Preparation method of nitrogen-doped graphene CIGS thin film cell tail gas purifying agent

Abstract

The application provides a preparation method of a nitrogen-doped graphene CIGS thin-film battery tail gas purifying agent, and is characterized in that the method comprises the following steps: S1, placing a nitrogen-doped graphene carrier and a composite copper source in a reaction kettle, adding ammonia water, stirring for 20-40 min, and obtaining a reaction product for standby; S2, adding a strong alkali solution into the reaction product in step S1, stirring for 20-30 min, washing, suction filtering, and drying to obtain the nitrogen-doped graphene CIGS thin-film battery tail gas purifying agent. The tail gas purifying agent has the characteristics of removing H2S and H2Se gas at room temperature, can be widely applied to the field of environmental protection material preparation, and has good commercial application value.

Description

Technical Field

[0001] This invention relates to the field of environmental protection material preparation, specifically to the field of room temperature high-efficiency purification materials, and particularly to a method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier. Background Technology

[0002] Solar energy, as a clean, efficient, and inexhaustible new energy source, has always been an important component of the national sustainable development strategy. Copper indium gallium selenide (CIGS) thin-film solar cells, as a novel type of photovoltaic cell, possess multiple advantages such as high efficiency, low cost, and long lifespan, while also making full use of my country's abundant indium resources, thus showing great promise. In CIGS thin-film solar cells, the CIGS absorber layer plays a crucial role.

[0003] In the fabrication of CIGS absorber layers, after selenization, a sulfidation process is often employed to dope sulfur atoms onto the film surface, replacing some selenium atoms. This adjusts the energy band, widens the bandgap, and increases the open-circuit voltage. The method used for sulfur doping involves exposing the device to an atmosphere filled with an H2S / N2 mixture to achieve recrystallization. Periodically, excess H2S / N2 is discharged as waste gas, containing a small amount of H2Se gas replaced by sulfur. Both H2S and H2Se in this mixture are highly toxic gases, posing serious health risks and causing severe environmental pollution. Therefore, purification treatment is necessary before release.

[0004] To address the removal of acidic gases such as H2S, various desulfurizing agents and methods have been developed, including activated carbon and metal oxide methods. However, most traditional desulfurizing agents require high operating temperatures to achieve high desulfurization efficiency. In contrast, the exhaust gas from CIGS thin-film battery production is at room temperature. Using traditional desulfurizing agents as exhaust gas purifiers results in low desulfurization efficiency. Copper-based desulfurizing agents have high sulfur capacity at room temperature, meeting the basic requirements for efficient room-temperature desulfurization. However, they suffer from drawbacks such as the easy reduction of divalent copper and low stability when used alone. To improve the stability of copper-based desulfurizing agents, copper-based materials are often loaded onto a porous carrier. However, insufficient active sites on the carrier lead to uneven loading, resulting in low desulfurization efficiency.

[0005] Patent publication number CN 112958078A discloses a CIGS tail gas treatment purifier and its preparation method. The purifier prepared by this application includes hydrotalcite, and the hydrotalcite is impregnated and loaded with permanganate ions, which can meet the requirements of low-temperature and high-efficiency removal of H2S and H2Se. However, the reaction process is exothermic, and if the heat dissipation is not timely, the bed temperature will rise, thereby affecting the tail gas purification performance of the purifier. In addition, the problem of insufficient active sites in hydrotalcite leading to insufficient loading has not been solved. Patent publication number CN 109439376B discloses a room temperature desulfurizing agent and its preparation method. The desulfurizing agent prepared by this application includes γ-alumina, nano zinc oxide, transition metal oxide and rare earth metal oxide. Among them, copper oxide is selected as the transition metal, and lanthanum oxide is selected as the rare earth metal, which has the best room temperature desulfurization effect. However, no improvement has been made on the stability of metal oxides, and there is still a risk of reduced desulfurization efficiency and poor durability.

