Carbon nano hollow sphere water photovoltaic power generation device with partition resistors and preparation method thereof

Abstract

The invention relates to a carbon nano hollow sphere water photovoltaic power generation device with partition resistors and a preparation method thereof. According to the scheme, the method comprises the following steps: dissolving glucose and poly (4-styrenesulfonic acid-co-maleic acid) sodium salt in water, and carrying out hydrothermal reaction; and carrying out solid-liquid separation on the obtained product, cleaning the solid, and carbonizing the obtained carbon nano hollow sphere precursor in an argon atmosphere at different temperatures to respectively obtain the high-resistance carbon nano hollow sphere and the low-resistance carbon nano hollow sphere. And respectively adding the two carbon nano hollow spheres, terpilenol, ethyl cellulose and glass fiber filter paper into absolute ethyl alcohol, stirring, and drying to obtain corresponding high-resistance slurry or low-resistance slurry. An electrode is drawn on a corundum substrate, the lower half portion and the upper half portion of a thin film area are coated with the high-resistance slurry and the low-resistance slurry in a blade coating mode respectively, and the carbon nano hollow sphere water photovoltaic power generation device with the regional resistance is manufactured after annealing. The preparation method is simple in process and low in cost, and the prepared product can effectively improve the charge transmission process and realize double optimization of voltage and current.

Description

Technical Field

[0001] This invention belongs to the field of carbon nanotube hollow sphere hydrovoltaic technology. Specifically, it relates to a carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance and its fabrication method. Background Technology

[0002] The water-powered photovoltaic effect refers to the process by which water, during its movement (such as flow or undulation), interacts directly with materials at the nanoscale, thereby converting water energy into electrical energy. Its principle is primarily based on the Debye shielding effect theory. When water flows over the surface of a solid material, an electric double layer forms at the solid-liquid interface. If the water flow channel is close to or smaller than the Debye radius of the solution, the double layer overlaps within the channel, causing ions to selectively pass through, creating a flow potential at both ends of the channel—the Debye shielding effect. The water-powered photovoltaic effect can fully utilize the Earth's abundant water resources for power generation and is currently a research hotspot in the field of energy conversion technology. Reported water-powered photovoltaic research mainly focuses on the development of material systems and the construction of water flow channels. Specific technologies are as follows: "A micro-ordered water-voltaic device and its fabrication method" (CN118739902A) describes a method based on nano-silica self-assembly technology. Although the fabricated water-voltaic power generation device is simple to operate and low in cost, and its ordered microstructure allows for easier micro-design, its open-circuit voltage is only about 0.15mV, indicating that there is still considerable room for improvement in terms of power output.

[0003] A patterned hydrovoltaic power generation device and its fabrication method are disclosed (CN120049764AS1). This method uses a printing device to print a precursor solution prepared from zinc salts and auxiliary materials onto a substrate. After curing, electrodes are fabricated to obtain the patterned hydrovoltaic power generation device. Although this device has a high open-circuit voltage output, its short-circuit current is low, with an average short-circuit current of only about 23 nA per device, resulting in low power output.

[0004] A photoresponsive photovoltaic device based on nano-tungsten oxide and its fabrication method (CN119582646A) uses tungsten oxide mixed with auxiliary materials to prepare a slurry. Although this device can generate an open-circuit voltage of 1.4~1.8V and a short-circuit current of 100nA~140nA, and the short-circuit current can increase with illumination, it is accompanied by a significant decrease in open-circuit voltage, and thus cannot effectively improve the power output.

[0005] This invention relates to a nanocellulose composite aerogel, its preparation method, and a water-voltaic power generation device (CN116790024A). The invention involves preparing dispersions of modified nanocellulose and carboxylated carbon nanotubes, uniformly mixing them under high-speed shear conditions, freezing the mixture, and then immersing it in anhydrous ethanol / metal salt solution for dissolution and crosslinking. The resulting product is then rinsed and dried to obtain a nanocellulose composite aerogel. A water-voltaic device is obtained by fixing wires to both ends of the aerogel. While this method is easy to operate and the resulting device can generate an open-circuit voltage of approximately 0.6V, the raw material cost is high, making large-scale production difficult.

[0006] The literature (Rahul Kumar, George Kay, Graham Beaton, et al. Tuning the Functionalization of Graphite for Hydrovoltaic Power Generation [J]. ACS Applied Materials & Interfaces, 2023, 15(5): 7511-7517.) reports a functionalized graphene hydrovoltaic power generation device. This device uses graphene as a raw material. The graphene is functionalized through acid treatment to enhance its electrical effect. Then, auxiliary materials are added to prepare a slurry, which is ultrasonically treated, drawn onto a substrate, and dried to obtain the hydrovoltaic power generation device. Although this device can generate approximately 53.3 μW / g of power per unit mass, it requires expensive graphene as a raw material, resulting in high costs for mass production.

[0007] The technical defects of the above-disclosed technology are: high cost, low power output, and difficulty in simultaneously increasing open-circuit voltage and short-circuit current. Summary of the Invention

[0008] The present invention aims to overcome the defects of the prior art and provides a low-cost method for preparing a partitioned resistive carbon nanotube hollow sphere water photovoltaic power generation device. The partitioned resistive carbon nanotube hollow sphere water photovoltaic power generation device prepared by this method has high open-circuit voltage and short-circuit current, and high power output.

[0009] To achieve the above objectives, the technical solution adopted by this invention comprises the following steps: Step 1: Dissolve 9-12 parts by weight of glucose and 0.5-0.8 parts by weight of sodium poly(4-styrenesulfonic acid-copolymer-maleic acid) in 50-55 parts by weight of deionized water and stir for the first time; then transfer to a high-pressure reactor and react at 180-190℃ for 8-12 h. Separate the solid and liquid products, and wash the solid with deionized water and ethanol 3-5 times each to obtain carbon nanotube hollow sphere precursor.

