemical detector with large photocurrent density and small dark current is obtained.
Description
Technical Field
The invention relates to the field of photoelectric detection, in particular to a photoelectrochemical working electrode, a preparation method thereof and a photoelectrochemical device.
Background
Photoelectric detection technology has important application prospect in the fields of military industry, aerospace, electronics, energy and the like. Photodetectors can be classified into photon detectors and heat-conducting detectors according to the operating mechanism. Among them, photoelectrochemical (PEC) detectors are considered to be one of the most important applications in photodetectors. Meanwhile, PEC decomposition of water is also a promising strategy for converting solar energy into chemical fuels. In addition, PEC photodetectors have attracted considerable academic attention due to the advantages of mild reaction conditions, simple preparation process, high photocurrent density, high sensitivity, ultra-fast response, high reliability, and the like. The nano semiconductor material has strong light absorption characteristic, the band gap of many nano semiconductor materials is matched with the wavelength of sunlight, and the nano semiconductor material can effectively absorb solar energy and convert the solar energy into strong electric signals.
In the process of realizing the invention, the applicant finds that the traditional working electrode of the photoelectric detector is complex to manufacture, has lower reliability and poor consistency, and cannot realize industrialized mass production.
Disclosure of Invention
First, the technical problem to be solved
The present invention provides a photoelectrochemical working electrode and a method for producing the same, and a photoelectrochemical device, which are expected to solve at least partially one of the technical problems in the background art.
(II) technical scheme
In a first aspect of the present invention, there is provided a photoelectrochemical working electrode comprising: a conductive substrate; a double-sided conductive adhesive tape which is in a two-dimensional shape, wherein a first side of the double-sided conductive adhesive tape is stuck on a conductive substrate; the nanometer semiconductor material is adhered to the second surface of the double-sided conductive adhesive tape.
In a second aspect of the present invention, there is provided a method of preparing a photoelectrochemical working electrode as above, comprising: step A, sticking a first surface of a double-sided conductive adhesive tape on a conductive substrate; step B, preparing a nano semiconductor material; and C, transferring the nano semiconductor material to the second surface of the double-sided conductive adhesive tape.
In a third aspect of the present invention, there is provided a photoelectrochemical device comprising: photoelectrochemical working electrode as above; wherein the photoelectrochemistry device is a photoelectrochemistry detector or a photoelectrochemistry hydrogen production device, the light source is monochromatic light or polychromatic light, and the wavelength range is 200-2000nm.
(III) beneficial effects
As can be seen from the technical scheme, compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The double-sided conductive adhesive tape is used as a conductive bridge, and is electrically connected with the conductive substrate and the nano semiconductor material, so that an increased current signal is obtained, the problems of large design difficulty, long time consumption, uncontrollable preparation process, small photocurrent density, large dark current and the like of a photoelectrochemical working electrode in the traditional preparation method are solved, the charge carrier transmission capacity at a polycrystalline nano semiconductor interface is improved, the performance of a photoelectrochemical detector is improved, and the photoelectrochemical detector with large photocurrent density and small dark current is obtained.
The invention adopts the commonly ignored technical means, solves the technical problem of poor contact between the nano semiconductor material and the electrode, has the advantages of compact and reliable connection, low cost, simple operation, good consistency and the like, is very suitable for being used in industrial production, and has wide application prospect in the fields of military industry, aerospace, energy sources, photoelectrons and the like.
(2) The supporting material is non-woven fabric; the viscoelastic material is epoxy resin and modified polyimide, the conductive tape with the conductive medium being carbon powder is used for manufacturing the photoelectric detector electrode, and experiments prove that the photoelectrochemical working electrode has good working performance and can be compared with the traditional photoelectrochemical working electrode with complex manufacturing.
(3) After the nano semiconductor material is stuck to the second surface of the double-sided conductive adhesive tape, the nano semiconductor material is pressed towards the direction of the double-sided conductive adhesive tape, so that on one hand, the contact between the nano semiconductor material and the conductive adhesive tape/conductive glue is increased, the current is increased, and on the other hand, the gap on the surface of the nano semiconductor material and the contact area between the nano semiconductor material and electrolyte are reduced, and the dark current is reduced.
Drawings
FIG. 1A is a schematic diagram of a photoelectrochemical working electrode according to an embodiment of the present invention.
FIG. 1B is a flow chart of a method of fabricating the photoelectrochemical working electrode of FIG. 1A.
FIG. 2 is a schematic diagram of the raw materials and processes for preparing photoelectrochemical working electrodes according to example 1 of the present invention. Wherein,,
(a) The preparation process is shown;
(b) Is used for preparing a physical photo of the raw material.
FIG. 3 is a microscopic characterization of the preparation of the starting material/preparation intermediate in example 1 of the present invention. Wherein,,
(a) And (b) a Scanning Electron Microscope (SEM) of a S-InSe/conductive paste/ITO glass sample;
(c) An X-ray diffraction pattern for an S-InSe sample; (d) Raman spectrum of S-InSe sample.
