Sandwich type energy storage heating glass containing carbon black

Abstract

The invention belongs to the field of glass, and particularly relates to carbon black-containing sandwich type energy storage heating glass which comprises first substrate glass, a first bonding layer, a carbon black photothermal conversion layer, a phase change energy storage layer, a second bonding layer and second substrate glass which are sequentially stacked, the carbon black photothermal conversion layer contains silane coupling agent modified carbon black; the phase change energy storage layer comprises a microencapsulated composite phase change material and a porous silicon dioxide carrier, and a phase change material in the microencapsulated composite phase change material comprises paraffin and stearic acid. The energy storage heating glass provided by the invention is low in production cost, good in light transmittance and photothermal conversion efficiency, and strong in stability and weather resistance.

Description

Technical Field

[0001] This invention belongs to the field of glass, and particularly relates to a sandwich-type energy storage and heating glass containing carbon black. Background Technology

[0002] In modern architecture and transportation, glass is widely used as an important material for lighting and enclosure. However, traditional glass faces some significant problems during use, which form the background technology for the development of energy storage heating glass.

[0003] First, in cold regions or during winter, glass surfaces are highly susceptible to frost or fogging due to low temperatures. This not only severely affects the glass's light transmission, reducing indoor lighting and visibility, but also directly impacts driving safety for vehicles such as cars and airplanes, increasing the operational burden and energy consumption of defrosting and defogging. Traditional solutions, such as using direct airflow from air conditioning or resistance heating, often suffer from slow heating speeds, high energy consumption, uneven heating, and potential impacts on the glass's aesthetics and structural strength.

[0004] Secondly, traditional glass typically has poor thermal insulation performance, making it a major source of heat loss in buildings and vehicles. This leads to a significant energy consumption in winter to maintain comfortable indoor or cabin temperatures, exacerbating energy shortages and carbon emissions. While the application of energy-efficient glass such as insulated glass and Low-E glass has improved thermal insulation to some extent, they lack active heating and energy storage capabilities, failing to fundamentally address the needs for frosting, fogging, and rapid temperature increases in low-temperature environments.

[0005] Furthermore, with the development of the new energy industry and the rise of concepts such as smart buildings and intelligent transportation, higher functional requirements have been placed on glass materials. People expect glass to not only meet basic lighting and decorative needs but also possess intelligent characteristics such as active temperature control and energy management. For example, in the utilization of solar energy, how to effectively collect, store, and release heat when needed to improve energy efficiency has become an important research direction.

[0006] Furthermore, in certain special environments or applications, such as greenhouses in cold regions and protective covers for outdoor electronic device displays, glass needs to maintain clear light transmission and a certain temperature at low temperatures to ensure the growth of plants or the normal operation of equipment inside. Traditional glass struggles to meet the precise temperature control and energy self-sufficiency requirements of these specific scenarios.

[0007] Therefore, to address the problems of traditional glass such as easy frost formation and fogging in low-temperature environments, limited thermal insulation performance, and low energy utilization efficiency, and to meet the urgent needs of modern society for energy-saving, intelligent, and safe materials, the development of energy-storage heating glass capable of storing heat and releasing it as needed to achieve active heating has become an inevitable trend. Energy-storage heating glass aims to combine energy storage materials with the glass substrate, utilizing the latent heat of phase change of the energy storage material to store and release energy, thereby achieving temperature regulation of the glass surface, effectively preventing frost formation, and assisting in raising the temperature of indoor or specific spaces, achieving energy-saving, intelligent, and safe effects. However, existing energy-storage heating glass suffers from problems such as high production costs, difficulty in balancing light transmittance and photothermal conversion efficiency, and poor stability. Summary of the Invention

[0008] In view of this, the purpose of the present invention is to provide a carbon black-containing sandwich energy storage heating glass. The energy storage heating glass provided by the present invention has low production cost, good light transmittance and photothermal conversion efficiency, and strong stability and weather resistance.