[0010] Step 2: Carbonize half of the carbon nanotube hollow sphere precursor at 550~650℃ in an argon atmosphere for 2~3 h, and ball mill for 0.5~1 h to obtain high-resistivity carbon nanotube hollow spheres.

[0011] Step 3: Carbonize the other half of the carbon nanotube hollow sphere precursor at 800~900℃ in an argon atmosphere for 2~3 hours, and then ball mill it for 0.5~1 hours to obtain low-resistivity carbon nanotube hollow spheres.

[0012] Step 4: Add 8-12 parts by weight of high-resistivity carbon nanotube hollow spheres and 8-12 parts by weight of low-resistivity carbon nanotube hollow spheres, respectively, along with 0.8-1.2 parts by weight of terpineol, 3-5 parts by weight of ethyl cellulose, and 1-1.2 parts by weight of shredded glass fiber filter paper, to 80-85 parts by weight of anhydrous ethanol. Stir for a second time and dry to obtain the corresponding high-resistivity slurry and low-resistivity slurry.

[0013] Step 5: Using conductive carbon paste, coat a large "L"-shaped electrode on the left side and near the bottom edge of an alumina substrate with a length L1 = 90~120mm and a width B1 = 40~60mm. Coat a small "L"-shaped electrode on the right side and near the top edge of the alumina substrate using conductive carbon paste. A thin film region is formed between two electrodes with a spacing L2 = (0.8~0.9)L1 along the long side of the corundum substrate and a spacing B2 = (0.5~0.6)B1 along the wide side of the corundum substrate. The high-resistance slurry and the low-resistance slurry are respectively coated onto the lower half and upper half of the thin film region to obtain a high-resistance thin film and a low-resistance thin film. Then, the film is annealed in a muffle furnace at 300~350℃ for 1~2 hours to obtain a carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance.

[0014] The solid-liquid separation refers to solid-liquid separation for 3 to 5 minutes under a rotation speed of 8000 to 10000 r / min.

[0015] The high-resistivity carbon nanotube hollow spheres have a particle size of 300~500nm, and the low-resistivity carbon nanotube hollow spheres have the same particle size as the high-resistivity carbon nanotube hollow spheres.

[0016] The area ratio of the high-resistivity film to the low-resistivity film is 1~2:1, and the thickness of the high-resistivity film and the low-resistivity film is the same, both being 300~500μm.

[0017] The area of ​​the shredded glass fiber filter paper is 1~10 mm². 2 .

[0018] The first stirring speed is 150~200 r / min, and the first stirring time is 1~2 h.

[0019] The drying temperature is 60~70℃, and the drying time is 4~5 hours.

[0020] The thickness of the large "L"-shaped electrode is 100~200μm; the thickness of the small "L"-shaped electrode is 100~200μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance L3 between the horizontal edge of the shaped electrode and the top edge of the corundum substrate is (0.05~0.1)L1. The distance between the horizontal side of the shaped electrode and the left side is B3 = (0.2~0.3)B1.

[0021] The second stirring speed is 150~200 r / min, and the second stirring time is 5~6 h.

[0022] By adopting the above technical solution, the present invention has the following advantages compared with the prior art: (1) This invention employs a partitioned resistor design, constructing high-resistance and low-resistance thin films in the partitioned resistor carbon nanotube hollow sphere photovoltaic device region to balance the charge transfer process within the carbon nanotube hollow sphere thin film. The high-resistance thin film facilitates charge accumulation, promoting the formation of a high open-circuit voltage; the low-resistance thin film facilitates charge transfer, promoting the formation of a high short-circuit current. The partitioned resistor carbon nanotube hollow sphere photovoltaic device fabrication technology provided by this invention can regulate the charge migration process of the partitioned resistor carbon nanotube hollow sphere photovoltaic device, thus achieving a dual increase in open-circuit voltage and short-circuit current.

[0023] (2) The carbon nanotube hollow spheres used in this invention are a typical carbon nanomaterial, possessing the excellent electrochemical properties of carbon-based materials. Furthermore, the synthesis process for preparing carbon nanotube hollow spheres is simple, involves no complex operations, and is easy to implement. The main raw material required for preparation is glucose, which is widely available and inexpensive. Therefore, the fabrication cost of the partitioned resistor carbon nanotube hollow sphere hydrovoltaic power generation device is low.

[0024] (3) The carbon nanotube hollow sphere water photovoltaic power generation device with partitioned resistance prepared in this invention can regulate the charge accumulation and transfer process by depending on the resistance of different regions, and realize the synchronous improvement of open circuit voltage and short circuit current. The open circuit voltage of the prepared water photovoltaic power generation device is 400~600mV and the short circuit current reaches 1~1.4μA. Therefore, the prepared carbon nanotube hollow sphere water photovoltaic power generation device with partitioned resistance has high power output.

[0025] Therefore, the present invention has low manufacturing cost, and the prepared partitioned resistive carbon nanotube hollow sphere water photovoltaic power generation device not only has high open-circuit voltage and short-circuit current, but also high power output. Attached Figure Description

[0026] Figure 1 This invention relates to the fabrication process of a partitioned resistor carbon nanotube hollow sphere hydrovoltaic power generation device. Figure 2 for Figure 1 SEM image of the fabricated carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance; Figure 3 for Figure 1 Vt curves of the fabricated carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance; Figure 4 for Figure 1 The It curve of the prepared partitioned resistor carbon nanotube hollow sphere hydrovoltaic device. Detailed Implementation

[0027] The present invention will be further described below with reference to specific embodiments, but this is not intended to limit the scope of protection thereof.

