Method for recycling copper from waste lithium batteries to synthesize perovskite nanocrystals and application of perovskite nanocrystals
By recycling copper from waste lithium batteries and doping it with carbon powder, the crystallinity and stability of perovskite nanocrystals are improved, and the problems of low crystallinity and insufficient stability of existing perovskite nanocrystals are solved, achieving efficient chloride ion detection and resource recovery.
Patent Information
- Application Number
- CN202510294459.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-13
- Publication Date
- 2025-06-13
AI Technical Summary
The existing perovskite nanocrystals have low crystallinity and insufficient stability, making it difficult to meet the demand for chloride ion detection.
By recovering copper from waste lithium batteries and doping with carbon powder, specific chemical reactions and treatment steps are adopted to improve the crystallinity and stability of perovskite nanocrystals.
It significantly improves the crystallinity and chemical stability of perovskite nanocrystals, improves its fluorescence performance and detection sensitivity, reduces production costs, and realizes resource recovery.
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Figure CN120136155A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a method for recovering copper from waste lithium batteries to synthesize perovskite nanocrystals and the application of the perovskite nanocrystals. Background Art
[0002] Currently, the detection methods for chloride ions mainly include titration method, atomic absorption method, spectrophotometry, and ion-selective electrode method. The titration method has a cumbersome operation process, requires the use of toxic chemical reagents, has a long detection period, and cannot meet the need for rapid detection and analysis; the atomic absorption method requires the use of special instrument equipment, which is expensive and cannot be popularized on a large scale; although the spectrophotometry has a low cost, it requires the use of toxic reagents such as silver nitrate and silver chromate, has poor biological safety, and is easy to cause environmental pollution; the ion-selective electrode method is easily damaged and fails, so it needs to be frequently replaced, which brings inconvenience to rapid detection and also increases the cost.
[0003] Perovskite nanocrystal test papers have application potential in the field of ion detection. By using the reaction of perovskite nanocrystals with chloride ions and testing the fluorescence spectrum of the obtained powder, the detection of chloride ions can be realized. However, the existing perovskite nanocrystals have low crystallinity and insufficient stability, so they need to be improved. Summary of the Invention
[0004] The purpose of the present invention is to provide a method for recovering copper from waste lithium batteries to synthesize perovskite nanocrystals and the application of the perovskite nanocrystals. By doping with carbon powder and copper, the crystallinity and stability of the perovskite nanocrystals can be effectively improved.
[0005] In order to achieve the above purpose, the technical solutions adopted by the present invention are as follows: A method for recovering copper from waste lithium batteries to synthesize perovskite nanocrystals, comprising the following steps: 1) Disassemble the waste lithium battery, dissolve the negative electrode containing copper foil and carbon powder with sulfuric acid, evaporate to dryness to obtain a mixture of copper sulfate and carbon powder, and then perform carbonization treatment to obtain cuprous oxide; 2) React cuprous oxide with hydrobromic acid in proportion to obtain cuprous bromide; 3) Mix cuprous bromide and cesium bromide in proportion, then grind the mixture, place the ground mixture in a vacuum environment for heating, and perform annealing treatment after heating to obtain perovskite powder; 4) Dissolve the perovskite powder in a solvent, coat the solution on a paper substrate, and perform annealing treatment to form perovskite nanocrystals.
[0006] Further, in step 1), the negative electrode containing copper foil and carbon powder is dissolved with dilute sulfuric acid with a mass fraction of 60 - 70%, the mass ratio of the negative electrode to the dilute sulfuric acid is (5 - 10):1, evaporate to dryness to obtain a mixture of copper sulfate and carbon powder, and carbonize it at a temperature of 600 - 650 °C for 3 - 6 h to obtain cuprous oxide.
[0007] Further, in step 2), cuprous oxide and hydrobromic acid are mixed at a molar ratio of 1:(1.8 - 2.3) to obtain cuprous bromide.
[0008] Further, in step 3), cesium bromide and cuprous bromide are mixed at a molar ratio of 1:(0.2 - 1.8), the mixture is ground in a zirconia ball mill pot, then sealed in a vacuumed quartz flask, and annealed at 400°C - 800°C for 2 - 5 h, and then cooled to room temperature.
[0009] Further, the solvent is N,N - dimethylformamide.