FIG. 4 is a microscopic characterization of the L-InSe/paste/ITO glass sample of example 1 of the present invention. Wherein,,
(a) Scanning Electron Microscopy (SEM) for the L-InSe/conductive paste/ITO glass sample;
(b) An X-ray diffraction pattern for L-InSe.
Fig. 5 shows the results of the photoelectric performance test of the photodetector according to embodiment 1 of the present invention. Wherein,,
(a) LSV curves for S-InSe and L-InSe-based detectors in darkness and under simulated sun lighting conditions;
(b) Photocurrent (zero bias voltage) of the S-InSe based detector under simulated solar illumination of different powers;
(c) Photocurrent (zero bias voltage) of the detector based on S-InSe under 365nm illumination with different powers;
(d) Is the photocurrent (zero bias voltage) of the S-InSe based detector under 700nm illumination of different powers.
FIG. 6 is a graph showing the results of a photoelectric property test of S-InSe samples. Wherein,,
(a) Is an absorption curve;
(b) Is a direct band gap and a cut-off wavelength;
(c) Is an indirect band gap and cut-off wavelength;
(d) Is a schematic diagram of transition of photogenerated carriers under illumination.
FIG. 7 shows LSV characteristics of each of the detectors in examples 2-5 of the present invention. Wherein,,
(a) LSV curves for the S-BP and L-BP based detectors of example 2 of the present invention in darkness and under simulated sun light conditions;
(b) Based on S-MoS in example 3 of the present invention 2 And L-MoS 2 LSV curves of the detector in darkness and under simulated sun lighting conditions;
(c) Based on S-BiFeO in example 4 of the present invention 3 And L-BiFeO 3 LSV curves of the detector in darkness and under simulated sun lighting conditions;
(d) LSV curves for hollow white substrates (conductive paste/ITO glass) in darkness and under simulated sun light conditions for example 5 of the present invention.
Detailed Description
The invention adopts a generally neglected technical means, takes the double-sided conductive adhesive tape as a conductive bridge, electrically connects the conductive substrate and the nano semiconductor material, obtains an increased current signal, can be applied to a photoelectrochemical detector or a photoelectrochemical hydrogen production device, and has good application prospect.
The present invention will be further described in detail below with reference to the accompanying drawings in order to make the objects, technical solutions and advantages of the present invention more apparent.
The invention provides a photoelectrochemical working electrode. FIG. 1A is a schematic diagram of a photoelectrochemical working electrode according to an embodiment of the present invention. As shown in fig. 1A, the photoelectrochemical working electrode of the present embodiment includes: a conductive substrate 10; a double-sided conductive tape 20 having a two-dimensional shape, a first side of which is adhered to the conductive substrate; a nano-semiconductor material 30 is attached to the second side of the double-sided conductive tape.
For the conductive substrate 10, it may be a rigid substrate or a flexible substrate, preferably an ITO (indium tin oxide) substrate or an FTO (fluorine doped SnO) 2 Conductive glass) substrate.
For the nano-semiconductor material 30, it may be a zero-dimensional (quantum dot), one-dimensional (nanowire), two-dimensional (nanoplatelet), or other shaped nanoparticle. Preferably, the nano semiconductor material is two-dimensional InSe (indium selenide) nano sheets. In the actual preparation process, the nano semiconductor material can be attached to a rubber belt, dispersed in a solvent or independently exist. Preferably, the two-dimensional nano-semiconductor material is peeled off by tape stripping.
For a double-sided conductive tape, it should have the following characteristics:
1. double-sided adhesive
The double-sided conductive tape can adhere to the conductive substrate and the nano-semiconductor material, comprising: conductive media, viscoelastic materials, support materials.
The support material is used to provide reliable support and protection for the conductive medium, the viscoelastic material, and the conductive connecting material, and may be one or more of a polyamide film/fiber, a polyester film/fiber (e.g., a nonwoven fabric). Preferably, the support material is selected from the group consisting of non-woven fabrics,
the support material has a viscoelastic material on both sides, which has elasticity in addition to tackiness, and may be one or more materials containing tacky components such as epoxy, polyurethane, polyisocyanate, silicone adhesive, acrylic, polyurethane, polyether, polyol, and the like. Preferably, the viscoelastic material is acrylic.
2. Conductivity of conductive material
For non-woven fabrics as support materials, the conductive medium may be carbon powder, aluminum powder, copper powder, gold powder, silver powder, or a coated film/wire having one or more of the above components, or other forms of conductive material, dispersed in a viscoelastic material, with a sheet resistance within 1000ohms/sq, preferably a sheet resistance <10ohms/sq.