[0028] A carbon nanotube hollow sphere hydrovoltaic power generation device with partitioned resistance and its fabrication method. The specific fabrication method of this embodiment is as follows: Step 1: Dissolve 9-12 parts by weight of glucose and 0.5-0.8 parts by weight of sodium poly(4-styrenesulfonic acid-copolymer-maleic acid) in 50-55 parts by weight of deionized water and stir for the first time; then transfer to a high-pressure reactor and react at 180-190℃ for 8-12 h. Separate the solid and liquid products, and wash the solid with deionized water and ethanol 3-5 times each to obtain carbon nanotube hollow sphere precursor.

[0029] Step 2: Carbonize half of the carbon nanotube hollow sphere precursor at 550~650℃ in an argon atmosphere for 2~3 h, and ball mill for 0.5~1 h to obtain high-resistivity carbon nanotube hollow spheres.

[0030] Step 3: Carbonize the other half of the carbon nanotube hollow sphere precursor at 800~900℃ in an argon atmosphere for 2~3 hours, and then ball mill it for 0.5~1 hours to obtain low-resistivity carbon nanotube hollow spheres.

[0031] Step 4: Add 8-12 parts by weight of high-resistivity carbon nanotube hollow spheres and 8-12 parts by weight of low-resistivity carbon nanotube hollow spheres, respectively, along with 0.8-1.2 parts by weight of terpineol, 3-5 parts by weight of ethyl cellulose, and 1-1.2 parts by weight of shredded glass fiber filter paper, to 80-85 parts by weight of anhydrous ethanol. Stir for a second time and dry to obtain the corresponding high-resistivity slurry and low-resistivity slurry.

[0032] Step 5: Using conductive carbon paste, coat a large "L"-shaped electrode on the left side and near the bottom edge of an alumina substrate with a length L1 = 90~120mm and a width B1 = 40~60mm. Coat a small "L"-shaped electrode on the right side and near the top edge of the alumina substrate using conductive carbon paste. A thin film region is formed between two electrodes with a spacing L2 = (0.8~0.9)L1 along the long side of the corundum substrate and a spacing B2 = (0.5~0.6)B1 along the wide side of the corundum substrate. The high-resistance slurry and the low-resistance slurry are respectively coated onto the lower half and upper half of the thin film region to obtain a high-resistance thin film and a low-resistance thin film. Then, the film is annealed in a muffle furnace at 300~350℃ for 1~2 hours to obtain a carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance.

[0033] The solid-liquid separation refers to solid-liquid separation for 3 to 5 minutes under a rotation speed of 8000 to 10000 r / min.

[0034] The high-resistivity carbon nanotube hollow spheres have a particle size of 300~500nm, and the low-resistivity carbon nanotube hollow spheres have the same particle size as the high-resistivity carbon nanotube hollow spheres.

[0035] The area ratio of the high-resistivity film to the low-resistivity film is 1~2:1, and the thickness of the high-resistivity film and the low-resistivity film is the same, both being 300~500μm.

[0036] The area of ​​the shredded glass fiber filter paper is 1~10 mm². 2 .

[0037] The first stirring speed is 150~200 r / min, and the first stirring time is 1~2 h.

[0038] The drying temperature is 60~70℃, and the drying time is 4~5 hours.

[0039] The thickness of the large "L"-shaped electrode is 100~200μm; the thickness of the small "L"-shaped electrode is 100~200μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance L3 between the horizontal edge of the shaped electrode and the top edge of the corundum substrate is (0.05~0.1)L1. The distance between the horizontal side of the shaped electrode and the left side is B3 = (0.2~0.3)B1.

[0040] The second stirring speed is 150~200 r / min, and the second stirring time is 5~6 h.

[0041] Example 1 A carbon nanotube hollow sphere hydrovoltaic power generation device with partitioned resistance and its fabrication method. The fabrication method described in this embodiment is as follows: Step 1: Dissolve 9 parts by weight of glucose and 0.5 parts by weight of sodium poly(4-styrenesulfonic acid-copolymer-maleic acid) in 50 parts by weight of deionized water and stir at 150 r / min for 1 h; then transfer to a high-pressure reactor and react at 180 °C for 8 h. Separate the solid and liquid products, and wash the solid three times each with deionized water and ethanol to obtain carbon nanotube hollow sphere precursor.

[0042] Step 2: Carbonize half of the carbon nanotube hollow sphere precursor at 550℃ in an argon atmosphere for 2 hours, and then ball mill for 0.5 hours to obtain high-resistivity carbon nanotube hollow spheres.

[0043] Step 3: Carbonize the other half of the carbon nanotube hollow sphere precursor at 800℃ in an argon atmosphere for 2 hours, and then ball mill it for 0.5 hours to obtain low-resistivity carbon nanotube hollow spheres.

[0044] Step 4: Add 8 parts by weight of high-resistivity carbon nanotube hollow spheres, 0.8 parts by weight of terpineol, 3 parts by weight of ethyl cellulose and 1 part by weight of shredded glass fiber filter paper to 80 parts by weight of anhydrous ethanol, stir at 150 r / min for 5 h, and dry to obtain a high-resistivity slurry.

[0045] Eight parts by weight of low-resistivity carbon nanotube hollow spheres, 0.8 parts by weight of terpineol, 3 parts by weight of ethyl cellulose and 1 part by weight of shredded glass fiber filter paper were added to 80 parts by weight of anhydrous ethanol and stirred for 5 hours at a speed of 150 r / min. The mixture was then dried to obtain a low-resistivity slurry.