[0010] Further, in step 4), 0.1 - 0.5 g of perovskite powder is dissolved in 40 - 60 ml of N,N - dimethylformamide at 150 - 250°C, the solution is coated on a paper substrate at a rotation speed of 1000 - 1500 r / min, and annealed at 80 - 120°C for 15 - 30 minutes.
[0011] The present invention also discloses the application of the perovskite nanocrystals prepared by the above method in chloride ion detection.
[0012] The present invention has the following beneficial effects: In the preparation process of perovskite nanocrystals, carbon powder is involved, which significantly improves the crystallinity of perovskite nanocrystals. At the same time, the recovered copper can optimize the lattice structure of perovskite, further enhancing its chemical stability. Perovskite nanocrystals themselves have excellent fluorescence properties, including high fluorescence quantum yield and tunable optical bandgap, and the doping of carbon powder can further improve their fluorescence characteristics, thereby enhancing the detection sensitivity.
[0013] At the same time, the introduction of carbon powder can enhance its surface activity, provide more active sites, and further improve the interaction with chloride ions. At the same time, the addition of carbon powder can also improve the dispersibility of perovskite nanocrystals, making their distribution in the solution more uniform, thereby improving the accuracy and reproducibility of detection.
[0014] This method has the advantages of low cost and environmental protection. By using copper and carbon powder in waste lithium batteries as raw materials, it not only reduces the production cost but also realizes resource recovery, meeting the concept of green chemistry. Description of the Drawings
[0015] Figure 1 It is the fluorescence spectrum diagram of the perovskite nanocrystals prepared in Example 1 at 310 - 560 nm under 290 nm excitation light.
[0016] Figure 2Fluorescence spectra of the perovskite nanocrystals prepared in Example 2 in the range of 310 - 560 nm under 290 nm excitation light.
[0017] Figure 3 Fluorescence spectra of the perovskite nanocrystals prepared in Example 3 in the range of 310 - 560 nm under 290 nm excitation light.
[0018] Figure 4 Fluorescence spectra of the perovskite nanocrystals prepared in Example 4 in the range of 310 - 560 nm under 290 nm excitation light.
[0019] Figure 5 Fluorescence spectra of the perovskite nanocrystals prepared in Example 5 in the range of 310 - 560 nm under 290 nm excitation light.
[0020] Figure 6 Fluorescence spectra of the perovskite nanocrystals prepared in Example 6 in the range of 310 - 560 nm under 290 nm excitation light.
[0021] Figure 7 Fluorescence spectra of the perovskite nanocrystals prepared in Example 1 after being placed for 24 h in the range of 310 - 560 nm under 290 nm excitation light.
[0022] Figure 8 Fluorescence spectra of the precipitate obtained by centrifugation after magnetic stirring for 2 hours of the perovskite nanocrystals prepared in Example 1 in the range of 310 - 560 nm under 290 nm excitation light in the chlorine - containing wastewater. Detailed implementation manners Example 1
[0023] A method for recovering copper from waste lithium batteries to synthesize perovskite nanocrystals, comprising the following steps: 1) Discharge and dry the waste lithium battery with brine, then disassemble it. Dissolve the negative electrode containing copper foil and carbon powder with 60% mass - fraction dilute sulfuric acid, and the mass ratio of the negative electrode to the dilute sulfuric acid is 5:1. After evaporation to dryness, a mixture of copper sulfate and carbon powder is obtained, and it is carbonized at 600 °C for 3 h to obtain cuprous oxide.
[0024] 2) Mix cuprous oxide and hydrobromic acid in a molar ratio of 1:2 for reaction to obtain cuprous bromide.
[0025] 3) Mix cesium bromide and cuprous bromide in a molar ratio of 1:0.5, place the mixture in a zirconia ball - mill pot for grinding, then seal it in a vacuum - pumped quartz flask, and then anneal it at 400 °C for 2 h and then naturally cool to room temperature to obtain perovskite powder; 4) Dissolve 0.1 g of perovskite powder in 40 ml of N,N-dimethylformamide at 150 °C. Coat the solution on a paper substrate at a rotation speed of 1000 r / min and anneal it at 80 °C for 15 minutes to prepare a perovskite nanocrystal test paper.
[0026] The fluorescence spectrum of the prepared perovskite nanocrystals at 310 - 560 nm under 290 nm excitation light is as Figure 1 shown.
