CN102694047B - A kind of energy storage photovoltaic CIGS solar cell and its preparation method - Google Patents

Abstract

The invention discloses an energy storage photoelectric CIGS solar cell, which is characterized in that: the structural layer of the energy storage photoelectric CIGS solar cell is sequentially arranged from top to bottom: the CIGS solar cell comprises a top surface conductive glass substrate, a CIGS electricity storage layer, a first electrolyte layer, a diaphragm, a second electrolyte layer, an electricity storage layer and a bottom surface conductive glass substrate, wherein the top surface conductive glass substrate and the bottom surface conductive glass substrate are used as counter electrodes. The invention does not need an external storage device, integrates the functions of light energy conversion electric energy and electric energy storage in the same structure, and has the non-light energy charging function.

Description

A kind of energy storage photovoltaic CIGS solar cell and its preparation method

technical field

The invention relates to the field of energy technology, in particular to a solar cell and a preparation method thereof.

Background technique

With the increasingly severe energy and environmental crisis, finding new and renewable energy sources is becoming an urgent problem to be solved. Solar energy is inexhaustible, and it is green and renewable. Among them, thin-film solar technology has been on the rise in recent years because of its light weight, low cost, and easy installation. Copper indium gallium selenide (CIGS) is the most efficient thin-film solar cell, but the existing solar cell is only a light energy converter, which converts solar energy into electrical energy output. The current research on solar energy is only how to improve the conversion rate. For The storage of electric energy is only an external energy storage device with a single function. Since the external device is not easy to carry, it directly limits the development of the miniaturization of solar cells.

Contents of the invention

The present invention provides an energy-storage photoelectric CIGS solar cell and a preparation method for avoiding the disadvantages of the above-mentioned prior art, with both functions of photoelectric conversion and energy storage, in order to obtain energy-storage photoelectric CIGS solar cells that can While converting light energy into electrical energy, a part of the electrical energy can be stored and the other part can be used for output.

The present invention adopts following technical scheme for solving technical problems:

The structural features of the energy storage photoelectric CIGS solar cell of the present invention are: the structural layers of the energy storage photoelectric CIGS solar cell are arranged in order from top to bottom: a top conductive glass substrate, a CIGS storage layer, a first electrolyte layer, The separator, the second electrolyte layer, the electricity storage layer and the bottom conductive glass substrate, use the top conductive glass substrate and the bottom conductive glass substrate as counter electrodes.

The characteristics of the energy storage photoelectric CIGS solar cell of the present invention also lie in:

The energy storage material used to prepare the CIGS electricity storage layer is carbon material or polyaniline material, and the energy storage material used to prepare the electricity storage layer is metal oxide or polyaniline material.

The carbon material is a nano-spherical carbon material prepared by carbon airgel; the metal oxide is MnO ₂ , NiO or Ni ₂ O ₃ ; the polyaniline material is polyaniline.

The CIGS storage layer has a thickness of 500-2000 μm.

The electrolyte in the first electrolyte layer and the second electrolyte layer is a liquid electrolyte, and the liquid electrolyte is one of dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate and ethyl methyl carbonate A mixture with one of monomethyltriethylammonium tetrafluoroborate and tetraethylammonium tetrafluoroborate, the molar ratio of the mixture is 1:1.

The membrane is ion-permeable.

The characteristics of the preparation method of the energy storage photoelectric CIGS solar cell of the present invention are as follows:

a. Copper, indium, gallium and energy storage materials are sputtered on the conductive surface of the top conductive glass substrate by hybrid sputtering method, and the CIGS storage layer is formed after selenization;

b. On the conductive surface of the conductive glass substrate on the bottom surface, an electric storage layer is formed by spraying or depositing an energy storage material;

c. Insert a separator between the CIGS storage layer and the storage layer, inject electrolyte after pressing, and form the first electrolyte layer between the CIGS storage layer and the separator, and form the second electrolyte layer between the storage layer and the separator. Electrolyte layer; the layer structure consisting of the top conductive glass substrate, CIGS storage layer, first electrolyte layer, diaphragm, second electrolyte layer, storage layer and bottom conductive glass substrate is sealed at the periphery Form energy storage photoelectric CIGS solar cells.

The preparation method of the energy storage photoelectric CIGS solar cell of the present invention is also characterized in that the temperature of the hybrid sputtering method in the step a is 200-500°C.

Compared with the prior art, the beneficial effects of the present invention are reflected in:

1. The CIGS layer of the energy storage material prepared by the hybrid sputtering method in the present invention, wherein the energy storage material and CIGS have a special structure, and at the same time increase the conductivity of the energy storage material itself, and at the same time add electrolyte and The diaphragm solves the problem of electron conduction in the energy storage process. Based on the above structure, the energy storage photoelectric CIGS solar cell of the present invention can convert light energy into electrical energy while storing a part of the electrical energy and using the other part of the electrical energy for output. .