3. Elasticity of
The ITO/FTO substrate is planar so the side of the viscoelastic material in contact with it does not need to be elastic, while the side of the viscoelastic material in contact with the nano-semiconductor material is not planar because the nano-semiconductor material is disordered. If one surface of the double-sided conductive adhesive tape contacted with the nano semiconductor material has no elasticity and does not deform under pressure, the contact area of the nano semiconductor material and the double-sided conductive adhesive tape is limited, so that the contact resistance is high on one hand, and the nano semiconductor material is easier to fall off on the other hand.
In this embodiment, the surface of the viscoelastic material contacting the nano semiconductor material has a certain elasticity, so that the nano semiconductor material is rearranged on the surface under pressure (for dry transfer), and the viscoelastic material contacts the double-sided conductive tape more fully, thereby reducing contact resistance and preventing falling off. From the performance parameter point of view, the thickness of the viscoelastic material on the side contacting the nano-semiconductor material is between 1 and 1000 μm, preferably 40 μm or more; the modulus of elasticity is between 2k and 20MPa, more preferably between 2M and 8 MPa.
In summary of the above parameters, in a preferred embodiment of the present invention, a double-sided conductive tape is: the supporting material is non-woven fabric; the conductive medium is carbon powder; the viscoelastic material is acrylic acid; wherein the thickness of the viscoelastic material is 40 μm or more, and the elastic modulus is 5 MPa.
In practical application, the double-sided conductive adhesive tape can be a commercially available double-sided conductive adhesive tape or a self-made product. In particular, the applicant finds that the double-sided conductive adhesive tape for the scanning electron microscope can meet the requirements and can be applied to the invention as a low-cost and low-quantity choice through a plurality of exploratory experiments.
The invention also provides a preparation method of the photoelectrochemical working electrode. FIG. 1B is a flow chart of a method of fabricating the photoelectrochemical working electrode of FIG. 1A. As shown in fig. 1B, the photoelectrochemical working electrode preparation method of the present embodiment includes:
step A, sticking a first surface of a double-sided conductive adhesive tape on a conductive substrate;
step B, preparing a nano semiconductor material;
step C, transferring the nano semiconductor material to the second surface of the double-sided conductive adhesive tape, and pressing the nano semiconductor material towards the direction of the double-sided conductive adhesive tape;
and D, taking the obtained working electrode as a working electrode of a photoelectrochemistry test system, testing dark current and photocurrent of the working electrode, and finally obtaining the photoelectrochemical property.
For the double-sided conductive tape, the conductive substrate, the nano-semiconductor material, reference may be made to the previous related description, and the description thereof will be omitted. The technical features related to the preparation method are mainly described in detail below.
In the step B, the nano semiconductor material is prepared by a tape stripping method or a liquid phase stripping method. In other words, the nano-semiconductor material may be attached to the tape, dispersed in a solvent, or exist independently. Preferably, the nano-semiconductor material is prepared by a mechanical peeling method and attached on an adhesive tape for standby, and can be performed in air at room temperature or in a glove box.
And C, transferring the nano semiconductor material to a double-sided conductive tape/conductive glue by using a dry transfer, wet transfer or coating nano semiconductor material dispersion liquid mode to obtain the composite nano structure photoelectric detector device. In particular, the implementation mode that needs to be emphasized is that the transfer method is dry transfer, and the steps are as follows: firstly, the nano semiconductor material which is peeled off by a mechanical peeling method and stuck on the peeling tape is stuck on the double-sided conductive tape, then the peeling tape is pressed by fingers or other tools, and finally the nano semiconductor material on the double-sided conductive tape is exposed. The whole operation was carried out in air or in a glove box at room temperature.
Based on the working electrode, the invention also provides a photoelectrochemical device. The photoelectrochemistry device is a photoelectrochemistry detector or a photoelectrochemistry hydrogen production device, the light source of the photoelectrochemistry device is monochromatic light or polychromatic light, the wavelength range of the photoelectrochemistry device is 200-2000nm, and the photoelectrochemistry device comprises the photoelectrochemistry working electrode.
Based on the above, for the photoelectrochemical working electrode of the present embodiment, the applicant needs to emphasize two points:
(1) Double-sided conductive tape communicates charge transport between nano-semiconductor material and substrate
The current preparation process of high-performance PEC detectors based on nano-semiconductor materials is also relatively complex. Common ways of applying the nano-dispersions obtained by liquid phase lift-off to conductive substrates utilize adhesives (such as polyvinylidene fluoride) to bond the nano-semiconductor materials to each other and to the substrate. However, due to poor conductivity of the adhesive, the nano semiconductor material is not fully contacted with the substrate, and the stacked nano semiconductor materials have larger contact resistance, so that the electric charge transmission is not facilitated, and the obtained electric signal is weak.
In the invention, a double-sided conductive adhesive tape is attached to a conductive substrate, and then a nano semiconductor is transferred to the double-sided conductive adhesive tape to obtain a working electrode of a photoelectrochemical detector. The double-sided conductive adhesive tape or conductive glue is used as a conductive bridge, so that charge transmission between the nano semiconductor material and the substrate is communicated, charge carrier transmission capacity at a polycrystalline nano semiconductor interface is improved, performance of the photoelectric detector is improved, and the photoelectric chemical detector with high photocurrent density and small dark current is obtained.