[0046] Step 5: Using conductive carbon paste, coat a large "L"-shaped electrode on the left side and near the bottom edge of a corundum substrate with a length L1 = 90 mm and a width B1 = 40 mm. Also coat a small "L"-shaped electrode on the right side and near the top edge of the corundum substrate using conductive carbon paste. A three-dimensional electrode is formed between two electrodes, with a distance of L2=0.8L1 along the long side of the corundum substrate and a distance of B2=0.5B1 along the wide side of the corundum substrate. The high-resistivity slurry is coated onto the lower half of the thin film region to obtain a high-resistivity thin film. The low-resistivity slurry is coated onto the upper half of the thin film region to obtain a low-resistivity thin film. Then, the film is annealed at 300°C for 1 hour in a muffle furnace to obtain a carbon nanotube hollow sphere hydrovoltaic device with zoned resistance.

[0047] The solid-liquid separation refers to solid-liquid separation for 3 minutes at a rotation speed of 8000 r / min.

[0048] The high-resistivity hollow carbon nanospheres have a particle size of 300 nm, and the low-resistivity hollow carbon nanospheres have the same particle size as the high-resistivity hollow carbon nanospheres.

[0049] The area ratio of the high-resistivity film to the low-resistivity film is 1:1, and the thickness of the high-resistivity film and the low-resistivity film is the same, both being 300 μm.

[0050] The area of ​​the shredded glass fiber filter paper is 1 mm². 2 .

[0051] The drying temperature is 60℃ and the drying time is 4 hours.

[0052] The thickness of the large "L"-shaped electrode is 100 μm; the thickness of the small "L"-shaped electrode is 100 μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance between the transverse edge of the shaped electrode and the upper edge of the corundum substrate is L3 = 0.05L1. The distance between the horizontal edge of the shaped electrode and the left side is B3 = 0.2B1.

[0053] The carbon nanotube hollow sphere hydrovoltaic device with partitioned resistors prepared in this embodiment was tested and found to have an open-circuit voltage of 400mV and a short-circuit current of 1μA.

[0054] Example 2 A carbon nanotube hollow sphere hydrovoltaic power generation device with partitioned resistance and its fabrication method. The fabrication method described in this embodiment is as follows: Step 1: Dissolve 10 parts by weight of glucose and 0.6 parts by weight of sodium poly(4-styrenesulfonic acid-copolymer-maleic acid) in 51 parts by weight of deionized water and stir at 160 r / min for 1.3 h; then transfer to a high-pressure reactor and react at 182 °C for 9 h. Separate the solid and liquid products, and wash the solid three times each with deionized water and ethanol to obtain carbon nanotube hollow sphere precursor.

[0055] Step 2: Carbonize half of the carbon nanotube hollow sphere precursor at 580℃ in an argon atmosphere for 2.3h, and then ball mill for 0.7h to obtain high-resistivity carbon nanotube hollow spheres.

[0056] Step 3: Carbonize the other half of the carbon nanotube hollow sphere precursor at 820℃ in an argon atmosphere for 2.3h, and then ball mill it for 0.7h to obtain low-resistivity carbon nanotube hollow spheres.

[0057] Step 4: Add 9 parts by weight of high-resistivity carbon nanotube hollow spheres, 0.9 parts by weight of terpineol, 3.5 parts by weight of ethyl cellulose and 1.1 parts by weight of shredded glass fiber filter paper to 81 parts by weight of anhydrous ethanol, stir at 160 r / min for 5.3 h, and dry to obtain a high-resistivity slurry.

[0058] Nine parts by weight of low-resistivity carbon nanotube hollow spheres, 0.9 parts by weight of terpineol, 3.5 parts by weight of ethyl cellulose and 1.1 parts by weight of shredded glass fiber filter paper were added to 81 parts by weight of anhydrous ethanol and stirred at 160 r / min for 5.3 h. The mixture was then dried to obtain a low-resistivity slurry.

[0059] Step 5: Using conductive carbon paste, coat a large "L"-shaped electrode on the left side and near the bottom edge of a corundum substrate with a length L1 = 100 mm and a width B1 = 45 mm. Coat a small "L"-shaped electrode on the right side and near the top edge of the corundum substrate using conductive carbon paste. A three-dimensional electrode is formed between two electrodes, with a distance of L2=0.8L1 along the long side of the corundum substrate and a distance of B2=0.5B1 along the wide side of the corundum substrate. The high-resistivity slurry is coated onto the lower half of the thin film region to obtain a high-resistivity thin film. The low-resistivity slurry is coated onto the upper half of the thin film region to obtain a low-resistivity thin film. Then, the film is annealed in a muffle furnace at 320°C for 1.3 hours to obtain a carbon nanotube hollow sphere hydrovoltaic device with zoned resistance.

[0060] The solid-liquid separation refers to solid-liquid separation for 3.5 minutes at a rotation speed of 8500 r / min.

[0061] The high-resistivity hollow carbon nanospheres have a particle size of 350 nm, and the low-resistivity hollow carbon nanospheres have the same particle size as the high-resistivity hollow carbon nanospheres.

[0062] The area ratio of the high-resistivity film to the low-resistivity film is 1.3:1, and the thickness of the high-resistivity film and the low-resistivity film is the same, both being 350 μm.

[0063] The area of ​​the shredded glass fiber filter paper is 3 mm². 2 .

[0064] The drying temperature was 62°C, and the drying time was 4.3 hours.

[0065] The thickness of the large "L"-shaped electrode is 125 μm; the thickness of the small "L"-shaped electrode is 125 μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance L3 = 0.06L1 between the horizontal edge of the shaped electrode and the upper edge of the corundum substrate is small. The distance between the horizontal edge of the shaped electrode and the left side is B3 = 0.2B1.

