阅读说明：本技术 一种高开压高效钙钛矿/晶硅叠层电池 (High-voltage and high-efficiency perovskite/crystalline silicon laminated battery ) 是由 张晓丹 陈兵兵 李兴亮 李玉成 王鹏阳 许盛之 黄茜 侯国付 魏长春 陈新亮 任 于 2020-04-01 设计创作，主要内容包括：一种高开压高效钙钛矿/晶硅叠层电池,采用更宽带隙的钙钛矿电池为顶电池,通过导电粘合剂与底部晶硅电池构成两端的叠层结构。通过采用更宽带隙的钙钛矿电池作为叠层电池的顶电池,可以获得更高的叠层开路电压,有望获得更高的转换效率。本发明公开了一种采用导电粘合剂来实现钙钛矿/晶硅两端叠层电池的新型结构设计,通过增大顶部宽带隙钙钛矿电池的受光面积,补偿顶电池的电流损失,实现顶、底电池的电流匹配,获得更高的开路电压以及更高的转换效率。可应用于电解水、二氧化碳还原等需要更高开压的研究中。(A high-voltage high-efficiency perovskite/crystalline silicon laminated cell adopts a wider band gap perovskite cell as a top cell and forms a laminated structure at two ends with a bottom crystalline silicon cell through a conductive adhesive. By adopting a wider band gap perovskite battery as the top battery of the laminated battery, higher laminated open-circuit voltage can be obtained, and higher conversion efficiency is expected to be obtained. The invention discloses a novel structural design for realizing a perovskite/crystalline silicon two-end laminated cell by adopting a conductive adhesive, which compensates the current loss of a top cell by increasing the light receiving area of a top wide-band-gap perovskite cell, realizes the current matching of the top cell and a bottom cell, and obtains higher open-circuit voltage and higher conversion efficiency. Can be applied to researches requiring higher open pressure such as electrolytic water reduction and carbon dioxide reduction.)

1. A high-voltage high-efficiency perovskite/crystalline silicon laminated cell is characterized in that a perovskite cell with a wider band gap of 1.75-2.0 eV is used as a top cell, and a laminated structure at two ends is formed by a conductive adhesive and a bottom crystalline silicon cell; the areas of the top battery and the bottom battery in the two-end laminated battery are not equal, the ratio of the area of the top battery to the area of the bottom battery is 1.1-2.0, the current of the top battery is compensated by increasing the area of the top perovskite battery, and the current matching of the top battery and the bottom battery is realized.

2. The high-voltage high-efficiency perovskite/crystalline silicon tandem cell according to claim 1, wherein the conductive adhesive is any one of the following: 1) a mixture comprising a binder resin, metal conductive particles or metal oxide conductive particles, and an organic solvent; the mixture is specifically low-temperature silver paste or ITO conductive adhesive; 2) a simple transparent conductive oxide thin film indium tin oxide semiconductor (ITO), zinc tin oxide semiconductor (IZO), or indium gallium zinc oxide semiconductor (IGZO); 3) gold, platinum, silver, or palladium metal nanoarrays; the conductive adhesive material is realized by a sputtering method, an evaporation method or a solution method.

3. The high-voltage high-efficiency perovskite/crystalline silicon tandem cell as claimed in claim 1, wherein the perovskite top cell is a wider band gap organic-inorganic hybrid perovskite material or an all-inorganic perovskite material; the perovskite roof battery material comprises the components of lead-based, non-lead-based or other mixed perovskite materials; the perovskite roof battery is prepared by a solution method of two-step sequential deposition or one-step anti-solvent deposition, or by evaporation deposition or chemical vapor deposition.

4. The high-voltage high-efficiency perovskite/crystalline silicon tandem cell as claimed in claim 1, wherein the structure of the perovskite top cell and the crystalline silicon cell is a pin type cell structure or an nip type cell structure.

5. The high-voltage high-efficiency perovskite/crystalline silicon tandem cell as claimed in claim 1, wherein the hole material of the perovskite cell is inorganic NiO_XMnS or CuSCN, or is an organic material PTAA, Spiro-OMeTAD or Spiro-TTB; the electron layer transmission material is inorganic SnO₂Or TiO₂Or organic material PCBM or C₆₀。

6. The perovskite/crystalline silicon tandem cell with high voltage and high efficiency as claimed in claim 1, wherein the transparent electrode material of the perovskite cell and the crystalline silicon cell is ITO, IZO, IO H or IZO.

7. The high-voltage high-efficiency perovskite/crystalline silicon tandem cell as claimed in claim 1, wherein the perovskite top cell is prepared on a rigid substrate or a flexible substrate PEN or PET.

8. The high-voltage high-efficiency perovskite/crystalline silicon tandem cell as claimed in claim 1, wherein the crystalline silicon bottom cell is a planar silicon cell, a single-sided textured or double-sided textured silicon solar cell, and the silicon cell is an n-type silicon wafer, a p-type silicon wafer, a CZ type or an FZ type.