(2) The double-sided conductive adhesive tape has elasticity, and the bonding performance of the nano semiconductor material is improved by adopting a pressing mode
In the conventional technology, since the nano semiconductor material is coated on the electrode and is freely piled up only under the action of gravity, many porous structures exist on the electrode, and dark current is large.
In the present invention, a double-sided conductive tape having elasticity on at least one side is used, and after transferring the nano semiconductor material to the double-sided conductive tape, the nano semiconductor material is pressed toward the double-sided conductive tape. Through the technical means, firstly, the porous structure on the electrode is reduced so as to reduce dark current; secondly, the contact with the conductive adhesive is increased, the contact resistance is reduced, and meanwhile, the falling-off of the nano semiconductor material is reduced, so that a high-stability detector is obtained; thirdly, the flatness of the surface of the photoelectrochemical working electrode is enhanced, and the subsequent integration of the device is facilitated. Therefore, the invention adopts a generally neglected technical means, solves the technical problem of poor contact between the nano semiconductor material and the electrode, and brings about corresponding technical effects.
(3) The adoption of the double-sided conductive adhesive tape greatly reduces the process difficulty and improves the consistency of the prepared devices
The process is simple and controllable, the production equipment cost is low, the automatic mass production is easy to realize, and the problems of high design difficulty, long time consumption, uncontrollable preparation process, poor consistency and the like of the working electrode in the traditional preparation method are solved. The invention has important engineering practical significance and wide application prospect in the fields of military industry, aerospace, energy, photoelectrons and the like.
Several examples of applications of the present invention are given below.
1. Example 1
FIG. 2 is a schematic diagram of the raw materials and processes for preparing photoelectrochemical working electrodes according to example 1 of the present invention. Wherein, (a) indicates the preparation process; (b) is a photograph of the raw material for production. In fig. 2, reference numeral 1 denotes an InSe block, reference numeral 2 denotes a peeling tape, reference numeral 3 denotes an InSe/peeling tape, reference numeral 4 denotes a double-sided conductive tape, reference numeral 5 denotes ITO glass, reference numeral 6 denotes double-sided conductive tape/ITO glass, reference numeral 7 denotes peeling tape/InSe/double-sided conductive tape/ITO glass, and reference numeral 8 denotes InSe/double-sided conductive tape/ITO glass. Reference numerals (1), (2), (3) and (4) denote implementation steps.
Referring to fig. 2 (a), the preparation process includes:
step (1), tearing off the nano semiconductor material from the InSe block 1 by using a stripping adhesive tape 2;
and (2) preparing the double-sided conductive adhesive tape/ITO.
And cutting a section of double-sided conductive adhesive tape 4, attaching the double-sided conductive adhesive tape on ITO glass 5, and pressing and pulling the double-sided conductive adhesive tape with fingers or other things to tightly adhere the double-sided conductive adhesive tape to the ITO glass 6.
Step (3), preparation of working electrode InSe/double-sided conductive adhesive tape/ITO
The stripping adhesive tape stuck with the nano semiconductor material is repeatedly folded and then stuck on the double-sided conductive adhesive tape on the ITO, and the stripping adhesive tape/InSe/double-sided conductive adhesive tape/ITO glass is pressed and pulled by fingers or other things as shown by the reference numeral (7) in the figure.
And (4) tearing off the adhesive tape, and obtaining the product, namely the S-InSe/double-sided conductive adhesive tape/ITO glass 8.
FIG. 3 is a microscopic characterization of the preparation of the starting material/preparation intermediate in example 1 of the present invention. The morphology of InSe/double-sided conductive tape/InSe on ITO was observed with scanning electron microscopy, as shown in fig. 3 (a) and (b). It can be seen that the sample surface is flat on a microscopic scale.
Diffraction data of the sample were obtained with an X-ray diffractometer, and it was seen that the diffraction peaks matched with the bragg diffraction peaks of the standard InSe crystal, as shown in fig. 3 (c), indicating that transferring InSe to the conductive paste did not damage the crystal structure. And (00 l) peak intensities were much higher than other diffraction peaks, indicating that the S-InSe sample was much larger in transverse/longitudinal dimension than in thickness. The raman peak further confirms the integrity of the sample crystal structure as shown in fig. 3 (d).
For comparison, the applicant also prepared photoelectrochemical working electrodes by a liquid phase stripping method of conventional technology. The preparation method comprises the following steps: and (1) weighing a proper amount of InSe, putting the InSe into an N-methylpyrrolidone solution, performing ultrasonic treatment, and performing centrifugal separation to obtain the L-InSe nano sheet. And (2) dispersing the L-InSe nano sheet into liquid drops on ITO glass, and drying under vacuum condition to obtain the L-InSe/ITO.
