KR102117925B1 - Triboelectric generator and its manufacturing method - Google Patents

Abstract

The present invention relates to a triboelectric generator of which output is improved than output of an existing triboelectric generator as a surface charge is controlled when an electron blocking layer of a material with a high dielectric constant is deposited on an electrode layer, and a manufacturing method thereof. The triboelectric generator comprises: a first electrode; a second electrode spaced apart from the first electrode at regular intervals in a state of being electrically connected to the first electrode; a friction layer in selective contact with the first electrode, provided between the first electrode and the second electrode, and formed of a material having a difference in electronegativity from the first electrode; and an electron blocking layer having one end coupled to the friction layer and the other end coupled to the second electrode, and formed of a material having a higher dielectric constant compared to the friction layer.

Description

Triboelectric generator and its manufacturing method{TRIBOELECTRIC GENERATOR AND ITS MANUFACTURING METHOD}

The present invention relates to a triboelectric generator for improving power, and in detail, an electrostatic barrier layer of a material having a high dielectric constant is deposited on an electrode layer to control the surface charge so that the triboelectric generator improves output compared to a conventional triboelectric generator. It relates to a manufacturing method.

Friction electricity generation generates electricity by friction, and unlike conventional eco-friendly energy such as solar cells, water power, wind power, etc., it is possible to extract minute vibrations generated in the surroundings or consumable mechanical energy generated during exercise as electrical energy.

The tribological nanogenerator is developed by using mutual contact and separation between two objects having different triboelectric properties, and most tribological nanogenerators require two electrode layers. Then, a conductive metal is attached to the surface of the thin film material that rubs against one electrode layer, and then the two electrode layers output power through contact and separation.

Therefore, the triboelectric nanogenerator (frictional electric nanogenerator) is evaluated as a promising next-generation energy generator due to desirable properties such as light weight, portability, environmental friendliness, and low cost. Technology has been proposed.

For example, Korean Patent Publication No. 10-2017-0126522 (published date: 2017.11.17) relates to a single-pole friction nanogenerator, a power generation method, and a self-driven tracking device, wherein a polymer material and a metal material have different frictions. A single-pole triboelectric generator is constructed by using a charging characteristic, and a tracking system based on the generator is manufactured.

However, there is a lack of technology development for a method or configuration for improving the output of a number of triboelectric nanogenerators, including the prior literature.

Korean Patent Publication No. 10-2017-0126522 (published date: 2017.11.17)

The present invention seeks to improve the output of a triboelectric generator.

The present invention is to provide an electron blocking layer between the electrode and the friction material to maintain a high surface charge density at the surface of the friction material.

The present invention relates to a triboelectric generator for improving power to achieve the above object, a first electrode, a second electrode spaced a predetermined distance in an electrically connected state with the first electrode, and the first electrode and optional And the first electrode and the second electrode, the friction layer and one end formed of a material having a difference in electronegativity from the first electrode and one end coupled to the friction layer, the other end It is coupled to the second electrode, and includes an electron blocking layer formed of a material having a higher dielectric constant than the friction layer.

Preferably, the electron blocking layer is deposited in the form of a thin film on the second electrode.

Preferably, the electron blocking layer is deposited on the second electrode by sputtering, and the friction layer is bonded on the electron blocking layer.

Preferably, the electron blocking layer is formed of oxide.

Preferably, the electron blocking layer includes at least one of TiOx, AlOx, and HfOx.

Preferably, the electron blocking layer is formed to a thickness of 80 to 120nm.

Preferably, the electron blocking layer is formed to a thickness of 100nm.

Preferably, the friction layer is formed of a material having a greater electronegativity or work function than the first electrode.

Preferably, the friction layer is formed of any one of PDMS, PTFE, FEP, PAN, and PVC.

Preferably, the first and second electrodes are formed of a metal material.

Preferably, the first and second electrodes are made of aluminum.

Preferably, a first electrode, a second electrode, a step of providing a friction layer made of a material having a difference in electronegativity from the first electrode, and an electron blocking layer having a higher dielectric constant than the friction layer on the second electrode. Depositing, bonding the friction layer over the electron blocking layer, disposing the first electrode at a predetermined distance from the friction layer, and electrically connecting the first electrode and the second electrode. do.

Preferably, the electron blocking layer is deposited on the second electrode in the form of a thin film by sputtering deposition.