9. The cell of claim 10, wherein the silicon cell is a silicon heterojunction cell, a TOP-Con cell, a POLO cell, a DASH cell or a homojunction cell.

10. The perovskite/crystalline silicon tandem cell with high voltage and high efficiency according to claim 1, wherein the structure of the perovskite cell is planar, mesoporous or organic.

Technical Field

The invention relates to the technical field of solar cells, in particular to design and preparation of a high-open-voltage and high-efficiency perovskite/crystalline silicon laminated solar cell.

Background

From the increasing efficiency and effective cost control, the crystalline silicon cell occupies more than 90% of the total photovoltaic market, and based on the continuous progress of the technology, the conversion efficiency of the single crystalline silicon cell reaches 26.7%, and approaches the theoretical limit efficiency (29.1%) of auger recombination. In order to break through the theoretical limit of single junction cells and obtain higher conversion efficiency, people gradually turn attention to the study of laminated cells. The organic-inorganic lead halogen perovskite battery is considered as the first choice for forming a laminated battery with a crystalline silicon battery due to the advantages of low preparation cost, high conversion efficiency (25.2%), adjustable band gap and the like, and is expected to realize higher conversion efficiency. The perovskite/crystalline silicon laminated structures at two ends are more compatible with the large-scale component preparation process in the current photovoltaic market, and become the key point of the current perovskite and crystalline silicon laminated cell research. Since the first perovskite/silicon two-terminal laminated solar cell prepared in 2015, the conversion efficiency of the laminated cell has been improved from 13.7% to 29.15%. At present, in order to match the current of the top perovskite cell and the current of the bottom crystalline silicon cell, perovskite materials with band gaps below 1.7eV are mostly adopted in the reported perovskite/crystalline silicon two-end laminated cell as the top cell, so that the highest open voltage of the laminated cell is only 1.88eV, which is far smaller than the highest open voltage value which can be realized after the two cells are stacked. In addition, in some special applications, such as applications of photoelectrochemical carbon dioxide reduction for preparing liquid fuel and the like, the open pressure of more than 2V is generally required, and the existing perovskite/crystalline silicon tandem cell cannot meet the requirements. In practical power supply applications, it is found that the same output power is obtained during two batteries with the same output power, that is, after the open-circuit voltage and the short-circuit current of the two batteries are multiplied. In the process of realizing power supply, the output end and the input end of the two batteries need to be connected by a conductive wire, and the conductive wire has certain resistance, so voltage loss of different degrees can occur in the transmission process. However, according to the formula of voltage, current and resistance, the voltage drop loss of the battery device with the same output power and smaller current in the transmission process is smaller.

In summary, we conclude that: the existing wide band gap perovskite and crystalline silicon battery laminated cell technology has the following defects: 1) a perovskite cell with a suitable wide band gap is selected as the top cell for current matching, but the wide band gap cells currently used do not achieve higher open voltage of the two-terminal tandem cell, such as 2V or even higher open voltage. 2) Some of the currently reported laminated batteries obtain higher open voltage, and the laminated current is also relatively higher, but in practical application, if the output power of the two batteries is the same, the voltage drop loss of the battery device with larger current in the transmission process is also larger.

Disclosure of Invention

The invention aims to solve the problems in the prior art, and provides a top battery which adopts wider band gap perovskite as a structure laminated with a crystalline silicon battery at two ends, and the current of the top battery is improved by increasing the light receiving area of the top perovskite battery, so that the current matching of the top battery and the bottom battery is obtained, and the high-efficiency perovskite/crystalline silicon laminated battery is realized.

The technical scheme of the invention is as follows:

a high-voltage high-efficiency perovskite/crystalline silicon laminated cell adopts a perovskite cell with a wider band gap of 1.75-2.0 eV as a top cell, and forms a laminated structure at two ends with a bottom crystalline silicon cell through a conductive adhesive, the laminated cell structure is designed to be mainly embodied in that the areas of the top cell and the bottom cell are not equal, the ratio of the area of the top cell to the area of the bottom cell is 1.1-2.0, and the area of the perovskite cell at the top is slightly larger than the area of the bottom crystalline silicon cell. The perovskite battery with wider band gap is used as the top battery of the laminated battery, the current available for the top battery is reduced, and if the laminated battery still adopts the existing structure, the top battery and the bottom battery are not matched, so that the battery efficiency is influenced. The area of the top perovskite battery is increased, so that the current loss of the top battery is compensated, and the current matching of the top battery and the bottom battery is realized. In addition, a wider band gap perovskite battery is adopted as a top battery, so that higher lamination open-circuit voltage can be obtained, and the method can be applied to researches such as photoelectrochemistry carbon dioxide reduction. In addition, the laminated battery can effectively reduce the energy loss of the battery in practical use and realize higher power supply efficiency.