FIG. 4 is a microscopic characterization of the L-InSe/paste/ITO glass sample of example 1 of the present invention. The morphology of L-InSe on L-InSe/ITO was observed with a scanning electron microscope, as shown in FIG. 4 (a). It can be seen that the surface of the piled L-InSe is rough and fluffy, and a plurality of holes exist. Diffraction data of the sample were obtained with an X-ray diffractometer, and it was seen that the diffraction peak matched with the bragg diffraction peak of the standard InSe crystal, as shown in (b) of fig. 4. Compared with the extremely strong (00L) peak in the XRD of the S-InSe, the intensity of the (00L) peak of the L-InSe is obviously reduced, diffraction peaks of other crystal faces appear, and further the transverse/longitudinal dimension of the L-InSe sample is obviously smaller than that of the S-InSe. The results indicate that the transverse/longitudinal dimensions of the samples obtained by liquid phase peeling are smaller than those obtained by tape peeling.
The LSV curves were tested under dark and simulated solar light conditions with S-InSe/double-sided conductive tape/ITO as working electrode, saturated calomel electrode as reference electrode, platinum as counter electrode, tris-HCl solution (1M) at pH 6.8 as electrolyte, as shown by the corresponding curves in fig. 5 (a), and the current-time (I-T) curves of the S-InSe-based detector under simulated solar light and at different wavelengths, as shown in fig. 5 (b), (c), (d), respectively. It can be seen that the detector exhibits good photodetection performance under sunlight and monochromatic light of different wavelengths. The photocurrent density and responsivity at zero bias voltage were both higher than those of other material photodetectors of the prior art, as shown in table 1. In table 1, the properties under sunlight are not indicated.
TABLE 1 preparation method, test conditions and response parameters to sunlight of photoelectrochemical working electrode
Reference to the literature
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Those skilled in the art will appreciate that in general, the higher the bias voltage, the greater the photocurrent density and responsivity. Further we analyzed the mechanism of photoelectric response. The absorption curve of InSe is shown in FIG. 6 (a), and has strong absorption for light of 200-1000 nm. The direct band gap was calculated by using the Tauc relationship and was 2.23eV, which corresponds to the cutoff wavelength of 556nm, as shown in fig. 6 (b). The indirect bandgap is 1.77eV, corresponding to a cut-off wavelength of 701nm, as shown in FIG. 6 (c). Therefore, it can be seen that the InSe detector corresponds to light with a wavelength of 701nm or less. When the wavelength is between 701 and 556nm, the electron absorption photon on the valence band is indirectly transited (mode (1)); when the wavelength is less than 556nm, the electrons in the valence band absorb photons while undergoing direct transition (mode (2)) and indirect transition. In addition, a photocurrent density at 365nm was also noted below the value of 700nm, because of the carrier transition regime, in addition to the above analysis, which affects the photocurrent density, as well as the number of carriers. At the same optical power, the number of photons with short wavelength is small, and the number of carriers excited is small, so that the photocurrent density at 365nm is lower than 700 nm.
The LSV curves were tested in dark and simulated sun light conditions, respectively, using L-InSe/ITO as the working electrode, a saturated calomel electrode as the reference electrode, platinum as the counter electrode, and Tris-HCl solution (1M) at pH 6.8 as the electrolyte, as shown by the corresponding curves in FIG. 5 (a). Comparing the photocurrent densities of the photoelectrochemical detectors based on S-InSe and L-InSe, it can be found that the photocurrent density of S-InSe is significantly greater than that of L-InSe, and the dark current of S-InSe is lower than that of L-InSe. The photocurrent of S-InSe is large for two reasons: first, L-InSe is a free stacked state, contact between the nano-sheets and the substrate ITO is insufficient, contact resistance is large, and a large current loss is generated. In comparison, the working electrode based on S is prepared under the applied pressure, the contact between S-InSe and the contact between the nano-sheet and the substrate conductive adhesive are better, and the contact resistance is smaller. The dark current of the S-InSe is small because the S-InSe on the double-sided conductive adhesive tape is subjected to external pressure, the surface is smoother, and as shown in (a) of fig. 3, the contact area with the electrolyte is small, and the dark current is small. In contrast, the freely stacked L-InSe on ITO is a fluffy state, has a rough surface, has many holes, and has a large contact area with the electrolyte as shown in fig. 4 (a), and has a large dark current.
The absorption spectrum of S-InSe was tested as shown in FIG. 6 (a). The indirect bandgap of 1.77eV was calculated by Tauc, as shown in fig. 6 (c). The above results indicate that the indirect bandgap semiconductor material-based detector prepared by the scheme has good photoelectric properties.
2. Example 2
In this embodiment, a description will be given taking a photoelectrochemical working electrode based on BP (black phosphorus) as an example.