Preferably, the electron blocking layer is deposited while the oxygen partial pressure is 0%.

Preferably, the electron blocking layer includes at least one material of TiOx, AlOx, and HfOx.

Preferably, the electron blocking layer is formed to a thickness of 80 to 120nm.

Preferably, the first electrode and the second electrode are formed of a metal material, and the friction layer is formed of a PDMS material.

The triboelectric generator according to the present invention has an effect of improving output power.

The present invention improves output power due to the coupling effect of the electron blocking of the electron blocking layer and the improved polarization.

The present invention has an effect of improving the output power according to the thickness and material of the electron blocking layer.

1 is a front view of a triboelectric generator according to the present invention,
2 is a view of the operating principle of the triboelectric generator according to the present invention,
3 is a charge density graph of the triboelectric generator according to the present invention,
4 is a COMSOL multiphysics simulation graph of a triboelectric generator according to the present invention,
5 is a graph of the output voltage and current according to the presence or absence of an electron blocking layer in the triboelectric generator according to the present invention,
6 is a result of comparing the surface potential according to the presence or absence of the electromagnetic blocking layer in the triboelectric generator according to the present invention,
7 is a graph comparing the output by the partial pressure of oxygen in the triboelectric generator according to the present invention,
8 is an oxygen K-edge XAS spectrum of the triboelectric generator according to the present invention,
9 is an enlarged view of the oxygen K-edge XAS spectrum of the triboelectric generator according to the present invention and a graph of relative regions related to oxygen voids,
10 is a schematic diagram of an electron trap mechanism according to oxygen deficiency of a triboelectric generator according to the present invention,
11 is a graph comparing the output voltage and current according to the thickness of the electromagnetic blocking layer in the triboelectric generator according to the present invention,
12 is an oxygen K-edge XAS spectrum according to the thickness of the electron blocking layer in the triboelectric generator according to the present invention,
13 is a graph of the relative ratio of the relative molecular orbital ratio as a function of the electron blocking layer in the triboelectric generator according to the present invention,
14 is a comparative view of the output change according to the deposition location of the charge blocking layer in the triboelectric generator according to the present invention,
15 is a comparative view of the output change according to the material constituting the charge blocking layer in the triboelectric generator according to the present invention,
16 is a flow chart for a method of manufacturing a triboelectric generator according to the present invention.

The specific structure or functional descriptions presented in the embodiments of the present invention are exemplified for the purpose of describing the embodiments according to the concept of the present invention, and the embodiments according to the concept of the present invention may be implemented in various forms. In addition, it should not be construed as being limited to the embodiments described herein, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

1 relates to a front view of a triboelectric generator according to the present invention.

The triboelectric generator 1 according to an embodiment of the present invention includes a first electrode 10, a second electrode 12 spaced a predetermined distance in a state of being electrically connected to the first electrode 10, and a first electrode The friction layer 20, which is selectively contacted with 10, is provided between the first electrode 10 and the second electrode 12, and is formed of a material having a difference in electronegativity from the first electrode 10. And one end coupled to the friction layer 20, the other end coupled to the second electrode 12, and an electron blocking layer 30 formed of a material having a higher dielectric constant than the friction layer 20.

The first electrode 10 and the second electrode 12 may be formed in a plate shape, or may be formed of a metal material through which electricity can flow. The first electrode 10 and the second electrode 12 may be formed of a metal material, for example, may be formed of a metal such as aluminum, copper or silver having high electrical conductivity. The first electrode 10 and the second electrode 12 may be formed of the same material, or may be formed of different materials.

The first electrode 10 and the second electrode 12 may be disposed spaced apart from each other by a predetermined distance. Between the first electrode 10 and the second electrode 12, the friction layer 30 selectively contacting the first electrode 10 and the friction layer 30 and the second electrode 12 are inserted between An electron blocking layer 30 may be provided.

Further, the first electrode 10 and the second electrode 12 may be electrically connected by wires such as wires through which electricity can flow, and the first electrode 10 is contacted and separated from the friction layer 20 In this case, electricity may flow through the wire.

The friction layer 20 is formed in a plate shape, and may be disposed to be selectively contacted with the first electrode 10 under the first electrode 10.