[0006] Therefore, there is an urgent need in the market for a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier that can efficiently remove H2S and H2Se gases under normal temperature conditions. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention selects nitrogen-doped graphene carrier and composite copper source as the main components of the purifier, and then adds ammonia water and strong alkaline solution to prepare and synthesize a nitrogen-doped graphene CIGS thin film battery exhaust gas purifier, which has the advantages of efficient removal of H2S and H2Se gases at room temperature.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] This invention provides a method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier, comprising the following steps:

[0010] S1. Place the nitrogen-doped graphene support and the composite copper source in a reaction vessel, add ammonia water, stir for 20-40 minutes, and obtain the reaction product for later use.

[0011] S2. Add the strong alkaline solution to the reaction product of step S1, stir for 20-30 minutes, wash, filter, and dry to obtain the nitrogen-doped graphene CIGS thin film battery exhaust gas purifier.

[0012] In some embodiments of the present invention, the method for preparing the nitrogen-doped graphene support includes the following steps:

[0013] (1) Dissolve graphene oxide, phenylboronic acid and adenine in deionized water, stir for 20-40 min, add methanol solution of cobalt nitrate hexahydrate, stir for 20-40 min, heat to 130-150℃, stir for 4-6 h to obtain product 1 for later use.

[0014] (2) Cool the product 1 from step (1) to room temperature, distill under reduced pressure, dry, and calcine under an inert atmosphere to obtain product 2 for later use.

[0015] (3) Dissolve xylan in citric acid solution, stir for 50-70 min, add product 2 from step (2), sonicate, wash, and dry to obtain nitrogen-doped graphene carrier.

[0016] In some embodiments of the present invention, in step (1), the mass ratio of graphene oxide to adenine is 1:(2-5); in step (3), the mass ratio of product 2 to xylan is 1:(31-35).

[0017] Preferably, the mass ratio of graphene oxide to adenine is 1:(3-5); in step (3), the mass ratio of product 2 to xylan is 1:(31-33).

[0018] More preferably, the mass ratio of graphene oxide to adenine is 1:4; in step (3), the mass ratio of product 2 to xylan is 1:33.

[0019] Graphene oxide is often used as a carrier for metal or non-metal materials due to its advantages such as large specific surface area, high mechanical strength, high flexibility and stable properties. Its internal cavity structure enables it to have a good purification effect on H2S and H2Se gases. However, the stacking between the layers of graphene oxide alone limits its purification effect on H2S and H2Se gases as well as its loading effect on metal ions.

[0020] On the one hand, the applicant used adenine as the nitrogen source, phenylboronic acid as the auxiliary carbon source, and boron as the doping agent for graphene oxide. By replacing C atoms with N and B, the active sites on graphene oxide were increased, enhancing the bonding between the composite copper source and the support, thereby improving the removal performance of H2S gas by the composite copper source. Furthermore, the imidazole group in adenine reacts with Cu... 2 + Coordination occurs between them, thereby increasing the bonding force between the carrier and the composite copper source, and improving the desulfurization efficiency of the purifying agent. Furthermore, the applicant introduces cobalt nitrate hexahydrate, and the N-doped graphite layer interacts with Co. 2+A Co-N complex was formed at the interface between the two materials, which enhanced electron transfer at the interface of the composite material, thereby increasing the loading activity of the carrier and effectively improving the desulfurization efficiency of the purifier. On the other hand, the applicant combined xylan with N, Co, and B doped graphene oxide, and used the hydroxyl and carboxyl groups in xylan to crosslink with the groups on the surface of graphene oxide to form a carrier structure with a larger specific surface area and improve the stability of graphene oxide. Furthermore, the xylan molecular chain contains many hydroxyl groups, which can adsorb metal ions in the composite copper source, thereby improving the removal efficiency of H2S and H2Se gases by the purifier.