The preparation process of the photoelectrochemical working electrode based on BP (black phosphorus) comprises the following steps:
step S22, tearing BP off the block by using a stripping adhesive tape;
step S24, preparation of double-sided conductive tape/ITO
And cutting a section of double-sided conductive adhesive tape, attaching the double-sided conductive adhesive tape to ITO glass, and pressing and pulling the double-sided conductive adhesive tape by fingers or other things to tightly adhere the double-sided conductive adhesive tape to the ITO glass.
Step S26, preparation of working electrode BP/double-sided conductive tape/ITO
Repeatedly folding the stripping adhesive tape adhered with BP, adhering the stripping adhesive tape to the double-sided conductive adhesive tape on ITO, pulling the stripping adhesive tape with fingers or other things, and tearing off the adhesive tape to obtain the BP/double-sided conductive adhesive tape/ITO.
The LSV curves were tested in dark and simulated sun light conditions, respectively, using BP/double sided conductive tape/ITO as the working electrode, saturated calomel electrode as the reference electrode, platinum as the counter electrode, tris-HCl solution (1M) at pH 6.8 as the electrolyte, as shown by the corresponding curves in FIG. 7 (a).
For comparison, the applicant also prepared a BP-based photoelectrochemical working electrode by a liquid phase stripping method of conventional technology, the preparation steps being as follows: weighing a proper amount of BP, putting the BP into an N-methyl pyrrolidone solution, performing ultrasonic treatment, and performing centrifugal separation to obtain an L-BP nanosheet; and dispersing BP nano-sheets on ITO glass in a liquid drop manner, and drying under vacuum condition to obtain BP/ITO. The LSV curves were tested in dark and simulated sunlight conditions, respectively, using BP/ITO as the working electrode, a saturated calomel electrode as the reference electrode, platinum as the counter electrode, and Tris-HCl solution (1M) at pH 6.8 as the electrolyte, as shown by the corresponding curves in FIG. 7 (a).
Referring to FIG. 7 (a), comparing the photocurrent densities of the photoelectrochemical detectors based on S-BP and L-BP, it can be found that the photocurrent density of S-BP is significantly higher than that of L-BP and the dark current of S-BP is lower than that of L-BP. The reason is as in example 1 and will not be described here. BP is well known as a direct bandgap semiconductor material. The above results indicate that the direct bandgap semiconductor material-based detector prepared by the scheme has good photoelectric properties.
3. Example 3
In the present embodiment, the method will be based on MoS 2 The photoelectrochemical working electrode of (molybdenum disulfide) is illustrated as an example.
The preparation process of the photoelectrochemical working electrode based on MoS2 (molybdenum disulfide) is as follows:
step S32, moS is carried out by using the stripping adhesive tape 2 Tearing off the block;
step S34, preparing double-sided conductive adhesive tape/ITO;
and cutting a section of double-sided conductive adhesive tape, attaching the double-sided conductive adhesive tape to ITO glass, and pressing and pulling the double-sided conductive adhesive tape by fingers or other things to tightly adhere the double-sided conductive adhesive tape to the ITO glass.
Step S36, working electrode MoS 2 Preparation of double-sided conductive tape/ITO.
Will be adhered with MoS 2 The stripping adhesive tape is repeatedly folded and then is stuck on the double-sided conductive adhesive tape on the ITO, and after being pressed and pulled by fingers or other things, the adhesive tape is torn off, thus obtaining the MoS product 2 Double-sided conductive tape/ITO.
In MoS 2 Double-sided conductive tape/ITO as working electrode, saturated calomel electrode as reference electrode, platinum as counter electrode, tris-HCl solution (1M) with pH of 6.8 as electrolyte, LSV curve was tested under dark and simulated sunlight conditions, respectively, as shown in the corresponding curve of FIG. 7 (b).
For comparison, the applicant has also prepared MoS-based using conventional techniques (liquid phase stripping) 2 The photoelectrochemical working electrode of the nano-sheet is prepared by the following steps: weighing a proper amount of MoS 2 Putting into N-methyl pyrrolidone solution, performing ultrasonic treatment, and centrifuging to separate L-MoS 2 A nano-sheet. MoS is carried out 2 The nano-sheet dispersion liquid is dripped on ITO glass, and is dried, thus obtaining MoS2/ITO. In MoS 2 ITO is used as a working electrode, a saturated calomel electrode is used as a reference electrode, platinum is used as a counter electrode, tris-HCl solution (1M) with pH of 6.8 is used as electrolyte, and LSV curves are tested under dark and simulated sunlight conditions respectively, as shown by the corresponding curve in (b) of FIG. 7.
Referring to FIG. 7 (b), the comparison is based on S-MoS 2 And L-MoS 2 The photocurrent density of the photoelectrochemical detector of (2) can be found as S-MoS 2 The photocurrent density of (C) is obviously higher than that of L-MoS 2 And S-MoS 2 Is lower than L-MoS 2 A kind of electronic device. The reason is as in example 1 and will not be described here.
4. Example 4
In this embodiment, the method is based on BiFeO 3 The photoelectrochemical working electrode of (bismuth ferrite) is illustrated as an example.