The friction layer 20 is formed of a material having a greater electronegativity than the first electrode 10. Accordingly, when the first electrode 10 and the friction layer 20 are in contact with each other, the electronegativity is greater. The layer 20 is charged with a negative charge, and the first electrode 10 having a smaller electronegativity than the friction layer 20 may be charged with a positive charge.

The friction layer 20 may be formed of a synthetic resin material, for example, PDMS material.

The electron blocking layer (EBL) 30 is deposited on the second electrode 12 in the form of a thin film, and may be formed of a material having a higher dielectric constant than the friction layer 20. Specifically, the electron blocking layer 30 may be formed of oxide, and may be formed of materials such as TiOx, AlOx, and HfOx.

In addition, the thickness of the electron blocking layer 30 is preferably 80 to 120 nm, from the viewpoint of improving the output of the generator, and preferably is formed to a thickness of 100 nm.

The electron blocking layer 30 of the triboelectric generator 1 may be deposited on the second electrode 12 by sputtering, and the friction layer 20 is coupled on the electron blocking layer 30.

 When the friction layer 20 is attached to the electron blocking layer 30, the triboelectric generator 1 can be completed.

That is, the first electrode 10 and the second electrode 12 and the friction layer 20 and the electron blocking layer 30 are sequentially stacked so that the triboelectric generator 1 can be contacted and separated in the vertical direction. It will be produced.

As the above-mentioned electron blocking layer 30 is inserted between the second electrode 12 and the friction layer 20, the output performance can be greatly improved as the surface charge density of the triboelectric generator 1 is improved. Detailed description will be described later.

Figure 2 shows a diagram of the operating principle of the triboelectric generator according to the present invention.

Among the pair of electrode layers 10 and 12, the electron blocking layer 30 is deposited between the second electrode 12 and the friction layer 20 and a generator that only has the friction layer 20 on the second electrode 12. The driving principle of the frictional electric generator 1 is compared.

The left view of FIG. 2 is a generator that does not deposit the electron blocking layer 30 on the second electrode 12, and the first electrode 10 of the generator that directly attaches the friction layer 20 to the second electrode 12 When the operation of attaching and dropping the second electrode 12 is repeated, the surface of the friction layer 20 is negatively charged. At this time, at the interface between the friction layer 20 and the second electrode 12, induction of positive charges is performed by the amount of negative charges charged on the surface of the friction layer 20. In addition, due to the negative charge, which is electrons existing in the second electrode 12, there is a positive charge that is screened out at the interface between the second electrode 12 and the friction layer 20, which is the charge on the surface of the friction layer 20. Density decreases.

On the other hand, in the case of the triboelectric generator 1 in which the electron blocking layer 30 is inserted between the second electrode 12 and the friction layer 20, the output characteristics of the friction layer 20 can be improved, and the electron blocking Through the dielectric constant of the layer 30, it is possible to control the output characteristics of the friction layer 20.

That is, the positive charge is maintained through the movement of free electrons by the oxygen vacancy portion existing in the electron blocking layer 30, and the output is improved by increasing the polarization due to the high dielectric constant.

In addition, the surface charge density of the triboelectric generator 1 can be improved by forming a composite with a polarization using high dielectric constant particles in the friction layer 20. That is, the electron blocking layer 30 uses aluminum oxide (Al2O3), titanium oxide (TiO2), and hafnium oxide (HfO2), which are oxidizing materials, which have a high dielectric constant because the dielectric constant is very high compared to the friction layer 20. The electron blocking layer 30 improves the polarization 44 of the friction layer 20 to improve output.

On the other hand, in order to measure the dielectric constant (εr) values of the electromagnetic blocking layer 30 and the friction layer 20 of the triboelectric generator 1, a capacitance-voltage (CV) is applied to the metal-insulator-metal (MIM) structure. You can get it through consciousness.

Equation (1)

은 마찰층(20) 또는 전자 차단층(30)의 두께,

는 커패시턴스-전압(C-V) 실험 결과의 최대값, A는 MIM 구조에서 상부 전극의 면적,

는 자유 공간의 유전율이며,

은 마찰층 또는 전자 차단층의 유전율이다. here,

The thickness of the silver friction layer 20 or the electron blocking layer 30,

Is the maximum value of the capacitance-voltage (CV) test result, A is the area of the upper electrode in the MIM structure,

Is the permittivity of free space,

Is the dielectric constant of the friction layer or electron blocking layer.