[0066] The carbon nanotube hollow sphere hydrovoltaic device with partitioned resistors prepared in this embodiment was tested and found to have an open-circuit voltage of 450mV and a short-circuit current of 1.1μA.

[0067] Example 3 A carbon nanotube hollow sphere hydrovoltaic power generation device with partitioned resistance and its fabrication method. The fabrication method described in this embodiment is as follows: Step 1: Dissolve 10 parts by weight of glucose and 0.6 parts by weight of sodium poly(4-styrenesulfonic acid-copolymer-maleic acid) in 53 parts by weight of deionized water and stir at 170 r / min for 1.5 h; then transfer to a high-pressure reactor and react at 185 °C for 10 h. Separate the solid and liquid products, and wash the solid with deionized water and ethanol 4 times each to obtain carbon nanotube hollow sphere precursor.

[0068] Step 2: Carbonize half of the carbon nanotube hollow sphere precursor at 600℃ in an argon atmosphere for 2.5h, and then ball mill for 0.6h to obtain high-resistivity carbon nanotube hollow spheres.

[0069] Step 3: Carbonize the other half of the carbon nanotube hollow sphere precursor at 850℃ in an argon atmosphere for 2.5h, and then ball mill it for 0.6h to obtain low-resistivity carbon nanotube hollow spheres.

[0070] Step 4: Add 10 parts by weight of high-resistivity carbon nanotube hollow spheres, 1 part by weight of terpineol, 4 parts by weight of ethyl cellulose and 1.1 parts by weight of shredded glass fiber filter paper to 82 parts by weight of anhydrous ethanol, stir at 170 r / min for 5.5 h, and dry to obtain a high-resistivity slurry.

[0071] Ten parts by weight of low-resistivity carbon nanotube hollow spheres, one part by weight of terpineol, four parts by weight of ethyl cellulose, and one and one parts by weight of shredded glass fiber filter paper were added to 82 parts by weight of anhydrous ethanol. The mixture was stirred at 170 r / min for 5.5 h and then dried to obtain a low-resistivity slurry.

[0072] Step 5: Using conductive carbon paste, coat a large "L"-shaped electrode on the left side and near the bottom edge of a corundum substrate with a length L1 = 100 mm and a width B1 = 50 mm. Also coat a small "L"-shaped electrode on the right side and near the top edge of the corundum substrate using conductive carbon paste. A thin film region is formed between two electrodes with a spacing of L2=0.8L1 along the long side of the corundum substrate and B2=0.5B1 along the wide side of the corundum substrate. The high-resistivity slurry is coated onto the lower half of the thin film region to obtain a high-resistivity thin film. The low-resistivity slurry is coated onto the upper half of the thin film region to obtain a low-resistivity thin film. Then, the film is annealed at 330°C for 1.5 hours in a muffle furnace to obtain a carbon nanotube hollow sphere hydrovoltaic device with zoned resistance.

[0073] The solid-liquid separation refers to solid-liquid separation for 4 minutes at a rotation speed of 9000 r / min.

[0074] The high-resistivity hollow carbon nanospheres have a particle size of 400 nm, and the low-resistivity hollow carbon nanospheres have the same particle size as the high-resistivity hollow carbon nanospheres.

[0075] The area ratio of the high-resistivity film to the low-resistivity film is 1.5:1, and the thickness of the high-resistivity film and the low-resistivity film is the same, both being 400 μm.

[0076] The area of ​​the shredded glass fiber filter paper is 5 mm². 2 .

[0077] The drying temperature is 65℃ and the drying time is 4.5 hours.

[0078] The thickness of the large "L"-shaped electrode is 150 μm; the thickness of the small "L"-shaped electrode is 150 μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance between the transverse edge of the shaped electrode and the upper edge of the corundum substrate is L3 = 0.07L1. The distance between the horizontal edge of the shaped electrode and the left side is B3 = 0.2B1.

[0079] The carbon nanotube hollow sphere hydrovoltaic device with partitioned resistors prepared in this embodiment was tested and found to have an open-circuit voltage of 500mV and a short-circuit current of 1.2μA.

[0080] Example 4 A carbon nanotube hollow sphere hydrovoltaic power generation device with partitioned resistance and its fabrication method. The fabrication method described in this embodiment is as follows: Step 1: Dissolve 11 parts by weight of glucose and 0.7 parts by weight of sodium poly(4-styrenesulfonic acid-copolymer-maleic acid) in 54 parts by weight of deionized water and stir at 180 r / min for 1.7 h; then transfer to a high-pressure reactor and react at 188 °C for 11 h. Separate the solid and liquid products, and wash the solid 5 times each with deionized water and ethanol to obtain carbon nanotube hollow sphere precursor.

[0081] Step 2: Carbonize half of the carbon nanotube hollow sphere precursor at 620℃ in an argon atmosphere for 2.7h, and then ball mill for 0.8h to obtain high-resistivity carbon nanotube hollow spheres.

[0082] Step 3: Carbonize the other half of the carbon nanotube hollow sphere precursor at 880℃ in an argon atmosphere for 2.7h, and then ball mill it for 0.8h to obtain low-resistivity carbon nanotube hollow spheres.

[0083] Step 4: Add 11 parts by weight of high-resistivity carbon nanotube hollow spheres, 1.1 parts by weight of terpineol, 4.5 parts by weight of ethyl cellulose and 1.2 parts by weight of shredded glass fiber filter paper to 84 parts by weight of anhydrous ethanol, stir at 180 r / min for 5.8 h, and dry to obtain a high-resistivity slurry.

[0084] 11 parts by weight of low-resistivity carbon nanotube hollow spheres, 1.1 parts by weight of terpineol, 4.5 parts by weight of ethyl cellulose and 1.2 parts by weight of shredded glass fiber filter paper were added to 84 parts by weight of anhydrous ethanol and stirred at 180 r / min for 5.8 h. The mixture was then dried to obtain a low-resistivity slurry.