[0009] The present invention provides a carbon black-containing sandwich energy storage and heating glass, comprising a first substrate glass, a first adhesive layer, a carbon black photothermal conversion layer, a phase change energy storage layer, a second adhesive layer, and a second substrate glass stacked sequentially.

[0010] The carbon black photothermal conversion layer contains carbon black modified with a silane coupling agent;

[0011] The phase change energy storage layer comprises a microencapsulated composite phase change material and a porous silica carrier, wherein the phase change material in the microencapsulated composite phase change material includes paraffin and stearic acid.

[0012] Preferably, the silane coupling agent modified carbon black is made from carbon black raw material after being modified by a silane coupling agent; the carbon black raw material is ordinary carbon black and / or conductive carbon black; the particle size of the carbon black raw material is 5~50nm; and the grade of the silane coupling agent is one or more of KH550, KH560, KH570 and KH590.

[0013] Preferably, the carbon black photothermal conversion layer also contains a binder.

[0014] Preferably, the adhesive is one or more of ethylene-vinyl acetate copolymer, polyvinyl butyral, and polyolefin elastomer; the mass ratio of silane coupling agent modified carbon black in the carbon black photothermal conversion layer to the adhesive is 1:(10~20).

[0015] Preferably, the thickness of the carbon black photothermal conversion layer is 30~150μm.

[0016] Preferably, the paraffin accounts for 50-90 wt% of the total mass of paraffin and stearic acid.

[0017] Preferably, the phase change material further includes palmitic acid; the content of palmitic acid in the phase change material is 10~30wt%.

[0018] Preferably, the particle size of the microencapsulated composite phase change material is 0.5~5μm.

[0019] Preferably, the mass ratio of the microencapsulated composite phase change material to the porous silica carrier in the phase change energy storage layer is (1~5):1.

[0020] Preferably, the thickness of the phase change energy storage layer is 1~5mm.

[0021] Compared with existing technologies, this invention provides a carbon black-containing sandwich-type energy storage and heating glass, comprising a first substrate glass, a first adhesive layer, a carbon black photothermal conversion layer, a phase change energy storage layer, a second adhesive layer, and a second substrate glass, stacked sequentially. The carbon black photothermal conversion layer contains silane coupling agent-modified carbon black. The phase change energy storage layer comprises a microencapsulated composite phase change material and a porous silica carrier, wherein the phase change material in the microencapsulated composite phase change material includes paraffin wax and stearic acid. The energy storage and heating glass provided by this invention has low production costs, good light transmittance and photothermal conversion efficiency, strong stability and weather resistance, and more specifically, at least the following advantages:

[0022] 1) Significant cost advantage: Using carbon black as the photothermal conversion material, the raw material cost is only 1 / 50 to 1 / 100 of that of graphene-based products;

[0023] 2) Excellent performance balance: Through modified carbon black dispersion design and composite phase change material optimization, a performance combination of visible light transmittance ≥55%, photothermal conversion efficiency ≥75%, and energy storage density ≥180kJ / kg is achieved, while the heat release duration is ≥8h, which can meet the building's nighttime heating needs;

[0024] 3) Strong stability and weather resistance: The dual protection of microcapsule encapsulation and porous carrier avoids leakage of phase change material; the silane coupling agent modification improves the bonding force between carbon black and substrate, so that the photothermal conversion layer does not crack or fall off in the range of -30℃ to 80℃, and the carbon black itself has strong weather resistance.

[0025] 4) Wide range of applications: It is suitable for building curtain walls, passive houses, photovoltaic integrated systems and other scenarios. Especially in cold northern regions, it can meet 15-30% of indoor heating needs through solar energy storage, reducing building energy consumption. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] The present invention provides a sandwich-type energy storage and heating glass containing carbon black, comprising a first substrate glass, a first adhesive layer, a carbon black photothermal conversion layer, a phase change energy storage layer, a second adhesive layer, and a second substrate glass, which are stacked sequentially.

[0028] In the energy storage heating glass provided by the present invention, the first substrate glass includes, but is not limited to, float glass, tempered glass, ultra-clear float glass or tempered laminated glass.