)이 높은 전자 차단층(30)과 마찰층(20)의 두께를 조절하여 마찰전기 발전기(1)를 제조할 수 있을 것이다.As can be seen from Equation (1), the value of the electrostatic capacitance (C) is inversely proportional to the thickness of the electron blocking layer 30, so that it will have a small electrostatic capacity of the thick friction layer 20. The dielectric constant (

) The frictional electric generator 1 may be manufactured by adjusting the thickness of the high electron blocking layer 30 and the friction layer 20.

Figure 3 shows the charge density graph of the triboelectric generator according to the present invention and Figure 4 shows the results of the COMSOL multiphysics simulation of the triboelectric generator according to the present invention.

A graph comparing the surface charge density of the generator according to the presence or absence of the electron blocking layer 30. When the electron blocking layer 30 is inserted between the second electrode 12 and the friction layer 20, the surface charge density It can be seen that is increased.

The generator 1 without the electron blocking layer 30 (W/O TiOx EBL) exhibited a surface charge density of about 15 μC/m 2, but the electron blocking layer 30 according to the present invention was inserted (With TiOx EBL). The triboelectric generator 1 reached 30 μC/m 2.

It relates to an image measured by COMSOL multi-physics simulation to compare the friction potential distribution of the triboelectric generator 1 according to the presence or absence of the electron blocking layer 30.

The friction potential distribution of the triboelectric generator 1 in which the electron blocking layer 30 on the right is inserted (With TiOx EBL) is more than the generator 1 without the electron blocking layer 30 on the left (W/O TiOx EBL). You can see that it is high.

Figure 5 shows a graph comparing the output voltage and current according to the presence or absence of the electromagnetic blocking layer in the triboelectric generator according to the present invention.

The generator without the electron blocking layer 30 (W/O TiOx EBL) generated a peak output voltage of ˜50 V and a peak output current of 2 μA. On the other hand, it can be seen that the triboelectric generator 1 in which the electron blocking layer 30 is inserted (with TiOx EBL) shows a very improved output value with output voltage and current of about 272 V and 9.1 μA, respectively.

This is because the electron blocking layer 30, which is an insulator material inserted at the interface between the second electrode 12 and the friction layer 20, is a material having very little electrons (negative charge) compared to the second electrode 12, so it is inserted at the interface. When it is, it plays the role of an electron blocking layer (EBL) 30 that reduces the amount of positive charge that is screened out at the interface.

In addition, the electron blocking layer 30 is a material having a high dielectric constant, and when inserted into the interface, maintains a high polarization state of the friction layer 20 to capture more electrons when contacting the first electrode 10. It becomes possible.

It can be explained that the output characteristics of the friction layer 20 in which the electron blocking layer 30, which is an oxide thin film, is inserted at the interface between the second electrode 12 and the friction layer 20 as two main causes are explained. will be.

Figure 6 relates to the results of comparing the surface potential according to the presence or absence of the electron blocking layer in the triboelectric generator according to the present invention.

Electrode layer 10, 12 for CPD analysis of the frictional charge amount on the surface of the friction layer 20 with or without the electron blocking layer 30 to demonstrate an approach for improving the output performance of the triboelectric generator 1 ) Is when the contact and separation are performed sequentially.

The CPD analysis method is achieved through contact and separation of the first electrode 10 and the second electrode 12 of the generator (a) without the electron blocking layer 30 and the generator (b) with the electron blocking layer 30 inserted. The contact potential induced on the surface of the friction layer 20 is measured.

In the case of contact between the first electrode 10 and the second electrode 12, the surface potential value of the friction layer 20 without the electron blocking layer 30 is 815 mV, and the friction layer with the electron blocking layer 30 ( The surface potential value of 20) is 395 mV. The reason that the surface potential of the friction layer 20 including the electron blocking layer 30 is remarkably low may be due to the improved polarization of the friction layer 20 caused by the electron blocking layer 30, and accordingly the friction layer The electrons present on the surface of (20) are canceled out.

That is, the reason why the surface potential value before contact is low is that the polarization of the first electrode 10 and the friction layer 20 is improved.

After the contact between the first electrode 10 and the second electrode 12, the surface potential value of the friction layer 20 without the electron blocking layer 30 is 954 mV, which is 130 mV greater than before friction, while the electron blocking layer 30 is In the case of the provided friction layer 20, it has a surface potential value of 1035 mV, and the potential value has increased by 640 mV through the processes before and after contact of the electrode layers 10 and 12.