[0027] It can be seen from Figure 1 that the perovskite nanocrystals have obvious fluorescence peaks near 410 nm and 510 nm, and the peak heights are relatively high, indicating that the material has a long light emission ability at these wavelengths, with high crystallinity and few defects. Example 2
[0028] A method for synthesizing perovskite nanocrystals by recycling copper from waste lithium batteries, comprising the following steps: 1) Discharge and dry the waste lithium battery in brine, then disassemble it. Dissolve the negative electrode containing copper foil and carbon powder in dilute sulfuric acid with a mass fraction of 65%. The mass ratio of the negative electrode to dilute sulfuric acid is 6:1. After evaporation to dryness, a mixture of copper sulfate and carbon powder is obtained, and it is carbonized at 600 °C for 4 h to obtain cuprous oxide.
[0029] 2) React cuprous oxide with hydrobromic acid at a molar ratio of 1:2.1 to obtain cuprous bromide.
[0030] 3) Mix cesium bromide and cuprous bromide at a molar ratio of 1:1. Put the mixture in a zirconia ball mill pot and grind it, then seal it in a quartz pot under vacuum. Anneal the mixture at 500 °C for 3 h, and then naturally cool it to room temperature to obtain perovskite powder; 4) Dissolve 0.2 g of perovskite powder in 45 ml of N,N-dimethylformamide at 180 °C. Coat the solution on a paper substrate at a rotation speed of 1100 r / min and anneal it at 90 °C for 18 minutes to prepare a perovskite nanocrystal test paper.
[0031] The fluorescence spectrum of the prepared perovskite nanocrystals at 310 - 560 nm under 290 nm excitation light is as Figure 2 shown.
[0032] It can be seen from Figure 2 that the perovskite nanocrystals still have obvious fluorescence peaks near 410 nm and 510 nm, indicating that the material has good light emission ability at these wavelengths, with good crystallinity and few defects. Example 3
[0033] A method for synthesizing perovskite nanocrystals by recycling copper from waste lithium batteries, comprising the following steps: 1) Discharge and dry the waste lithium battery through brine, then disassemble it. Dissolve the negative electrode containing copper foil and carbon powder with dilute sulfuric acid with a mass fraction of 70%. The mass ratio of the negative electrode to the dilute sulfuric acid is 7:1. After evaporation to dryness, a mixture of copper sulfate and carbon powder is obtained, and it is carbonized at a temperature of 600 °C for 5 h to obtain cuprous oxide.
[0034] 2) React cuprous oxide with hydrobromic acid at a molar ratio of 1:2.2 to obtain cuprous bromide.
[0035] 3) Mix cesium bromide and cuprous bromide at a molar ratio of 1:1.5. Put the mixture in a zirconia ball mill pot for grinding, then seal it in a vacuumed quartz pot. Anneal the mixture at 600 °C for 4 h, and then naturally cool it to room temperature to obtain perovskite powder; 4) Dissolve 0.3 g of perovskite powder in 50 ml of N,N-dimethylformamide at 200 °C. Coat the solution on a paper-based substrate at a rotation speed of 1200 r / min and anneal it at 100 °C for 20 minutes to make a perovskite nanocrystal test paper.
[0036] The fluorescence spectrum of the prepared perovskite nanocrystals at 310 - 560 nm under 290 nm excitation light is as Figure 3 shown.
[0037] It can be seen from Figure 3 that the perovskite nanocrystals still have obvious fluorescence peaks near 410 nm and 510 nm, and the peak values are relatively low, indicating that the material has good light emission ability, good crystallinity and fewer defects in these regions, and the stability of the material is relatively high. Example 4
[0038] A method for recycling copper from waste lithium batteries to synthesize perovskite nanocrystals, comprising the following steps: 1) Discharge and dry the waste lithium battery through brine, then disassemble it. Dissolve the negative electrode containing copper foil and carbon powder with dilute sulfuric acid with a mass fraction of 70%. The mass ratio of the negative electrode to the dilute sulfuric acid is 8:1. After evaporation to dryness, a mixture of copper sulfate and carbon powder is obtained, and it is carbonized at a temperature of 650 °C for 6 h to obtain cuprous oxide.
[0039] 2) React cuprous oxide with hydrobromic acid at a molar ratio of 1:2.3 to obtain cuprous bromide.