[0029] In the energy storage heating glass provided by the present invention, the thickness of the first substrate glass is preferably 2 to 10 mm, specifically 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm.

[0030] In the energy storage heating glass provided by the present invention, the components of the first adhesive layer include, but are not limited to, one or more of ethylene-vinyl acetate copolymer (EVA), polyvinyl butyral (PVB), and polyolefin elastomer (POE).

[0031] In the energy storage heating glass provided by the present invention, the thickness of the first adhesive layer is preferably 0.2~2mm, specifically 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm or 2mm.

[0032] In the energy storage heating glass provided by this invention, the carbon black photothermal conversion layer contains silane coupling agent modified carbon black; the silane coupling agent modified carbon black is preferably made from carbon black raw material after silane coupling agent modification treatment; the carbon black raw material is preferably ordinary carbon black and / or conductive carbon black; the particle size of the carbon black raw material is preferably 5~50nm, specifically 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, etc. nm, 45nm or 50nm; the grade of the silane coupling agent is preferably one or more of KH550, KH560, KH570 and KH590; the mass ratio of the carbon black raw material to the silane coupling agent is preferably 1:(0.1~0.5), specifically 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5.

[0033] In the energy storage heating glass provided by this invention, the silane coupling agent modified carbon black is preferably prepared according to the following steps: mixing carbon black raw material with an aqueous solution of silane coupling agent, ultrasonically dispersing, and drying to obtain silane coupling agent modified carbon black. The concentration of the aqueous solution of silane coupling agent is preferably 2-10 wt%, specifically 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%; the power of the ultrasonic dispersion is preferably 500-1000 W, specifically 500 W, 600 W, 700 W, 800 W, 900 W, or 1000 W; the frequency of the ultrasonic dispersion is preferably 20-40 kHz, specifically 20 kHz, 23 kHz, 25 kHz, 28 kHz, 30 kHz, 32 kHz, 35 kHz, 37 kHz, or 40 kHz; the time of the ultrasonic dispersion is preferably 30-60 min, specifically 30 min, 35 min, 40 min, or 45 min. The drying time is preferably 50 min, 55 min, or 60 min; the drying method is preferably vacuum drying; the drying temperature is preferably 60~100℃, specifically 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, or 100℃; the vacuum degree of the drying is preferably -0.06~-0.1MPa, specifically -0.06MPa, -0.065MPa, -0.07MPa, -0.075MPa, -0.08MPa, -0.085MPa, -0.09MPa, 0.095MPa, or -0.1MPa; the drying time is preferably 2~6h, specifically 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, or 6h.

[0034] In the energy storage heating glass provided by the present invention, the carbon black photothermal conversion layer preferably also contains an adhesive; the adhesive is preferably one or more of ethylene-vinyl acetate copolymer, polyvinyl butyral, and polyolefin elastomer; the mass ratio of silane coupling agent modified carbon black to adhesive in the carbon black photothermal conversion layer is preferably 1:(10~20), specifically 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20.

[0035] In the energy storage heating glass provided by the present invention, the thickness of the carbon black photothermal conversion layer is preferably 30~150μm, specifically 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm, 100μm, 110μm, 120μm, 130μm, 140μm or 150μm.

[0036] In the energy storage heating glass provided by the present invention, the carbon black photothermal conversion layer is preferably formed by coating a mixture of silane coupling agent modified carbon black and binder; the mixture is preferably subjected to high-speed shearing and high-pressure homogenization treatment before coating to ensure that the carbon black is uniformly dispersed in the binder.

[0037] In the energy storage heating glass provided by the present invention, the phase change energy storage layer comprises a microencapsulated composite phase change material and a porous silica carrier; wherein, the phase change material in the microencapsulated composite phase change material comprises paraffin wax and stearic acid; the paraffin wax preferably accounts for 50-90 wt% of the total mass of paraffin wax and stearic acid, specifically 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90 wt%; the phase change material preferably also includes palmitic acid; the content of palmitic acid in the phase change material is preferably 10-30 wt%, specifically 10 wt%, 12 wt%, 15 wt%, 17 wt%, 20 wt%, 23 wt%, 25 wt%, 27 wt%, or 30 wt%.