[0021] In some embodiments of the present invention, the method for preparing the composite copper source includes the following steps:

[0022] 1) Mix ferric nitrate hexahydrate and ethylene glycol, and stir at 50-60℃ for 20-30 min to obtain mixture 1 for later use;

[0023] 2) Mix triethylamine nitrate and copper nitrate, stir for 5-10 minutes, heat to 60-70℃ and stir for 2-4 hours to obtain mixture 2 for later use;

[0024] 3) Take mixture 1 from step 1) and add it to mixture 2 from step 2), stir for 30-50 minutes to obtain the composite copper source.

[0025] In some embodiments of the present invention, the molar ratio of ferric nitrate hexahydrate to copper nitrate is (0.2-0.6):1.

[0026] Preferably, the molar ratio of ferric nitrate hexahydrate to copper nitrate is 0.4:1.

[0027] Both copper-based and iron-based desulfurizers have high desulfurization capacity under normal temperature conditions and are good desulfurizers for treating acidic substances such as H2S in the exhaust gas of CIGS thin-film batteries. However, copper-based substances alone are easily reduced to elemental copper, while iron-based substances alone have the disadvantages of low desulfurization strength and easy pulverization when exposed to water, both of which will lead to a decrease in their desulfurization performance.

[0028] On the one hand, the applicant used Fe 3+ Using ethylene glycol as a raw material, a eutectic solvent was prepared, Fe 3+ It can directly undergo a redox reaction with H2S and the product is Fe. 2+ The purifying agent can be regenerated through oxygen oxidation, giving it the advantage of cyclic regeneration. Furthermore, hydrogen bonds with coordination effects are formed between ferric nitrate hexahydrate and ethylene glycol, allowing the eutectic solvent to remain stable and function effectively. On the other hand, the applicant prepares an ionic liquid using triethylamine nitrate and copper nitrate. This ionic liquid is environmentally friendly and possesses both amine and nitrate groups. The amine groups contribute to increasing the system's alkalinity, thereby promoting Cu...2+ The removal of H2S gas, and the amino groups and Fe in triethylamine nitrate. 3+ Coordination occurs between them, which is beneficial to Fe 3+ and Cu 2+ A bimetallic coupled desulfurization system is formed, thereby synergistically removing acidic gases such as H2S and improving the desulfurization efficiency of the purifying agent; furthermore, the applicant selects a eutectic solvent and an ionic liquid as the medium to remove Fe 3+ and Cu 2+ Introducing nitrogen-doped graphene into the carrier helps improve the dispersion of metal ions in the carrier, thereby enhancing the desulfurization activity of metal ions and improving the removal efficiency of the purifier for H2S and H2Se gases.

[0029] In some embodiments of the present invention, the mass ratio of nitrogen-doped graphene support to composite copper source in step S1 is 1:(0.6-1).

[0030] Preferably, in step S1, the mass ratio of nitrogen-doped graphene support to composite copper source is 1:0.8.

[0031] In some embodiments of the present invention, the mass ratio of the composite copper source and ammonia in step S1 is 1:(0.8-1.2), and the concentration of ammonia is 3-5 mol / L.

[0032] Preferably, in step S1, the mass ratio of the composite copper source to ammonia is 1:1, and the concentration of ammonia is 4 mol / L.

[0033] In some embodiments of the present invention, the strong alkaline solution in step S2 is a sodium hydroxide solution with a concentration of 1-2 mol / L.

[0034] In some embodiments of the present invention, the mass ratio of the composite copper source to the strong alkaline solution is 1:(0.2-0.3).

[0035] Preferably, the mass ratio of the composite copper source to the strong alkaline solution is 1:0.25.

[0036] In another aspect, the present invention provides a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier obtained by the preparation method described above, wherein the H2S conversion rate is not less than 93.5% and the H2Se conversion rate is not less than 92%.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] (1) The present invention selects nitrogen-doped graphene carrier and composite copper source as the main components of the purifier, and then adds ammonia water and strong alkaline solution to prepare and synthesize a nitrogen-doped graphene CIGS thin film battery tail gas purifier. Through the synergistic effect between the components, the purifier has the advantages of high efficiency removal of H2S and H2Se gases at room temperature.