[0085] Step 5: Using conductive carbon paste, coat a large "L"-shaped electrode on the left side and near the bottom edge of an alumina substrate with a length L1 = 110 mm and a width B1 = 55 mm. Also coat a small "L"-shaped electrode on the right side and near the top edge of the alumina substrate using conductive carbon paste. A three-dimensional electrode is formed between two electrodes, with a distance of L2=0.9L1 along the long side of the corundum substrate and a distance of B2=0.6B1 along the wide side of the corundum substrate. The high-resistivity slurry is coated onto the lower half of the thin film region to obtain a high-resistivity thin film. The low-resistivity slurry is coated onto the upper half of the thin film region to obtain a low-resistivity thin film. Then, the film is annealed in a muffle furnace at 340°C for 1.8 hours to obtain a carbon nanotube hollow sphere hydrovoltaic device with zoned resistance.

[0086] The solid-liquid separation refers to solid-liquid separation for 4.5 minutes at a rotation speed of 9500 r / min.

[0087] The high-resistivity carbon nanotube hollow spheres have a particle size of 450 nm, and the low-resistivity carbon nanotube hollow spheres have the same particle size as the high-resistivity carbon nanotube hollow spheres.

[0088] The area ratio of the high-resistivity film to the low-resistivity film is 1.7:1, and the thickness of the high-resistivity film and the low-resistivity film is the same, both being 450 μm.

[0089] The area of ​​the shredded glass fiber filter paper is 7 mm². 2 .

[0090] The drying temperature was 68°C, and the drying time was 4.8 hours.

[0091] The thickness of the large "L"-shaped electrode is 175 μm; the thickness of the small "L"-shaped electrode is 175 μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance between the transverse edge of the shaped electrode and the upper edge of the corundum substrate is L3 = 0.08L1. The distance between the horizontal side of the shaped electrode and the left side is B3 = 0.3B1.

[0092] The carbon nanotube hollow sphere hydrovoltaic device with partitioned resistors prepared in this embodiment was tested and found to have an open-circuit voltage of 550mV and a short-circuit current of 1.3μA.

[0093] Example 5 A carbon nanotube hollow sphere hydrovoltaic power generation device with partitioned resistance and its fabrication method. The fabrication method described in this embodiment is as follows: Step 1: Dissolve 12 parts by weight of glucose and 0.8 parts by weight of sodium poly(4-styrenesulfonic acid-copolymer-maleic acid) in 55 parts by weight of deionized water and stir at 200 r / min for 2 h; then transfer to a high-pressure reactor and react at 190 °C for 12 h. Separate the solid and liquid products, and wash the solid 5 times each with deionized water and ethanol to obtain carbon nanotube hollow sphere precursor.

[0094] Step 2: Carbonize half of the carbon nanotube hollow sphere precursor at 650℃ in an argon atmosphere for 3 hours, and then ball mill for 1 hour to obtain high-resistivity carbon nanotube hollow spheres.

[0095] Step 3: Carbonize the other half of the carbon nanotube hollow sphere precursor at 900℃ in an argon atmosphere for 3 hours, and then ball mill it for 1 hour to obtain low-resistivity carbon nanotube hollow spheres.

[0096] Step 4: Add 12 parts by weight of high-resistivity carbon nanotube hollow spheres, 1.2 parts by weight of terpineol, 5 parts by weight of ethyl cellulose and 1.2 parts by weight of shredded glass fiber filter paper to 85 parts by weight of anhydrous ethanol, stir at 200 r / min for 6 h, and dry to obtain a high-resistivity slurry.

[0097] 12 parts by weight of low-resistivity carbon nanotube hollow spheres, 1.2 parts by weight of terpineol, 5 parts by weight of ethyl cellulose and 1.2 parts by weight of shredded glass fiber filter paper were added to 85 parts by weight of anhydrous ethanol and stirred at 200 r / min for 6 h. After drying, a low-resistivity slurry was obtained.

[0098] Step 5: Using conductive carbon paste, coat a large "L"-shaped electrode on the left side and near the bottom edge of a corundum substrate with a length L1 = 120 mm and a width B1 = 60 mm. Also coat a small "L"-shaped electrode on the right side and near the top edge of the corundum substrate using conductive carbon paste. A three-dimensional electrode is formed between two electrodes, with a distance of L2=0.9L1 along the long side of the corundum substrate and a distance of B2=0.6B1 along the wide side of the corundum substrate. The high-resistivity slurry is coated onto the lower half of the thin film region to obtain a high-resistivity thin film. The low-resistivity slurry is coated onto the upper half of the thin film region to obtain a low-resistivity thin film. Then, the film is annealed at 350°C for 2 hours in a muffle furnace to obtain a carbon nanotube hollow sphere hydrovoltaic device with zoned resistance.

[0099] The solid-liquid separation refers to solid-liquid separation for 5 minutes at a rotation speed of 10000 r / min.

[0100] The high-resistivity hollow carbon nanospheres have a particle size of 500 nm, and the low-resistivity hollow carbon nanospheres have the same particle size as the high-resistivity hollow carbon nanospheres.

[0101] The area ratio of the high-resistivity film to the low-resistivity film is 2:1, and the thickness of the high-resistivity film and the low-resistivity film is the same, both being 500 μm.

[0102] The area of ​​the shredded glass fiber filter paper is 10 mm². 2 .

[0103] The drying temperature is 70℃ and the drying time is 5 hours.