[0040] 3) Mix cesium bromide and cuprous bromide at a molar ratio of 1:2. Put the mixture in a zirconia ball mill pot for grinding, then seal it in a vacuumed quartz pot. Anneal the mixture at 700 °C for 5 h, and then naturally cool it to room temperature to obtain perovskite powder; 4) Dissolve 0.4 g of perovskite powder in 60 ml of N,N-dimethylformamide at 250 °C, coat the solution on a paper substrate at a rotation speed of 1300 r / min, and anneal it at 110 °C for 25 minutes to prepare a perovskite nanocrystal test paper.
[0041] The fluorescence spectrum of the prepared perovskite nanocrystals at 310 - 560 nm under 290 nm excitation light is as Figure 4 shown.
[0042] It can be seen from Figure 4 that there are no obvious fluorescence peaks near 310 nm and 560 nm for the perovskite nanocrystals, indicating that the optical properties of the perovskite nanocrystals are poor, the chemical composition deviates from the ideal ratio, the material crystallinity is low, and there are many defects in the material, resulting in the non-obvious or missing fluorescence peaks. Example 5
[0043] A method for recycling copper from waste lithium batteries to synthesize perovskite nanocrystals, comprising the following steps: 1) Discharge and dry the waste lithium battery with brine, then disassemble it, dissolve the negative electrode containing copper foil and carbon powder with 60% by mass of dilute sulfuric acid, the mass ratio of the negative electrode to the dilute sulfuric acid is 9:1, evaporate to dryness to obtain a mixture of copper sulfate and carbon powder, and carbonize it at 600 °C for 6 h to obtain cuprous oxide.
[0044] 2) React cuprous oxide with hydrobromic acid at a molar ratio of 1:2.4 to obtain cuprous bromide.
[0045] 3) Mix cesium bromide and cuprous bromide at a molar ratio of 1:2.5, place the mixture in a zirconia ball mill pot for grinding, then seal it in a vacuumed quartz flask, anneal the mixture at 800 °C for 5 h, and then naturally cool it to room temperature to obtain perovskite powder; 4) Dissolve 0.5 g of perovskite powder in 40 ml of N,N-dimethylformamide at 150 °C, coat the solution on a paper substrate at a rotation speed of 1400 r / min, and anneal it at 120 °C for 30 minutes to prepare a perovskite nanocrystal test paper.
[0046] The fluorescence spectrum of the prepared perovskite nanocrystals at 310 - 560 nm under 290 nm excitation light is as Figure 5 shown.
[0047] It can be seen from Figure 5 that there are no obvious fluorescence peaks near 310 nm and 560 nm for the perovskite nanocrystals, indicating that the optical properties of the perovskite nanocrystals are poor, the chemical composition deviates from the ideal ratio, the material crystallinity is low, and there are many defects in the material, resulting in the non-obvious or missing fluorescence peaks. Example 6
[0048] Method for recycling copper from waste lithium batteries to synthesize perovskite nanocrystals, comprising the following steps: 1) Discharge and dry the waste lithium batteries with brine, then disassemble them. Dissolve the negative electrode containing copper foil and carbon powder with dilute sulfuric acid with a mass fraction of 70%. The mass ratio of the negative electrode to the dilute sulfuric acid is 10:1. After evaporation to dryness, a mixture of copper sulfate and carbon powder is obtained, and it is carbonized at a temperature of 600 °C for 6 h to obtain cuprous oxide.
[0049] 2) React cuprous oxide with hydrobromic acid at a molar ratio of 1:2.5 to obtain cuprous bromide.
[0050] 3) Mix cesium bromide and cuprous bromide at a molar ratio of 1:3.5, place the mixture in a zirconia ball mill pot for grinding, then seal it in a vacuumed quartz flask. Anneal the mixture at 800 °C for 5 h, and then naturally cool it to room temperature to obtain perovskite powder; 4) Dissolve 0.5 g of perovskite powder in 60 ml of N,N - dimethylformamide at 250 °C, coat the solution on a paper substrate at a rotation speed of 1500 r / min, and anneal it at 120 °C for 30 minutes to make a perovskite nanocrystal test paper.
[0051] The fluorescence spectrum of the prepared perovskite nanocrystals at 310 - 560 nm under 290 nm excitation light is as Figure 6 shown.