[0039] (2) In this invention, graphene oxide is doped with N, B and Co and combined with xylan to prepare nitrogen-doped graphene support. By increasing the active sites and specific surface area of ​​graphene oxide, the support can be better combined with the copper source, thereby improving the removal efficiency of H2S and H2Se gases.

[0040] (3) The present invention uses Fe 3+ The prepared eutectic solvent and Cu 2+ The prepared ionic liquid mixture utilizes the amino groups and Fe in triethylamine nitrate. 3+ Coordination occurs between them to form Fe 3+ and Cu 2+ The bimetallic coupling desulfurization system improves the removal efficiency of the purifier for H2S and H2Se gases.

[0041] (4) The nitrogen-doped graphene CIGS thin film battery exhaust gas purifier prepared by the present invention has the characteristics of efficient removal of H2S and H2Se gases at room temperature, and can be widely used in the field of efficient purification materials at room temperature, and has good commercial application value. Detailed Implementation

[0042] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0043] In the following examples, except for the nitrogen-doped graphene carrier and the composite copper source, all other compound monomers and related reagents used can be purchased from the market. Among them, xylan was purchased from Hebei Jiuxing Chemical Products Co., Ltd.

[0044] Preparation Example 1

[0045] The synthesis method of nitrogen-doped graphene support A includes the following steps:

[0046] (1) Dissolve 0.2g graphene oxide, 0.5g phenylboronic acid and 0.8g adenine in 80ml deionized water, stir for 30min, add 40ml 30wt% methanol solution of cobalt nitrate hexahydrate, stir for 30min, heat to 140℃, stir for 5h, and obtain product 1 for later use.

[0047] (2) Cool product 1 to room temperature, distill under reduced pressure, dry at 80°C for 12 hours, and calcine at 800°C for 1 hour under N2 to obtain product 2 for later use.

[0048] (3) Dissolve 33g xylan in 100ml of 10wt% citric acid solution, stir for 60min, add 1g of product 2 from step (2), sonicate for 30min, wash 3 times with deionized water, and dry at 60℃ for 12h to obtain nitrogen-doped graphene carrier A.

[0049] Preparation Example 2

[0050] Nitrogen-doped graphene carrier B is implemented in the same way as nitrogen-doped graphene carrier A, except that the mass of adenine in step (1) is replaced with 0.36g.

[0051] Preparation Example 3

[0052] Nitrogen-doped graphene carrier C is implemented in the same way as nitrogen-doped graphene carrier A, except that the mass of xylan in step (3) is replaced with 30.5g.

[0053] Preparation Example 4

[0054] The synthesis method of composite copper source A includes the following steps:

[0055] 1) Mix 0.04 mol of ferric nitrate hexahydrate and 60 ml of ethylene glycol, and stir at 55 °C for 25 min to obtain mixture 1 for later use;

[0056] 2) Mix 20g of triethylamine nitrate and 0.1mol of copper nitrate, stir for 10min, heat to 65℃ and stir for 3h to obtain mixture 2 for later use;

[0057] 3) Take mixture 1 from step 1) and add it to mixture 2 from step 2), stir for 40 minutes to obtain composite copper source A.

[0058] Preparation Example 5

[0059] Composite copper source B is implemented in the same way as composite copper source A, except that in step 1), the number of moles of ferric nitrate hexahydrate is replaced with 0.015 mol.

[0060] Preparation Example 6

[0061] The composite copper source C is implemented in the same way as the composite copper source A, except that in step 1), the number of moles of ferric nitrate hexahydrate is replaced with 0.07 mol. Example 1

[0062] A method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier includes the following steps:

[0063] S1. Place 10g of nitrogen-doped graphene support A and 8g of composite copper source A in a reaction vessel, add 8g of 4mol / L ammonia water, stir for 30min, and obtain the reaction product for later use.