Based on BiFeO 3 The photoelectrochemical working electrode of (bismuth ferrite) is prepared as follows:
step S42, preparing BiFeO by using sol-gel method 3 A nano powder. Dipping BiFeO with stripping tape 3 A nano powder;
step S44, preparation of double-sided conductive tape/ITO
And cutting a section of double-sided conductive adhesive tape, attaching the double-sided conductive adhesive tape to ITO glass, and pressing and pulling the double-sided conductive adhesive tape by fingers or other things to tightly adhere the double-sided conductive adhesive tape to the ITO glass.
Step S46, working electrode BiFeO 3 Preparation of double-sided conductive tape/ITO.
Dipping BiFeO 3 Repeatedly folding the nano-powder stripping adhesive tape, attaching the nano-powder stripping adhesive tape on the double-sided conductive adhesive tape on ITO, pulling with fingers or other things, and tearing off the adhesive tape to obtain the BiFeO product 3 Double-sided conductive tape/ITO.
By BiFeO 3 Double-sided conductive tape/ITO as working electrode, saturated calomel electrode as reference electrode, platinum as counter electrode, tris-HCl solution (1M) with pH of 6.8 as electrolyte, LSV curve was tested under dark and simulated sunlight conditions, respectively, as shown in the corresponding curve of FIG. 7 (c).
For comparison, the applicant has also prepared BiFeO-based using conventional techniques 3 The preparation process of the photoelectrochemical working electrode is as follows: biFeO preparation by sol-gel method 3 Nanopowder, and dispersion with NMP. BiFeO is prepared 3 Dispersing nano particles and dripping on ITO glass, and drying to obtain BiFeO 3 ITO. By BiFeO 3 ITO is used as a working electrode, a saturated calomel electrode is used as a reference electrode, platinum is used as a counter electrode, tris-HCl solution (1M) with pH of 6.8 is used as electrolyte, and LSV curves are tested under dark and simulated sunlight conditions respectively, as shown by the corresponding curve in (c) of FIG. 7.
Referring to FIG. 7 (c), biFeO adhered on the conductive adhesive is compared 3 (S) and BiFeO drop on ITO glass 3 The photocurrent density of the photoelectrochemical detector of (L) was found to be S-BiFeO 3 The photocurrent density is obviously higher than that of L-BiFeO 3 And S-BiFeO 3 Dark current lower than L-BiFeO 3 A kind of electronic device. For the same reasons as in example 1. The above results indicate that the solution is equally applicable to the preparation of high performance photodetectors based on other types of semiconductor materials than two-dimensional materials.
5. Example 5
In this embodiment, a photoelectrochemical working electrode based on double-sided conductive tape/ITO will be described as an example.
The preparation process of the photoelectrochemical working electrode based on the double-sided conductive tape/ITO is as follows:
step S52, preparation of double-sided conductive tape/ITO
And cutting a section of double-sided conductive adhesive tape, attaching the double-sided conductive adhesive tape to ITO glass, and pressing and pulling the double-sided conductive adhesive tape by fingers or other things to tightly adhere the double-sided conductive adhesive tape to the ITO glass.
The LSV curves were tested in dark and simulated sunlight conditions, respectively, using double-sided conductive tape/ITO as the working electrode, saturated calomel electrode as the reference electrode, platinum as the counter electrode, and Tris-HCl solution (1M) at pH 6.8 as the electrolyte, as shown in fig. 7 (d). It can be seen that there is no significant difference in LSV curves in darkness and light. The results indicate that the photocurrent obtained in the above examples was derived from the semiconductor material itself, rather than double sided conductive tape/ITO glass.
Thus, various embodiments of the present invention have been described.
In summary, the invention provides a bridge for electrical connection between a conductive substrate and a nano semiconductor material by using a double-sided conductive tape, and further, an elastic double-sided conductive tape is used, and the mechanical property and the electrical property of the electrical connection between the nano semiconductor material and the double-sided conductive tape are improved by using a pressing manner. Meanwhile, the process is simple and controllable, the production equipment cost is low, the automatic mass production is easy to realize, the problems of large design difficulty, long time consumption, uncontrollable preparation process, small photocurrent density, large dark current and the like of a working electrode in the traditional preparation method are solved, the process has important engineering practical significance, and the process has wide application prospect in the fields of military industry, aerospace, energy, photoelectrons and the like.
It should be noted that, the directional terms, such as "upper" and "lower", etc., in the embodiments are only referring to the directions of the drawings, and are not intended to limit the scope of the present invention. Throughout the drawings, the shapes and dimensions of the various elements in the drawings do not reflect actual sizes and proportions, but merely illustrate the contents of embodiments of the present invention.
In the description of the present invention, it should be noted that, unless explicitly stated and limited otherwise, the terms "connected" and "connected" should be interpreted broadly, and for example, they may be directly connected, or they may be indirectly connected through an intermediate medium, or they may be in communication with each other between two elements. The specific meaning of the terms described above will be understood by those of ordinary skill in the art as the case may be.