2. The complete energy-storage photoelectric CIGS solar cell prepared by the method of the present invention is irradiated by a solar simulator for 1-4 hours, and its open circuit voltage is 0.5-0.7V, compared with a CIGS solar cell with only photoelectric conversion , the open circuit voltage of the energy storage photoelectric CIGS solar cell has not decreased, and the energy storage photoelectric CIGS solar cell irradiated by the solar simulator is placed in a dark place for 200-400 hours, and its open circuit voltage is 0.2-0.3V.

Description of drawings

Fig. 1 is the structural representation of energy storage photovoltaic CIGS solar cell of the present invention;

Numbers in the figure: 1 top conductive glass substrate; 2 CIGS electric storage layer; 3 first electrolyte layer; 4 separator; 5 second electrolyte layer; 6 electric storage layer; 7 bottom conductive glass substrate.

Detailed ways

Example 1:

Sputter 0.45g of copper, 0.15g of indium, 0.35g of gallium and 1g of carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering at 200°C, and then perform selenization in a selenium atmosphere to form For the CIGS storage layer 2 with a thickness of 500 μm, in the process of mixed sputtering and selenization, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:20;

Spray metal oxide NiO on the bottom conductive glass substrate 7, sinter at 300°C to form the storage layer 6, insert the separator 4 between the CIGS storage layer 2 and the storage layer 6, and press them, and then press them Tetraethylammonium tetrafluoroborate and dimethyl carbonate are injected into the device at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then seal the periphery of the device to form an energy storage Photovoltaic CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment was irradiated by a solar simulator for 2 hours, and its open circuit voltage was 0.67V; the energy storage photoelectric CIGS solar cell after irradiation was placed in a dark place for 400 hours, and its open circuit voltage was 0.23V. After 5,000 times of fast simulated charging and discharging under the solar simulator, the attenuation was 9.6%, and the measured open circuit voltage was 0.60V.

Example 2:

Sputter 0.45g copper, 0.15g indium, 0.35g gallium and 1.2g carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering method at 200°C, and then perform selenization under a selenium atmosphere A CIGS storage layer 2 with a thickness of 700 μm is formed. During the mixed sputtering and selenization process, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:24;

Spray polyaniline on the conductive glass substrate 7 on the bottom surface, sinter at 300°C to form the storage layer 6, insert the separator 4 between the CIGS storage layer 2 and the storage layer 6, and press them, and then put them into the pressed device Inject monomethyltriethylammonium tetrafluoroborate and dimethyl carbonate at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then seal the periphery of the device to form a reservoir. Energy photoelectric CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment was irradiated by a solar simulator for 2 hours, and its open circuit voltage was 0.70V; the energy storage photoelectric CIGS solar cell after irradiation was placed in a dark place for 380 hours, and its open circuit voltage was 0.26V.

Example 3:

Sputter 0.45g copper, 0.15g indium, 0.35g gallium and 1.4g carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering method at 300°C, and then perform selenization under a selenium atmosphere A CIGS storage layer 2 with a thickness of 900 μm is formed, and in the process of mixed sputtering and selenization, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:28;

Spray metal oxide MnO ₂ on the bottom conductive glass substrate 7, sinter at 300°C to form the electricity storage layer 6, insert the separator 4 between the CIGS electricity storage layer 2 and the electricity storage layer 6, press them, and then press them together Tetraethylammonium tetrafluoroborate and diethyl carbonate are injected into the device at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then seal the periphery of the device to form a reservoir Energy photoelectric CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment was irradiated by a solar simulator for 2.5 hours, and its open circuit voltage was 0.69V; the energy storage photoelectric CIGS solar cell after irradiation was placed in a dark place for 350 hours, and its open circuit voltage was 0.22V.

Example 4:

Sputter 0.45g copper, 0.15g indium, 0.35g gallium and 1.6g carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering method at 300°C, and then perform selenization under a selenium atmosphere A CIGS storage layer 2 with a thickness of 1100 μm is formed, and in the process of mixed sputtering and selenization, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:32;

Metal oxide Ni ₂ O ₃ is sprayed on the bottom conductive glass substrate 7, sintered at 300°C to form the storage layer 6, the separator 4 is inserted between the CIGS storage layer 2 and the storage layer 6, and then pressed together, and then Inject monomethyltriethylammonium tetrafluoroborate and diethyl carbonate into the laminated device at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then in the periphery of the device Sealing is performed to form energy storage photoelectric CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment is irradiated by a solar simulator for 2.5 hours, and its open circuit voltage is 0.67V; the energy storage photoelectric CIGS solar cell after irradiation is placed in a dark place for 400 hours, and its open circuit voltage is 0.23V.

Example 5:

Sputter 0.45g copper, 0.15g indium, 0.35g gallium and 1.8g carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering method at 400°C, and then perform selenization under a selenium atmosphere A CIGS storage layer 2 with a thickness of 1300 μm is formed, and in the process of mixed sputtering and selenization, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:36;

Spray metal oxide NiO on the bottom conductive glass substrate 7, sinter at 300°C to form the storage layer 6, insert the separator 4 between the CIGS storage layer 2 and the storage layer 6, and press them, and then press them Tetraethylammonium tetrafluoroborate and propylene carbonate are injected into the device at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then seal the periphery of the device to form an energy storage photoelectric CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment was irradiated by a solar simulator for 3 hours, and its open circuit voltage was 0.70V; the energy storage photoelectric CIGS solar cell after irradiation was placed in a dark place for 370 hours, and its open circuit voltage was 0.21V.