This is because the electron blocking layer 30 is provided between the second electrode 12 and the friction layer 20 of the triboelectric generator 1, so that the blocking effect of the electrons and the polarization coupling effect are improved, so that the surface of the friction layer 20 is high. It has a surface charge density.

Figure 7 relates to a graph comparing the output by the partial pressure of oxygen in the triboelectric generator according to the present invention.

When the relative humidity is maintained at 38% and the second electrode 12 and the electron blocking layer 30 are deposited, the oxygen partial pressure is adjusted to 0%, 1%, and 2%, respectively, to thereby characterize the friction layer 20. It was investigated. However, the output voltage and current of the triboelectric generator 1 equipped with the electron blocking layer 30 (TiOx EBL) are greater than the generator without the electron blocking layer 30 (W/O TiOx EBL) regardless of the oxygen partial pressure. You can see that it is high.

The magnitude of the output voltage and current of the triboelectric generator 1 according to the degree of oxygen partial pressure is when the second electrode 12 and the electron blocking layer 30 are deposited in a state where the oxygen partial pressure is lower than when the oxygen partial pressure is high. The output voltage and current of the triboelectric generator 1 were higher. Therefore, when the electron blocking layer 30 is deposited on the second electrode 12, the frictional electric generator 1 will have a high output voltage only when deposition is performed in an atmosphere where the oxygen partial pressure is 0%.

That is, as the oxygen partial pressure increases, the electron blocking property of the electron blocking layer 30 decreases. The main cause of this change can be seen through the analysis of the electronic structure of the electron blocking layer 30 through X-ray absorption spectroscopy, and details of this will be described below.

8 relates to the oxygen K-edge XAS spectrum of the triboelectric generator according to the present invention.

The correlation between the electronic structure of the electron blocking layer 30 and the energy conversion mechanism of the triboelectric generator 1 using the electron blocking layer 30 was investigated. The function of the oxygen partial pressure measured by XAS is the electron blocking layer 30 ) Shows the molecular orbital structure hybridized in the conduction band.

The normalized intensity of the oxygen K-edge spectrum of the electron blocking layer 30 directly reflects molecular orbital hybridization between the Ti orbit (3d and 4sp states) and the O orbit (2p state) based on local atomic bond symmetry. The oxygen K-edge spectrum reverts to six distinct Gaussian absorption peaks for the second derivative of the oxygen K-edge spectrum used to determine the energy level of the molecular orbital state.

As the oxygen partial pressure increases from 0% to 2%, the relative area of the conduction band decreases, and the transport of charges improves due to an increase in the unoccupied absorption state that occurs by adding a hybridized state to the extended conduction band region. .

In other words, when the oxygen partial pressure increases, the area of the conduction band of the electron blocking layer 30 decreases. This means a reduction in the non-occupied state in the conduction band in the electronic structure of the electron blocking layer 30, and consequently, the transport ability of electrons in the electron blocking layer 30 may be weakened.

9 is an enlarged view of the oxygen K-edge XAS spectrum of the triboelectric generator according to the present invention and a relative area related to oxygen vacancies, and FIG. 10 is a schematic diagram of an electron trap mechanism according to oxygen deficiency of the triboelectric generator according to the present invention .

The results of the analysis of the defect state closely related to the oxygen void existing in the band gap located under the conduction band are shown. As the oxygen partial pressure increases, the relative area of the defect state tends to decrease. .

Oxygen vacancy is one of the defects found in oxides. It is an anion vacancy that occurs when oxygen escapes. Therefore, the defects occurring in the oxide occur in the direction of matching the electrical neutrality in the material, and in the case of oxygen, it has a -2 valence charge, so it tries to occupy two electrons to match the electrical neutrality of this vacancies. When oxygen vacancies occur, the conduction band becomes wider than the stable state, which means that the electrical conductivity increases.

Oxygen pores have positive charges, so electrons or oxygen ions with negative charge characteristics can be trapped. Therefore, it can be seen that in order to improve the electron blocking property, an electronic structure including many defect states capable of trapping electrons is advantageous.

That is, the change in the band edge state associated with oxygen deficiency may affect the electron blocking properties of the electron blocking layer 30, and the degree of negative charge traps including electrons and oxygen ions may change.