[0038] In the energy storage heating glass provided by the present invention, the particle size of the microencapsulated composite phase change material is preferably 0.5~5μm, specifically 0.5μm, 1μm, 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 4μm, 4.5μm or 5μm.

[0039] In the energy storage heating glass provided by the present invention, the microencapsulated composite phase change material is preferably prepared according to any one of the following two preparation methods:

[0040] Method 1: The phase change material is melt-mixed and then mixed with a melamine-formaldehyde resin solution to form an emulsion; the emulsion is heated to react and obtain a microencapsulated composite phase change material. The concentration of the melamine-formaldehyde resin solution is preferably 7-15 wt%, specifically 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt%. Before the heating reaction, ammonium chloride is preferably mixed into the emulsion, and the amount of ammonium chloride is preferably 2-7 wt% of the emulsion mass, specifically 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, or 7 wt%. The heating reaction temperature is preferably 50-80℃, specifically 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, or 80℃. The heating reaction time is preferably 60-150 min, specifically 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, or 150 min.

[0041] Method 2: The phase change material is melt-mixed and then emulsified with urea-formaldehyde resin prepolymer to form microdroplets; the microdroplets are then reacted with oxalic acid to obtain a microencapsulated composite phase change material. The preferred mixing and emulsification speed is 6000~12000 r / min, specifically 6000 r / min, 7000 r / min, 8000 r / min, 9000 r / min, 10000 r / min, 11000 r / min, or 12000 r / min; the preferred mixing reaction temperature is 50~60℃, specifically 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, or 60℃; the preferred mixing reaction time is 30~90 min, specifically 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, or 90 min.

[0042] In the energy storage heating glass provided by this invention, the encapsulation rate of the microencapsulated composite phase change material is preferably 75-90%, specifically 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%. In this invention, the encapsulation rate is calculated as follows: Encapsulation rate (%) = Mass of core material (phase change material) actually encapsulated in the microcapsule ÷ Total mass of core material used during preparation × 100%.

[0043] In the energy storage heating glass provided by the present invention, the pore size of the porous silica carrier is preferably 20~200nm, specifically 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm or 200nm.

[0044] In the energy storage heating glass provided by the present invention, the mass ratio of the microencapsulated composite phase change material to the porous silica carrier in the phase change energy storage layer is preferably (1~5):1, specifically 1:1, 1.2:1, 1.5:1, 1.7:1, 2:1, 2.3:1, 2.5:1, 2.7:1, 3:1, 3.2:1, 3.5:1, 3.7:1, 4:1, 4.2:1, 4.5:1, 4.7:1 or 5:1.

[0045] In the energy storage heating glass provided by the present invention, the microencapsulated composite phase change material in the phase change energy storage layer fills the pores of the porous silica carrier.

[0046] In the energy storage heating glass provided by the present invention, the phase change temperature range of the phase change energy storage layer is preferably 5~45℃, specifically 25~35℃, 8~15℃, 15~40℃ or 20~32℃; the latent heat of phase change of the phase change energy storage layer is preferably 100~150J / g, specifically 100J / g, 105J / g, 110J / g, 115J / g, 120J / g, 125J / g, 130J / g, 135J / g, 140J / g, 145J / g or 150J / g.

[0047] In the energy storage heating glass provided by the present invention, the thickness of the phase change energy storage layer is preferably 1 to 5 mm, specifically 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm or 5 mm.

[0048] In the energy storage heating glass provided by the present invention, the phase change energy storage layer is preferably formed by mixing microencapsulated composite phase change material with a porous silica carrier and then compacting the mixture; the compaction pressure is preferably 3~20MPa, specifically 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa or 20MPa.

[0049] In the energy storage heating glass provided by the present invention, the components of the second adhesive layer include, but are not limited to, one or more of ethylene-vinyl acetate copolymer, polyvinyl butyral, and polyolefin elastomer.