[0052] It can be seen from Figure 6 that there are no obvious fluorescence peaks near 310 nm and 560 nm for the perovskite nanocrystals, indicating that the optical properties of the perovskite nanocrystals are poor, the chemical composition deviates from the ideal ratio, the crystallinity of the material is low, and there are many defects in the material, resulting in the non - obvious or missing fluorescence peaks. Example 7
[0053] After placing the perovskite nanocrystals prepared in Example 1 for 24 h, its fluorescence spectrum at 310 - 560 nm under 290 nm excitation light is as Figure 7 shown.
[0054] It can be seen from Figure 7 that there are obvious fluorescence peaks near 410 nm and 510 nm for the perovskite powder, and the peak heights are relatively high, and there is not much difference from Figure 1 which indicates that the material has good stability under normal conditions, the crystal structure of the material is relatively stable, and it is not prone to photodegradation.
[0055] Dissolve 0.05 g of sodium chloride in water and make up the volume to 10 ml to prepare a 5 g / L sodium chloride solution. Add 3 - 4 drops of concentrated sulfuric acid and adjust the pH to 1 to prepare the chlorine-containing wastewater. Take 0.5 g of the above perovskite nanocrystals and place them in the chlorine-containing wastewater. After stirring for 2 h with a magnetic stirrer, centrifuge them in a centrifuge, pour off the supernatant, and put the precipitate into an oven at 80 °C for 40 min to dry the precipitate. The fluorescence spectrum of the precipitate at 310 - 560 nm under 290 nm excitation light is as Figure 8 shown.
[0056] It can be seen from Figure 8 that the precipitate has obvious fluorescence peaks near 410 nm and 510 nm, the peak height is relatively low, and the overall peak shape is not much different from Figure 7 . It shows that the material can be used for the detection of chloride ions and the material has good stability.
[0057] The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, several improvements can be made without departing from the principle of the present invention, and these improvements should also be regarded as the protection scope of the present invention.
Claims
1. A method for recovering copper from waste lithium batteries to synthesize perovskite nanocrystals, characterized in that: The steps include: 1) Dismantle discarded lithium batteries, use sulfuric acid to dissolve the negative electrode containing copper foil and carbon powder, evaporate to dryness to obtain a mixture of copper sulfate and carbon powder, and then carbonize to obtain cuprous oxide; 2) Mix cuprous oxide and hydrobromic acid to react to obtain cuprous bromide; 3) mixing cuprous bromide and cesium bromide to react, then grinding the mixture, heating it in a vacuum environment, and annealing it after heating to obtain perovskite powder; 4) The perovskite powder is dissolved in a solvent, and the resulting solution is coated on a paper-based substrate. After annealing, perovskite nanocrystals are formed.
2. The method for recovering copper-synthesized perovskite nanocrystals from waste lithium batteries according to claim 1, characterized in that: In step 1), the negative electrode containing copper foil and carbon powder is dissolved in dilute sulfuric acid with a mass fraction of 60-70%, and the mass ratio of the negative electrode to the dilute sulfuric acid is (5-10):
1. After evaporation, a mixture of copper sulfate and carbon powder is obtained, which is carbonized at a temperature of 600-650°C for 3-6h to obtain cuprous oxide.
3. The method for recovering copper-synthesized perovskite nanocrystals from waste lithium batteries according to claim 1, characterized in that: In step 2), cuprous oxide and hydrobromic acid are mixed in a molar ratio of 1:(1.8-2.3) to obtain cuprous bromide.
4. The method for recovering copper-synthesized perovskite nanocrystals from waste lithium batteries according to claim 1, characterized in that: In step 3), cesium bromide and cuprous bromide are mixed in a molar ratio of 1: (0.2-1.8), the mixture is ground in a zirconia ball mill, and then sealed in a vacuum quartz pot, annealed at 400°C-800°C for 2-5h, and then cooled to room temperature.
5. The method for recovering copper-synthesized perovskite nanocrystals from waste lithium batteries according to claim 1, characterized in that: The solvent is N,N-dimethylformamide.
6. The method for recovering copper-synthesized perovskite nanocrystals from waste lithium batteries as claimed in claim 5, characterized in that: In step 4), 0.1-0.5 g of perovskite powder is dissolved in 40-60 ml of N,N-dimethylformamide at 150-250° C., the solution is coated on a paper-based substrate at a rotation speed of 1000-1500 r / min, and annealed at 80-120° C. for 15-30 minutes.
7. Use of the perovskite nanocrystals prepared by the method according to any one of claims 1 to 6 in chloride ion detection.