As a result, it can be seen that the increase in the band edge state is correlated with the improvement of the electron blocking property of the electron blocking layer 30.

11 relates to a graph comparing the output voltage and the current according to the thickness of the electron blocking layer in the triboelectric generator according to the present invention.

The output voltage and current characteristics of the triboelectric generator 1 having the electron blocking layer 30 are measured as a function of the thickness of the electron blocking layer 30 measured at a relative humidity of 65% (however, the electron blocking layer 30 ) Is deposited at 0% oxygen partial pressure)

The electron blocking layer 30 deposited on the second electrode 12 has a different color depending on the thickness of the electron blocking layer 30 when viewed from the optics. This phenomenon is caused by different thicknesses of the electron blocking layer 30. Because of the interference effect.

That is, as the thickness of the electron blocking layer 30 increases from 20 nm to 100 nm, the output voltage and current increase significantly from 128 V and 3.5 μA to 272 V and 9.1 μA, respectively, and the thickness of the electron blocking layer 30 is approximately 80 to In the case of 120 nm, it was confirmed that the output current increased compared to other thicknesses. In particular, when the thickness of the electron blocking layer 30 was 100 nm, it was confirmed that the maximum output voltage and output current appeared.

This is an XRD analysis to investigate how the physical structure of the electron blocking layer 30 changes at various thicknesses. As a result, the thickness of the electron blocking layer 30 does not affect the physical structure, and the amorphous structure is preserved. Therefore, when the thickness of the electron blocking layer 30 is increased, electron blocking characteristics are improved due to an increase in the relative amount of oxygen vacancies.

However, considering the total capacitance of the capacitors connected in series, the total capacitance decreases due to an increase in the thickness of the electron blocking layer 30, which means a decrease in power generation.

Equation (2)

는 총 커패시턴스,

및

는 각 재료의 상대 유전율이며,

및

는 각 층의 두께이다. 따라서, 전자 차단층(30)의 두께 변화는 전자 차단 특성과 총 커패시턴스 사이의 트레이드 오프 관계를 갖게 된다.here

Is the total capacitance,

And

Is the relative permittivity of each material,

And

Is the thickness of each layer. Therefore, the thickness change of the electron blocking layer 30 has a trade-off relationship between electron blocking properties and total capacitance.

12 is an oxygen K-edge XAS spectrum according to the thickness of the electron blocking layer in the triboelectric generator according to the present invention, and FIG. 13 is a relative ratio of the relative molecular orbital ratio as a function of the electron blocking layer in the triboelectric generator according to the present invention It is about.

In order to understand the change in the output performance of the triboelectric generator 1 according to the thickness of the electron blocking layer 30 as an electronic structure, a hybrid molecular orbital structure analysis is performed. As the thickness of the electron blocking layer 30 is changed, The ratio between the conduction band state and the 4sp state changes.

과

의 분자 궤도 대칭성이 향상되어 d-궤도 상태의 균일한 분포가 유도된다. For example, if the number of states increases,

and

Improves the molecular orbital symmetry of, resulting in a uniform distribution of the d-orbital state.

This change in d-orbital alignment can improve charge transfer due to the symmetrical distribution of the empty state in three-dimensional orbits in five directions.

Another increase in the relative proportions of the 4sp trajectory can lead to an increase in charge transport due to the improvement of the spherically symmetric s-orbital compared to the directional d-orbit, which is optimized charge transport when the thickness of the electron blocking layer 30 is 100 nm. This is possible.

When the electron blocking layer 30 is 100 nm thick, charge transport can easily move electrons within the electron blocking layer 30. Since the electrons easily move even when there is an oxygen gap in the same amount as the electron blocking layer 30, it is possible to reduce the trapping time τT of the electrons due to the oxygen gap and increase the trap speed νT, thereby blocking the electron blocking layer 30 ), the electron blocking property is improved.

14 relates to a comparison of the output change according to the deposition position of the charge blocking layer in the triboelectric generator according to the present invention.

It relates to a graph comparing the degree of output according to the deposition position of the electron blocking layer 30, Type1 does not have an electron blocking layer 30, between the first electrode 10 and the second electrode 12 It is a generator made of the friction layer 20, and Type2 is a generator in which an electron blocking layer 30 is deposited on the top of the friction layer 20 in Type1. Finally, Type3 is a triboelectric generator 1 according to the present invention, in which the first electrode 10, the friction layer 20, the electron blocking layer 30 and the second electrode 12 are sequentially stacked.