[0064] S2. Add 2g of 1.5mol / L sodium hydroxide solution to the reaction product of step S1, stir for 25min, wash three times with deionized water, filter, and dry at 30℃ for 24h to obtain nitrogen-doped graphene CIGS thin film battery exhaust gas purifier. Example 2

[0065] A method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier includes the following steps:

[0066] S1. Place 10g of nitrogen-doped graphene support A and 6g of composite copper source A in a reaction vessel, add 4.8g of 3mol / L ammonia water, stir for 20min, and obtain the reaction product for later use.

[0067] S2. Add 1.2g of 1mol / L sodium hydroxide solution to the reaction product of step S1, stir for 20min, wash three times with deionized water, filter, and dry at 30℃ for 24h to obtain nitrogen-doped graphene CIGS thin film battery exhaust gas purifier. Example 3

[0068] A method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier includes the following steps:

[0069] S1. Place 10g of nitrogen-doped graphene support A and 10g of composite copper source A in a reaction vessel, add 14.4g of 5mol / L ammonia water, stir for 40min, and obtain the reaction product for later use.

[0070] S2. Add 3.6g of 2mol / L sodium hydroxide solution to the reaction product of step S1, stir for 30min, wash three times with deionized water, filter, and dry at 30℃ for 24h to obtain nitrogen-doped graphene CIGS thin film battery exhaust gas purifier. Example 4

[0071] This invention provides a method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier. The specific implementation method is the same as in Example 1, except that the mass of the composite copper source A in step S1 is replaced with 5g. Example 5

[0072] This invention provides a method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier. The specific implementation method is the same as in Example 1, except that the mass of the composite copper source A in step S1 is replaced with 12g. Example 6

[0073] This invention provides a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier and its preparation method. The specific implementation method is the same as in Example 1, except that nitrogen-doped graphene carrier B replaces nitrogen-doped graphene carrier A in an equal amount. Example 7

[0074] This invention provides a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier and its preparation method. The specific implementation method is the same as in Example 1, except that nitrogen-doped graphene carrier C replaces nitrogen-doped graphene carrier A in an equal amount. Example 8

[0075] This invention provides a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier and its preparation method. The specific implementation method is the same as in Example 1, except that composite copper source B replaces composite copper source A in an equal amount. Example 9

[0076] This invention provides a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier and its preparation method. The specific implementation method is the same as in Example 1, except that composite copper source C replaces composite copper source A in an equal amount.

[0077] Comparative Example 1

[0078] This comparative example provides a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier and its preparation method. The specific implementation method is the same as in Example 1, except that graphene is used instead of nitrogen-doped graphene carrier A.

[0079] Comparative Example 2

[0080] This comparative example provides a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier and its preparation method. The specific implementation method is the same as in Example 1, except that copper hydroxide is used instead of composite copper source A.

[0081] The removal performance of the nitrogen-doped graphene CIGS thin-film battery exhaust gas purifiers described in Examples 1-9 and Comparative Examples 1-2 on H2S and H2Se gases at room temperature was tested, and the test results are shown in Table 1.

[0082] The effectiveness of the purification agent in removing H2S and H2Se gases at room temperature was determined through exhaust gas treatment performance testing.

[0083] The nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier obtained by drying was pulverized and ground to obtain 100-mesh powder. The powder was then placed in the mold of a tablet press and pressed into a sheet material at 10 MPa. The sheet material was briefly cut into smaller thin sheets, and then mixed evenly with 100-mesh quartz sand at a mass ratio of 1:1 before being placed in the experimental area of ​​the reaction tube.

[0084] Then, the CIGS industrial simulated exhaust gas (a mixture of N2 / H2S / H2Se, H2S=3000ppm, H2Se=500ppm, with the remainder being N2) was directly introduced into the reaction tube for purification at a rate of 500ml / min. Finally, the hose at the outlet of the reaction tube was introduced into the exhaust gas absorption device (40wt% NaOH solution), the main gas valve was closed, and the flow meter was adjusted to zero.