[0104] The thickness of the large "L"-shaped electrode is 200 μm; the thickness of the small "L"-shaped electrode is 200 μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance between the transverse edge of the shaped electrode and the upper edge of the corundum substrate is L3 = 0.1L1, which is small. The distance between the horizontal side of the shaped electrode and the left side is B3 = 0.3B1.

[0105] The carbon nanotube hollow sphere hydrovoltaic device with partitioned resistors prepared in this embodiment was tested and found to have an open-circuit voltage of 600mV and a short-circuit current of 1.4μA.

[0106] This specific implementation method has the following advantages compared with the prior art: 1. The preparation method and product properties of this specific embodiment are shown in the accompanying drawings of the specification: Figure 1 The fabrication process of the partitioned resistor carbon nanotube hollow sphere hydrovoltaic power generation device in Example 3; Figure 2 for Figure 1 SEM images of the fabricated carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance: [Image of the device would be inserted here] Figure 2 (a) is a SEM image of the low-resistivity thin film. Figure 2 (b) is a SEM image of the high-resistivity thin film; Figure 3 for Figure 1 Vt curves of the fabricated carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance; Figure 4 for Figure 1 The It curve of the prepared partitioned resistor carbon nanotube hollow sphere hydrovoltaic device.

[0107] from Figure 1 It can be seen that: Figure 1 (a) A large "L"-shaped electrode is scraped onto the left side and near the bottom edge of an alumina substrate with a length L1 = 120 mm and a width B1 = 60 mm using conductive carbon paste. A small "L"-shaped electrode is scraped onto the right side and near the top edge of the alumina substrate using conductive carbon paste. A "shaped electrode" is formed between the two electrodes, with a thin film region between them having a distance of L2=0.8L1 along the long side of the corundum substrate and a distance of B2=0.6B1 along the wide side of the corundum substrate. Figure 1 (b) involves coating the high-resistivity slurry onto the lower half of the film area to obtain a high-resistivity film; Figure 1 (c) The low-resistivity slurry is coated onto the upper half of the thin film area to obtain a low-resistivity thin film. This forms a film with a large "L"-shaped electrode as the negative electrode and a small "L"-shaped electrode as the negative electrode. "Unfired carbon nanotube hollow sphere water photovoltaic device blank with shaped electrode as positive electrode." from Figure 2 It can be seen that: Figure 2 (a) Low-resistivity carbon nanotube hollow spheres are densely distributed in the low-resistivity film, which are stacked together to form water flow channels, and glass fibers are interspersed in them as support. Figure 2 (b) The high-resistivity thin film contains densely distributed high-resistivity carbon nanotube hollow spheres, and the rest is the same as the low-resistivity thin film.

[0108] from Figure 3 It can be seen that the open-circuit voltage of the prepared partitioned resistor carbon nanotube hollow sphere hydrovoltaic device is 500mV.

[0109] from Figure 4 It can be seen that the short-circuit current of the prepared partitioned resistor carbon nanotube hollow sphere hydrovoltaic device is 1.2μA.

[0110] 2. This specific embodiment employs a partitioned resistor design. By constructing high-resistance and low-resistance thin films in the partitioned resistor region of the carbon nanotube hollow sphere photovoltaic device, the charge transfer process within the carbon nanotube hollow sphere thin film is balanced. The high-resistance thin film facilitates charge accumulation, promoting the formation of a high open-circuit voltage; the low-resistance thin film facilitates charge transfer, promoting the formation of a high short-circuit current. The partitioned resistor carbon nanotube hollow sphere photovoltaic device fabrication technology provided in this specific embodiment can regulate the charge migration process of the partitioned resistor carbon nanotube hollow sphere photovoltaic device, thus achieving a dual increase in open-circuit voltage and short-circuit current.

[0111] 3. The carbon nanotube hollow spheres used in this specific embodiment are a typical carbon nanomaterial, possessing the excellent electrochemical properties of carbon-based materials. Furthermore, the synthesis process for preparing carbon nanotube hollow spheres is simple, involves no complex operations, and is easy to implement. The main raw material required for preparation is glucose, which is widely available and inexpensive. Therefore, the fabrication cost of the described partitioned resistor carbon nanotube hollow sphere hydrovoltaic power generation device is low.

[0112] 4. The partitioned resistivity carbon nanotube hollow sphere water-voltaic power generation device prepared in this specific embodiment can regulate the charge accumulation and transfer process by relying on the resistance of different regions, thereby achieving a simultaneous increase in open-circuit voltage and short-circuit current. The prepared water-voltaic power generation device was tested and found to have an open-circuit voltage of 400~600mV and a short-circuit current of 1~1.4μA. Therefore, the prepared partitioned resistivity carbon nanotube hollow sphere water-voltaic power generation device has high power output.

[0113] The testing method used in this specific embodiment is as follows: using an electrochemical workstation, the large "L"-shaped electrode of the partitioned resistivity carbon nanotube hollow sphere hydrovoltaic device is connected to the counter electrode and the reference electrode, and the small "L"-shaped electrode is connected to the counter electrode and the reference electrode. The L-shaped electrode is connected to the working electrode. The carbon nanotube hollow sphere hydrovoltaic device with partitioned resistance is placed in a 250mL beaker, and deionized water is added until it covers the horizontal edge of the large L-shaped electrode. The open-circuit voltage is then tested. The short-circuit current test procedure and electrode connection method are the same as those for the open-circuit voltage test.

[0114] Therefore, the preparation cost of this specific embodiment is low, and the prepared partitioned resistor carbon nanotube hollow sphere water photovoltaic power generation device not only has high open-circuit voltage and short-circuit current, but also high power output.