Unless clearly indicated to the contrary, the numerical parameters in the specification and claims of the present invention may be approximations that may vary depending upon the context in which the present invention is utilized. In particular, all numbers expressing quantities of ingredients, reaction conditions, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about", and the term "about" is intended to mean that the term "about" is intended to include variations of about 10% by a specified amount in some embodiments.
It should also be noted that, for some implementations, if they are not critical to the present invention and are well known to those of ordinary skill in the art, they are not described in detail in the drawings or the specification, and may be understood with reference to the related art. Moreover, it will be appreciated that the embodiments described above are provided solely for the purpose of enabling the invention to meet the requirements of law and that this invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Furthermore, the above definitions of the elements and methods are not limited to the specific structures, shapes or modes mentioned in the embodiments, and may be simply modified or replaced by those of ordinary skill in the art.
Similarly, it should be appreciated that in the above description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. However, the method of the invention should not be interpreted as reflecting the intention: the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. In addition, the embodiments can be mixed and matched with each other or other embodiments based on design and reliability, i.e. the technical features of different embodiments can be freely combined to form more embodiments. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
The above embodiments are provided to illustrate the objects, technical means and advantageous effects of the present invention in detail, and it should be understood that the detailed description is intended to more clearly understand the present invention and is not intended to limit the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. A photoelectrochemical working electrode, comprising:
a conductive substrate;
a double-sided conductive adhesive tape which is in a two-dimensional shape, and a first side of the double-sided conductive adhesive tape is stuck on the conductive substrate;
and the nano semiconductor material is adhered to the second surface of the double-sided conductive adhesive tape.
2. The photoelectrochemical working electrode of claim 1 wherein said double-sided conductive tape comprises: a support material, a viscoelastic material, and a conductive medium; wherein:
a support material for providing support for the conductive medium, the viscoelastic material and the conductive connecting material, in the form of a film or a fiber, the material being selected from one or more of the following: polyamides, polyimides, polyesters;
a viscoelastic material arranged on the supporting material and used for bonding the supporting material, the conductive substrates at two sides of the supporting material and the nano semiconductor material; the elastic modulus is between 2k and 20MPa, the thickness is between 1 and 1000 mu m, and the material is selected from one or more of the following materials: epoxy resins, polyurethanes, polyisocyanates, silicone gums, acrylic, polyurethanes, polyols;
a conductive medium dispersed in the viscoelastic material for transmitting charges, wherein the conductive medium is in the form of powder, coating or wire, and the conductive medium is one or more of the following materials: carbon, aluminum, copper, gold, silver.
3. The photoelectrochemical working electrode of claim 2 wherein, for said double sided conductive tape:
the supporting material is non-woven fabric;
the conductive medium is carbon powder;
the viscoelastic material is acrylic acid;
wherein the thickness of the viscoelastic material is 40 μm or more.
4. The photoelectrochemical working electrode of claim 2, wherein the double-sided conductive tape has a sheet resistance of less than 1000ohms/sq; preferably less than 10ohms/sq.
5. The photoelectrochemical working electrode according to claim 1, wherein,
the conductive substrate is a rigid substrate or a flexible substrate; and/or
The nano semiconductor material is a zero-dimensional, one-dimensional or two-dimensional nano semiconductor material.
6. The photoelectrochemical working electrode according to claim 5, wherein,
the conductive substrate is an ITO substrate or an FTO substrate;
the nano semiconductor material is a two-dimensional InSe nano sheet;
the double-sided conductive adhesive tape is a conductive adhesive tape for a scanning electron microscope.
7. A method of manufacturing a photoelectrochemical working electrode according to any of claims 1 to 6, comprising:
step A, sticking a first surface of a double-sided conductive adhesive tape on a conductive substrate;
step B, preparing a nano semiconductor material;
and C, transferring the nano semiconductor material to the second surface of the double-sided conductive adhesive tape.
8. The method of claim 7, wherein the double-sided conductive tape in the photoelectrochemical working electrode comprises: a conductive medium, a viscoelastic material, and a support material;
one surface of the viscoelastic material, which is adhered with the nano semiconductor material, has elasticity;
the step C further comprises the following steps: pressing the nano semiconductor material towards the direction of the double-sided conductive tape.
9. The method according to claim 8, wherein,
in the step B, preparing the nano semiconductor material by an adhesive tape stripping method or a liquid phase stripping method; and/or
In the step C, the nano semiconductor material is transferred on the second surface of the double-sided conductive adhesive tape by dry transfer, wet transfer or coating nano semiconductor material dispersion liquid.
10. A photoelectrochemical device, comprising: the photoelectrochemical working electrode of any one of claims 1 to 5;
wherein the photoelectrochemical device is a photoelectrochemical detector or a photoelectrochemical hydrogen production device, the light source is monochromatic light or polychromatic light, and the wavelength range is 200-2000nm.
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