[0050] In the energy storage heating glass provided by the present invention, the thickness of the second adhesive layer is preferably 0.2~2mm, specifically 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm or 2mm.

[0051] In the energy storage heating glass provided by the present invention, the second substrate glass includes, but is not limited to, float glass, tempered glass, ultra-clear float glass or tempered laminated glass.

[0052] In the energy storage heating glass provided by the present invention, the thickness of the second substrate glass is preferably 2 to 10 mm, specifically 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm.

[0053] In this invention, the carbon black-containing sandwich-type energy storage and heating glass is preferably manufactured by vacuuming and hot-pressing a first substrate glass, a first adhesive layer, a carbon black photothermal conversion layer, a phase change energy storage layer, a second adhesive layer, and a second substrate glass, which are stacked sequentially. The vacuuming time is preferably 10-60 minutes, specifically 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes. Preheating is preferably performed before hot pressing, with a preheating temperature preferably 60-90°C, specifically 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, or 90°C. The preheating time is preferably 15-45 minutes, specifically 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, or 45 minutes. The hot-pressing temperature is preferably 120-150°C. Specifically, the temperature can be 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, or 150℃; the pressure of the hot pressing is preferably 0.5~1.5MPa, specifically 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, or 1.5MPa; the hot pressing time is preferably 30~90min, specifically 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, or 90min.

[0054] For clarity, the following examples will be used to provide a detailed description.

[0055] Example 1

[0056] Medium-temperature energy storage heated glass for building exterior walls

[0057] 1) Preparation of modified carbon black:

[0058] 10 kg of conductive carbon black particles with a particle size of 20-30 nm were selected and added to 50 L of a 5% (w / w) aqueous solution prepared from silane coupling agent KH550 and deionized water. The mixture was placed in an ultrasonic disperser, and ultrasonically dispersed for 45 min at a power of 800 W and a frequency of 25 kHz to form a uniform suspension. The suspension was then transferred to a vacuum oven and dried at 80 °C and -0.09 MPa for 4 h to obtain modified carbon black particles, which showed a 60% improvement in dispersibility compared to unmodified carbon black.

[0059] 2) Preparation of carbon black photothermal conversion layer:

[0060] The modified carbon black and EVA granules were mixed at a mass ratio of 1:15 and added to a high-speed shear mill. The mixture was sheared at 1200 r / min for 30 min, and then homogenized twice under 80 MPa pressure using a high-pressure homogenizer to ensure uniform dispersion of carbon black in the compound, thus obtaining the photothermal conversion compound. This compound was then coated onto the surface of the first adhesive layer (EVA sheet, 0.5 mm thick) using a roller coating process, with the coating thickness controlled at 80 μm, forming a composite structure of a carbon black photothermal conversion layer and the first adhesive layer.

[0061] 3) Phase change energy storage layer preparation:

[0062] Paraffin wax and stearic acid were weighed at a mass ratio of 7:3, heated to 70℃ to completely melt and stirred evenly to obtain a composite phase change material. This material was added to a 10% (w / w) melamine-formaldehyde resin solution, stirred at high speed to form an emulsion, and then 5% (w / w) of ammonium chloride catalyst was added. The mixture was reacted at 60℃ for 90 min to obtain a microencapsulated paraffin wax-stearic acid composite phase change material with a particle size of 1-3 μm and an encapsulation efficiency of 85%. Using a porous silica carrier with a pore size of 50-100 nm, the microencapsulated composite phase change material was mixed evenly with the porous silica carrier at a mass ratio of 3:2 and compacted under 10 MPa pressure to form a 2 mm thick phase change energy storage layer with a latent heat of phase change of 120 J / g and a phase change temperature range of 25-35℃.