Claims

1. A preparation method of a carbon nanohorn water-vapor power generation device with a partitioned resistance, characterized by The preparation method is: Step one, 9-12 parts by mass of glucose and 0.5-0.8 parts by mass of poly(4-styrene sulfonic acid-co-maleic acid) sodium salt are dissolved in 50-55 parts by mass of deionized water, and first stirring is performed; then the mixture is transferred to a high-pressure reaction kettle and reacted at 180-190°C for 8-12 hours, the obtained product is subjected to solid-liquid separation, the solid is washed with deionized water and ethanol for 3-5 times, and a carbon nanohollow sphere precursor is obtained; Step two, half of the carbon nanohollow sphere precursor is carbonized at 550-650°C in an argon atmosphere for 2-3 hours, and is subjected to ball milling for 0.5-1 hour, and a high-resistance carbon nanohollow sphere is obtained; Step three, the other half of the carbon nanohollow sphere precursor is carbonized at 800-900°C in an argon atmosphere for 2-3 hours, and is subjected to ball milling for 0.5-1 hour, and a low-resistance carbon nanohollow sphere is obtained; Step four, 8-12 parts by mass of the high-resistance carbon nanohollow sphere and 8-12 parts by mass of the low-resistance carbon nanohollow sphere are respectively added to 0.8-1.2 parts by mass of terpineol, 3-5 parts by mass of ethyl cellulose and 1-1.2 parts by mass of cut glass fiber filter paper in 80-85 parts by mass of anhydrous ethanol, and second stirring is performed, and drying is performed, and a corresponding high-resistance slurry and a low-resistance slurry are obtained; Step five, a large "L" shaped electrode is scraped on the left side and near the bottom edge of the corundum substrate with length L1=90~120mm, width B1=40~60mm by using conductive carbon paste, and a small "L" shaped electrode is scraped on the right side and near the top edge of the corundum substrate by using conductive carbon paste, the thin film area is formed between the two electrodes with the long edge interval L2=(0.8~0.9)L1 along the corundum substrate and the wide edge distance B2=(0.5~0.6)B1 along the corundum substrate; the high resistance slurry and the low resistance slurry are correspondingly scraped on the lower half and the upper half of the thin film area to obtain high resistance thin film and low resistance thin film; then annealing is carried out in a muffle furnace at 300~350℃ for 1~2h to prepare a carbon nanohollow sphere water-vapor power generation device with partition resistance. Step five, a large "L" shaped electrode is scraped on the left side and near the bottom edge of the corundum substrate with length L1=90~120mm, width B1=40~60mm by using conductive carbon paste, and a small "L" shaped electrode is scraped on the right side and near the top edge of the corundum substrate by using conductive carbon paste, the thin film area is formed between the two electrodes with the long edge interval L2=(0.8~0.9)L1 along the corundum substrate and the wide edge distance B2=(0.5~0.6)B1 along the corundum substrate; the high resistance slurry and the low resistance slurry are correspondingly scraped on the lower half and the upper half of the thin film area to obtain high resistance thin film and low resistance thin film; then annealing is carried out in a muffle furnace at 300~350℃ for 1~2h to prepare a carbon nanohollow sphere water-vapor power generation device with partition resistance.

2. The method of claim 1, wherein the carbon nanohorn water volage device is a carbon nanohorn water volage device with a partitioned resistance. The solid-liquid separation refers to solid-liquid separation at a rotation speed of 8000-10000 r / min for 3-5 minutes.

3. The method of claim 1, wherein the carbon nanohorn water volage device is a carbon nanohorn water volage device with a partitioned resistance. The particle size of the high-resistance carbon nanohollow sphere is 300-500 nm, and the particle size of the low-resistance carbon nanohollow sphere is the same as that of the high-resistance carbon nanohollow sphere.

4. The method of claim 1, wherein the carbon nanohorn water volage device is a resistive partitioned carbon nanohorn water volage device. The area ratio of the high-resistance film and the low-resistance film is 1-2:1, the thicknesses of the high-resistance film and the low-resistance film are the same, and both are 300-500 μm.

5. The method of claim 1, wherein the carbon nanohorn water volage device is a resistive partitioned carbon nanohorn water volage device. The area of the cut glass fiber filter paper is 1 to 10 mm 2 .

6. The method of claim 1, wherein the carbon nanohorn water volage device is a resistive partitioned carbon nanohorn water volage device. The rotation speed of the first stirring is 150-200 r / min, and the time of the first stirring is 1-2 hours.

7. The method of claim 1, wherein the carbon nanohorn water volage device is a resistive partitioned carbon nanohorn water volage device. The temperature of the drying is 60-70°C, and the time of the drying is 4-5 hours.

8. The method of claim 1, wherein the carbon nanohorn water volage device is a resistive partitioned carbon nanohorn water volage device. The thickness of the large "L"-shaped electrode is 100~200μm; the thickness of the small "L"-shaped electrode is 100~200μm. The thickness of the "L"-shaped electrode is the same as the thickness of the large "L"-shaped electrode, and the small "L"-shaped electrode... The distance L3 between the transverse edge of the shaped electrode and the upper edge of the corundum substrate is (0.05~0.1)L1. The distance between the horizontal side of the shaped electrode and the left side is B3 = (0.2~0.3)B1.

9. The method of claim 1, wherein the method further comprises the step of: 9-1) annealing the carbon nanohorn at a temperature of 3000C to 4000C for 1 to 10 hours in an inert gas atmosphere. The rotation speed of the second stirring is 150-200 r / min, and the time of the second stirring is 5-6 hours.

10. A carbon nanohorn water-vapo(u)r power generating device with partitioned resistance, characterized by The carbon nanohollow sphere water-voltage power generation device with a partitioned resistance is prepared according to the preparation method of the carbon nanohollow sphere water-voltage power generation device with a partitioned resistance according to any one of claims 1-9.

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