[0085]

[0086] As shown in Table 1, the nitrogen-doped graphene CIGS thin-film battery exhaust gas purifiers in Examples 1-3 of this invention exhibit high H2S and H2Se conversion rates. Specifically, Examples 4-5 altered the reaction ratio between the nitrogen-doped graphene support and the composite copper source, resulting in insufficient loading of the composite copper source onto the nitrogen-doped graphene support, hindering its stable desulfurization function and leading to a decrease in H2S and H2Se conversion rates. Examples 6-7 altered the nitrogen doping ratio during the preparation of the nitrogen-doped graphene support and the loading ratio between xylan and nitrogen-doped graphene, reducing the active sites and specific surface area of ​​graphene oxide, thereby decreasing the H2S and H2Se conversion rates. Examples 8-9 altered the Fe content in the composite copper source. 3+ and Cu 2+ The ratio of H2S to H2Se reduces the synergistic effect between metals, resulting in a significant decrease in the conversion rates of both H2S and H2Se.

[0087] Comparative Examples 1 and 2 used graphene and copper hydroxide to replace nitrogen-doped graphene support A and composite copper source A, respectively. The tests showed that the H2S and H2Se conversion rates of the prepared CIGS thin-film battery exhaust gas purifiers were poor.

[0088] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier, characterized in that... Includes the following steps: S1. Place the nitrogen-doped graphene support and the composite copper source in a reaction vessel, add ammonia water, and stir for 20-40 minutes to obtain the reaction product for later use; the preparation method of the nitrogen-doped graphene support includes the following steps: (1) Dissolve graphene oxide, phenylboronic acid and adenine in deionized water, stir for 20-40 min, add methanol solution of cobalt nitrate hexahydrate, stir for 20-40 min, heat to 130-150℃, stir for 4-6 h to obtain product 1 for later use. (2) Cool the product 1 from step (1) to room temperature, distill under reduced pressure, dry, and calcine under an inert atmosphere to obtain product 2 for later use. (3) Dissolve xylan in citric acid solution, stir for 50-70 min, add product 2 from step (2), sonicate, wash, and dry to obtain nitrogen-doped graphene carrier; The method for preparing the composite copper source includes the following steps: 1) Mix ferric nitrate hexahydrate and ethylene glycol, and stir at 50-60℃ for 20-30 min to obtain mixture 1 for later use; 2) Mix triethylamine nitrate and copper nitrate, stir for 5-10 minutes, heat to 60-70℃ and stir for 2-4 hours to obtain mixture 2 for later use; 3) Take mixture 1 from step 1), add it to mixture 2 from step 2), and stir for 30-50 minutes to obtain the composite copper source; S2. Add the strong alkaline solution to the reaction product of step S1, stir for 20-30 minutes, wash, filter, and dry to obtain the nitrogen-doped graphene CIGS thin film battery exhaust gas purifier.

2. The preparation method of the nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier according to claim 1, characterized in that: In step (1), the mass ratio of graphene oxide to adenine is 1:(2-5); in step (3), the mass ratio of product 2 to xylan is 1:(31-35).

3. The preparation method of the nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier according to claim 1, characterized in that: The molar ratio of ferric nitrate hexahydrate to copper nitrate is (0.2-0.6):

1.

4. The preparation method of the nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier according to claim 1, characterized in that: In step S1, the mass ratio of nitrogen-doped graphene support to composite copper source is 1:(0.6-1).

5. The preparation method of the nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier according to claim 1, characterized in that: In step S1, the mass ratio of the composite copper source to ammonia is 1:(0.8-1.2), and the concentration of ammonia is 3-5 mol / L.

6. The method for preparing a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier according to claim 1, characterized in that: In step S2, the strong alkaline solution is a sodium hydroxide solution with a concentration of 1-2 mol / L.

7. The preparation method of a nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier according to claim 6, characterized in that, The mass ratio of the composite copper source to the strong alkaline solution is 1:(0.2-0.3).

8. A nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier prepared by the preparation method according to any one of claims 1-7, characterized in that: The nitrogen-doped graphene CIGS thin-film battery exhaust gas purifier has an H2S conversion rate of not less than 93.5% and an H2Se conversion rate of not less than 92%.

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