Embodiment 6:

Sputter 0.45g copper, 0.15g indium, 0.35g gallium and 2g carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering method at 200°C, and then perform selenization in a selenium atmosphere to form For the CIGS storage layer 2 with a thickness of 1500 μm, in the process of mixed sputtering and selenization, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:40;

Metal oxide Ni ₂ O ₃ is sprayed on the bottom conductive glass substrate 7, sintered at 300°C to form the storage layer 6, the separator 4 is inserted between the CIGS storage layer 2 and the storage layer 6, and then pressed together, and then Inject monomethyltriethylammonium tetrafluoroborate and propylene carbonate into the pressed device at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then carry out the process on the periphery of the device. Sealed to form energy storage photoelectric CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment was irradiated by a solar simulator for 3 hours, and its open circuit voltage was 0.67V; the energy storage photoelectric CIGS solar cell after irradiation was placed in a dark place for 360 hours, and its open circuit voltage was 0.25V.

Embodiment 7:

Sputter 0.45g copper, 0.15g indium, 0.35g gallium and 2.2g carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering method at 500°C, and then perform selenization under a selenium atmosphere A CIGS storage layer 2 with a thickness of 1700 μm is formed, and in the process of mixed sputtering and selenization, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:44;

Spray metal oxide NiO on the bottom conductive glass substrate 7, sinter at 300°C to form the storage layer 6, insert the separator 4 between the CIGS storage layer 2 and the storage layer 6, and press them, and then press them Tetraethylammonium tetrafluoroborate and ethylene carbonate are injected into the device at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then seal the periphery of the device to form an energy storage photoelectric CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment was irradiated by a solar simulator for 3.5 hours, and its open circuit voltage was 0.68V; the energy storage photoelectric CIGS solar cell after irradiation was placed in a dark place for 370 hours, and its open circuit voltage was 0.23V.

Embodiment 8:

Sputter 0.45g copper, 0.15g indium, 0.35g gallium and 2.4g carbon microspheres onto the conductive surface of the top conductive glass substrate 1 by hybrid sputtering method at 500°C, and then perform selenization under a selenium atmosphere A CIGS storage layer 2 with a thickness of 500 μm is formed. During the mixed sputtering and selenization process, the mass ratio of copper: indium: gallium: selenium: carbon microspheres is 9:3:7:15:48;

Spray polyaniline on the conductive glass substrate 7 on the bottom surface, sinter at 300°C to form the storage layer 6, insert the separator 4 between the CIGS storage layer 2 and the storage layer 6, and press them, and then put them into the pressed device Inject monomethyltriethylammonium tetrafluoroborate and ethylene carbonate at a volume ratio of 1:1 to form the first electrolyte layer 3 and the second electrolyte layer 5 respectively, and then seal the periphery of the device to form energy storage Photovoltaic CIGS solar cells.

The energy storage photoelectric CIGS solar cell prepared in this embodiment was irradiated by a solar simulator for 4 hours, and its open circuit voltage was 0.70V; the energy storage photoelectric CIGS solar cell after irradiation was placed in a dark place for 350 hours, and its open circuit voltage was 0.25V.

Claims (4)

1. An energy storage photoelectric CIGS solar cell is characterized in that: the structural layers of the energy storage photoelectric CIGS solar cell are arranged as follows from top to bottom: top surface conductive glass substrate (1), CIGS electricity storage layer (2 ), the first electrolyte layer (3), the separator (4), the second electrolyte layer (5), the storage layer (6) and the bottom conductive glass substrate (7), with the top conductive glass substrate (1) and bottom surface conductive glass substrate (7) as counter electrode; The energy storage material that is used to prepare described CIGS electricity storage layer (2) is carbon material or polyaniline material, is used to prepare described electricity storage layer ( 6) The energy storage material is a metal oxide or polyaniline material; the carbon material is a nano-spherical carbon material prepared by carbon airgel; the metal oxide is MnO2, NiO or Ni2O3; the polyaniline The material is polyaniline. 2. The energy storage photoelectric CIGS solar cell according to claim 1, characterized in that, the CIGS storage layer (2) has a thickness of 500-2000 μm. 3. The energy storage photovoltaic CIGS solar cell according to claim 1, characterized in that, the electrolyte in the first electrolyte layer (3) and the second electrolyte layer (5) is a liquid electrolyte, and the liquid electrolyte It is a mixture of one of dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate and ethyl methyl carbonate and one of monomethyltriethylammonium tetrafluoroborate and tetraethylammonium tetrafluoroborate , the molar ratio of the mixture is 1:1. 4. The energy storage photoelectric CIGS solar cell according to claim 1, characterized in that the separator (4) has ion permeability.