The conductive adhesive is any one of the following: 1) a mixture comprising a binder resin, metal conductive particles or metal oxide conductive particles, and an organic solvent; the mixture is specifically low-temperature silver paste or ITO conductive adhesive; 2) a simple transparent conductive oxide thin film indium tin oxide semiconductor (ITO), zinc tin oxide semiconductor (IZO), or indium gallium zinc oxide semiconductor (IGZO); 3) gold, platinum, silver or palladium metal nanoarrays. The conductive adhesive material is realized by a sputtering method, an evaporation method, or a solution method.

The perovskite roof battery is an organic-inorganic hybrid perovskite material with a wider band gap or an all-inorganic perovskite material; the perovskite roof battery material comprises a lead-based, non-lead-based or other mixed perovskite material. The film is prepared by a solution method of two-step sequential deposition or one-step anti-solvent deposition, or by evaporation deposition or chemical vapor deposition. The hole material of the perovskite battery is inorganic NiO_XMnS or CuSCN, or is an organic material PTAA, Spiro-OMeTAD or Spiro-TTB; the electron layer transmission material is inorganic SnO₂Or TiO₂Or organic material PCBM or C₆₀. The transparent electrode material of the perovskite cell and the crystalline silicon cell is ITO, IZO, IO: H or IZO.

In the process of preparing the battery, the perovskite battery at the top and the crystalline silicon battery at the bottom are prepared independently, wherein the area of the top battery is properly larger than that of the crystalline silicon battery at the bottom, and finally the top battery and the bottom battery are connected through the middle conductive adhesive to realize the structure of the laminated battery at two ends. The structure of the perovskite top battery and the crystalline silicon battery can be a pin type battery structure or an nip type battery structure. The perovskite top battery is prepared on a hard substrate or a flexible substrate PEN or PET; the structure of the perovskite battery is a planar type, a mesoporous type or an organic structure type.

The crystalline silicon bottom cell is a planar silicon cell, a single-sided textured or double-sided textured silicon solar cell. The silicon battery is an n-type silicon chip, a p-type silicon chip, a CZ type or an FZ type; is a silicon heterojunction battery, a TOP-Con battery, a POLO battery, a DASH battery, or a homojunction battery.

The invention has the advantages and positive effects that:

the perovskite battery with a wider band gap is used as the top battery of the laminated battery, so that the problem of unmatched current caused by the fact that the band gap of the top battery is too wide is solved, the current loss of the top battery is compensated by adjusting the effective battery area of the top battery and the bottom battery, and the current matching of the top battery and the bottom battery is realized; meanwhile, on the premise of ensuring the high efficiency of the laminated battery, the open-circuit voltage of the battery can be further improved, and the laminated battery is further applied to researches requiring higher open-circuit voltage such as carbon dioxide reduction and the like; on the other hand, the perovskite battery with wider band gap and the crystalline silicon battery form a laminated battery, so that the open-circuit voltage loss of the battery in the transmission process can be effectively reduced, and the energy loss of the laminated battery in the transmission process is smaller when the same power is obtained.

The mechanism analysis of the invention is as follows:

according to the invention, the current loss caused by the increase of the band gap of the top battery is compensated by increasing the effective absorption area of the top perovskite battery, the open-circuit voltage of the laminated battery can be further improved, and the higher efficiency of the perovskite and crystalline silicon laminated battery is hopefully realized; in addition, the wider band gap perovskite battery can obtain higher laminated open circuit voltage, so that the battery can be applied to researches of water electrolysis, carbon dioxide reduction and the like; finally, the laminated battery has smaller energy loss in the transmission process when the same power is obtained, and can obtain higher power supply efficiency.

Drawings

Fig. 1 is a schematic structural diagram of an nip type wider band gap organic-inorganic hybrid perovskite/silicon heterojunction tandem solar cell used in the invention.

FIG. 2 is a schematic structural diagram of a pin type wider band gap organic-inorganic hybrid perovskite/silicon heterojunction tandem solar cell adopted in the invention.

Fig. 3 is a schematic structural diagram of a stacked solar cell adopting an nip-type all-inorganic perovskite/silicon heterojunction in the invention.

Fig. 4 is a schematic diagram of the solar cell employing an nip type wider band gap organic-inorganic hybrid perovskite/silicon heterojunction tandem solar cell of the present invention, wherein the conductive binder is selected to be Pt nanoparticles.

FIG. 5 is a schematic structural diagram of a solar cell adopting a nip type wider band gap organic-inorganic hybrid perovskite/TOP-Con tandem solar cell.

Fig. 6 is a schematic structural diagram of a stacked solar cell adopting an nip type wider band gap organic-inorganic hybrid perovskite/silicon heterojunction, wherein the silicon heterojunction is a double-sided texturing structure.

FIG. 7 is a schematic structural diagram of a stacked solar cell adopting an nip type wider band gap organic-inorganic hybrid perovskite/silicon heterojunction, wherein perovskite is grown on a flexible transparent substrate.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.