[0063] 4) Lamination assembly:

[0064] Two pieces of float glass, each measuring 1200mm × 600mm × 6mm, were selected as the first and second substrates. They were stacked in the following order: first substrate glass - first adhesive layer (including photothermal conversion layer) - phase change energy storage layer - second adhesive layer (pure EVA film, 0.5mm thickness) - second substrate glass, and then placed in a vacuum laminator. The laminator's process parameters were set as follows: vacuuming time 30 min, preheating temperature 80℃, preheating time 30 min, hot pressing temperature 140℃, hot pressing pressure 0.8MPa, and holding time 60 min. The glass was then allowed to cool naturally to room temperature to obtain the finished energy storage and heating glass product.

[0065] The core performance test data of the energy storage heating glass product prepared in this embodiment are as follows: photothermal conversion efficiency 75% (GB / T 39759-2021 standard test); after storing energy at 20℃ for 1 hour, it can maintain the glass surface temperature at 28~32℃ for 4 hours, and the energy storage density reaches 110kJ / m³. 2 With a visible light transmittance of 65% and an infrared absorption rate of 88%, it meets the requirements for lighting and insulation of building exterior walls.

[0066] Example 2

[0067] Low-temperature energy storage heated glass for vehicle windshields

[0068] 1) Preparation of modified carbon black:

[0069] Eight kilograms of high-structure carbon black with a particle size of 10-20 nm were added to 40 L of an 8% aqueous solution prepared from silane coupling agent KH560 and deionized water. The mixture was placed in an ultrasonic disperser and ultrasonically dispersed for 30 min at a power of 1000 W and a frequency of 30 kHz to form a uniform suspension. The suspension was then transferred to a vacuum oven and dried at 90 °C and -0.1 MPa for 3 h to obtain modified carbon black particles. The sedimentation rate of these particles in the organic binder was reduced by 75% compared to that of unmodified carbon black.

[0070] 2) Preparation of carbon black photothermal conversion layer:

[0071] The modified carbon black and PVB compound were mixed at a mass ratio of 1:12 and added to a high-speed shear mill. The mixture was sheared at 1500 r / min for 20 min, and then homogenized three times under 100 MPa pressure using a high-pressure homogenizer to ensure uniform dispersion of carbon black in the compound, thus obtaining the photothermal conversion compound. This compound was then coated onto the surface of the first adhesive layer (PVB film, 0.5 mm thick) using a slot coating process, with the coating thickness controlled at 50 μm, forming a composite structure of a carbon black photothermal conversion layer and the first adhesive layer.

[0072] 3) Phase change energy storage layer preparation:

[0073] Paraffin wax and stearic acid were weighed at a mass ratio of 6:4, heated to 70℃ to completely melt and stirred evenly to obtain a composite phase change material. This material was added to a urea-formaldehyde resin prepolymer and emulsified at 8000 rpm in an emulsifier to form microdroplets. Oxalic acid catalyst was added and the mixture was cured at 55℃ for 60 min to obtain a microencapsulated paraffin wax-stearic acid composite phase change material with a particle size of 0.5–2 μm and an encapsulation efficiency of 82%. Using porous silica with a pore size of 30–80 nm, the microencapsulated composite phase change material and a porous silica carrier were mixed evenly at a mass ratio of 4:1 and compacted under 5 MPa pressure to form a 1.5 mm thick phase change energy storage layer with a latent heat of phase change of 105 J / g and a phase change temperature range of 8–15℃, suitable for the low-temperature environment requirements of vehicles.

[0074] 4) Lamination assembly:

[0075] Two pieces of tempered glass, each 500mm × 300mm × 3mm, were used as the first and second substrates. They were stacked in the following order: first substrate glass - first adhesive layer (including photothermal conversion layer) - phase change energy storage layer - second adhesive layer (pure PVB film, 0.5mm thickness) - second substrate glass, and fed into a continuous laminator. The laminator's process parameters were set as follows: vacuuming time 15 min, preheating temperature 70℃, preheating time 30 min, hot pressing temperature 130℃, hot pressing pressure 1.0 MPa, and holding time 30 min. Afterward, the glass was allowed to cool naturally to below 40℃ before being removed, yielding the finished energy storage and heating glass product.