When each generator is generated, it can be seen that the type 3 generator has the highest output voltage and current, and it can be seen that the output is high in the order of type 1 and type 2. That is, the output of the triboelectric generator 1 according to the present invention was the highest, and the output of the generator provided with the type 2 electromagnetic blocking layer 30 on the top of the triboelectric layer 20 was the lowest.

This strengthens the polarization of the friction layer 20 as the electron blocking layer 30 is positioned between the second electrode 10 and the friction layer 20, and reduces the separation of the electrons 40 of the friction layer 20 This is because it acts to increase the output voltage and current of the triboelectric generator 1.

15 shows a comparison of the output change according to the material constituting the charge blocking layer in the triboelectric generator according to the present invention.

When the material constituting the electron blocking layer (EBL) 30 among the generator without the electron blocking layer 30 (W/O EBL) and the triboelectric generator 1 according to the present invention is made of TiOx, AlOx and HfOx The output is compared and graphed.

The output of the generator without the electron blocking layer 30 (W/O TiOx EBL) was the lowest, and the output of the triboelectric generator 1 of the electron blocking layer 30 made of AlOx did not have the electron blocking layer 30. It can be seen that it is slightly higher than the output of the generator. On the other hand, the output of the generator of the electron blocking layer 30 made of TiOx and AlOx is very high.

The reason why the output of the generator of the electron blocking layer 30 made of TiOx and AlOx is high is that TiOx and AlOx have a relatively high dielectric constant and a small band gap. That is, TiOx has a higher output than the generator of the electron blocking layer 30 made of AlOx, which is a band in which TiOx has a higher dielectric constant than AlOx and does not exist in the state of electrons between the TiOx materials. This is because the band gap is smaller. Due to this, the output of the triboelectric generator 1 made of the electron blocking layer 30 of TiOx is the largest.

16 relates to a flow chart for a method of manufacturing a triboelectric generator according to the present invention.

The process of manufacturing the triboelectric generator 1 includes preparing a friction layer made of a material having a difference in electronegativity from the first electrode, the second electrode, and the first electrode (S10), and comparing the frictional layer to the second electrode. Depositing an electron blocking layer having a high dielectric constant (S20), combining a friction layer on the electron blocking layer (S30), and disposing the first electrode at a predetermined distance from the friction layer, and placing the first electrode and the second electrode. And electrically connecting (S40).

The first electrode, the second electrode, and the step of providing a friction layer of a material having a difference in electronegativity from the first electrode (S10) is a metal material made of a plate-like electrode layer 10, 12, and the same size and material The electrode layers 10 and 12 made of are positioned to be spaced apart at predetermined intervals. Preferably, an aluminum foil having a size of 3×3 cm 2 and having a thickness of 80 μm may be used as the electrode layers 10 and 12. And it is formed of a PDMS material, and has a friction layer 20 made of a material having a greater electronegativity than the first electrode 10.

The friction layer 20 may be manufactured through imprint lithography (SIL) technology using a doctor-blade and a Teflon template as a mold.

Looking at the manufacturing process, the friction layer 20 is mixed with a base resin and a curing agent (Sylgard 184A: Sylgard 184B) in a weight ratio of 10:1, laminated to a Teflon mold by doctor blade technology and cured at 80° C. for 4 hours. . When the cured friction layer 20 is carefully peeled from the Teflon mold, the fabrication is completed with a flat PDMS having a thickness of about 200 μm.

The step of depositing the electron blocking layer 30 having a higher dielectric constant than the friction layer on the second electrode (S20) is to deposit the electron blocking layer 30 on the second electrode 12, preferably for radio frequency sputtering. Thereby, the electron blocking layer 30 is deposited on the second electrode 12.

More specifically, the first electrode 10 and the second electrode 10 are commercial aluminum foils, sized to 3×3 cm 2 and 80 μm thick, washed with ethanol, and dried with N 2 gas.

Then, an electron blocking layer 30 is deposited on one surface of the electrode layer 10 in order to manufacture the second electrode 12 of the triboelectric generator 1. At this time, the second electrode 12 and the electron blocking layer 30 should not have any voids between the deposited layers, and the second electrode 12 on which the electron blocking layer 30 is deposited is cured at 100° C. for 8 hours. Order.

In the step of bonding the friction layer over the electron blocking layer (S30 ), the friction layer 20 is attached to the electron blocking layer 30 of the second electrode 12. The friction layer 20 is a mixture of a base resin and a curing agent in a weight ratio of 10:1, laminated to a Teflon mold by doctor blade technology and cured at 80° C. for 4 hours, flat friction of about 200 μm thickness in the Teflon mold The layer 20 is obtained.

Disposing the first electrode at a predetermined distance from the friction layer, and electrically connecting the first electrode and the second electrode (S40), the electrode layers 10 and 12 are spaced apart in an electrically connected state by wires or the like. By doing so, the first electrode 10 and the second electrode 12 may be arranged to be selectively contacted and separated vertically.

The electromagnetic blocking layer 30 installed on the second electrode 12 strengthens the polarization of the friction layer 20 and prevents the electrons 40 on the surface of the friction layer 20 from being screened out, thereby generating a frictional electric generator ( The output of 1) is improved.

The present invention described above is not limited by the above-described embodiments and accompanying drawings, and various substitutions, modifications, and changes are possible within the scope of the present invention without departing from the technical spirit of the present invention. It will be obvious to those who have the knowledge of.

1: triboelectric generator 10: first electrode
12: second electrode 20: friction layer
30: electron blocking layer 40: electron
42: positive charge 44: polarization

Claims (17)

A first electrode;
A second electrode spaced a predetermined distance in a state of being electrically connected to the first electrode;
A friction layer selectively contacted with the first electrode, provided between the first electrode and the second electrode, and formed of a material having a difference in electronegativity from the first electrode; And
An electron blocking layer having one end coupled to the friction layer and the other end coupled to the second electrode;
It includes,
The electron blocking layer has an oxygen vacancy portion and is made of a material having a higher dielectric constant than the friction layer, and a triboelectric generator that enhances polarization of the friction layer. According to claim 1,
The electron blocking layer is a triboelectric generator that is deposited in the form of a thin film on the second electrode. According to claim 2,
The electron blocking layer is deposited on the second electrode by sputtering, and the friction layer is a triboelectric generator coupled to the electron blocking layer. According to claim 1,
The electron blocking layer is a triboelectric generator formed of oxide. The method of claim 4,
The electron blocking layer is a triboelectric generator comprising at least one material of TiOx, AlOx and HfOx. According to claim 1,
The electron blocking layer is a triboelectric generator formed to a thickness of 80 to 120nm. The method of claim 6,
The electron blocking layer is a triboelectric generator formed to a thickness of 100nm. According to claim 1,
The friction layer is a triboelectric generator formed of a material having a greater electronegativity or work function than the first electrode. The method of claim 8,
The friction layer is a triboelectric generator formed of any one of PDMS, PTFE, FEP, PAN, and PVC. According to claim 1,
The first and second electrodes are triboelectric generators formed of a metal material. The method of claim 10,
The first and second electrodes are triboelectric generators made of aluminum. Providing a first electrode, a second electrode, and a friction layer of a material having a difference in electronegativity from the first electrode;
Depositing an electron blocking layer having an oxygen vacancy portion on the second electrode and made of a material having a higher dielectric constant than the friction layer to enhance polarization of the friction layer;
Bonding the friction layer over the electron blocking layer; And
Placing the first electrode at a predetermined distance from the friction layer, and electrically connecting the first electrode and the second electrode;
Method of manufacturing a triboelectric generator comprising a. The method of claim 12,
The electron blocking layer is a method of manufacturing a triboelectric generator deposited on the second electrode in a thin film form by a sputtering deposition method. The method of claim 12,
The electron blocking layer is a method of manufacturing a triboelectric generator that is deposited in a state where the partial pressure of oxygen is 0%. The method of claim 12,
The electron blocking layer is a method of manufacturing a triboelectric generator formed of an oxide containing at least one of TiOx, AlOx and HfOx. The method of claim 12,
The electron blocking layer is 80 to 120nm to form a triboelectric generator manufacturing method. The method of claim 12,
The first electrode and the second electrode is formed of a metal material, the friction layer is a method of manufacturing a triboelectric generator formed of a PDMS material.

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