[0076] The performance test data of the energy storage heated glass product prepared in this embodiment for vehicle windshield scenarios are as follows: In a -5℃ environment, the surface temperature rises from -5℃ to 5℃ within 3 minutes, with a heating rate of 3.3℃ / min; after storing energy at 30℃ for 4 hours, it can maintain a temperature above 0℃ for 2 hours in a -10℃ environment, with a low-temperature energy storage density of 95 kJ / m³. 2 Light transmittance is 72% (meets the light transmittance requirements for automotive safety glass in GB 9656-2021).

[0077] Example 3

[0078] Wide-temperature-range energy storage heating glass for agricultural greenhouses

[0079] 1) Preparation of modified carbon black:

[0080] 12 kg of ordinary carbon black with a particle size of 30-50 nm was added to 60 L of a 4% (w / w) aqueous solution prepared from silane coupling agent KH570 and deionized water. The mixture was placed in an ultrasonic disperser, and ultrasonically dispersed for 60 min at a power of 600 W and a frequency of 20 kHz to form a uniform suspension. The suspension was then transferred to a vacuum oven and dried at 70 °C and -0.08 MPa for 5 h to obtain modified carbon black particles, which showed significantly improved compatibility with resin.

[0081] 2) Preparation of carbon black photothermal conversion layer:

[0082] The modified carbon black and POE granules were mixed at a mass ratio of 1:18 and added to a high-speed shear mill. The mixture was sheared at 1000 r / min for 40 min, and then homogenized twice under a high-pressure homogenizer at 60 MPa to ensure uniform dispersion of carbon black in the compound, thus obtaining the photothermal conversion compound. This compound was then coated onto the surface of the first adhesive layer (POE film, 0.5 mm thick) using a roller coating process, with the coating thickness controlled at 100 μm, forming a composite structure of a carbon black photothermal conversion layer and the first adhesive layer.

[0083] 3) Phase change energy storage layer preparation:

[0084] Paraffin wax, stearic acid, and palmitic acid were weighed in a mass ratio of 5:3:2, heated until completely melted, and stirred evenly to obtain a wide-temperature-range composite phase change material. This material was added to a 10% (w / w) melamine-formaldehyde resin solution and reacted at 70℃ for 120 min to obtain a microencapsulated paraffin-stearic acid-palmitic acid composite phase change material with a particle size of 2-4 μm and an encapsulation rate of 80%. Using porous silica with a pore size of 80-150 nm, the microencapsulated composite phase change material and the porous silica carrier were mixed evenly in a mass ratio of 5:2 and compacted under 15 MPa pressure to form a 3 mm thick phase change energy storage layer with a latent heat of phase change of 130 J / g and a phase change temperature range of 15-40℃, suitable for greenhouse diurnal temperature variations.

[0085] 4) Lamination assembly:

[0086] Two pieces of ultra-clear float glass, each measuring 1500mm × 800mm × 5mm, were selected as the first and second substrates. They were stacked in the following order: first substrate glass - first adhesive layer (including photothermal conversion layer) - phase change energy storage layer - second adhesive layer (pure POE film, 0.5mm thick) - second substrate glass, and then placed in an intermittent laminator. The laminator's process parameters were set as follows: vacuuming for 40 minutes, preheating temperature 85℃, preheating time 30 minutes, hot pressing temperature 145℃, temperature and pressure 0.6MPa, and holding time 90 minutes. The glass was then slowly cooled to room temperature to obtain the finished energy storage and heating glass product.

[0087] The core performance test data of the energy storage heating glass product prepared in this embodiment are as follows: photothermal conversion efficiency 72% (GB / T 39759-2021 standard test); after storing energy for 2 hours at 30℃, it can release heat at night to maintain the temperature inside the greenhouse at 18~22℃ for 6 hours, reducing the day-night temperature difference by 8℃; the ultra-white glass substrate allows visible light transmittance to reach 88%, which is beneficial to crop photosynthesis; the ultraviolet transmittance is ≤0.5%, which can reduce crop scorching.

[0088] Example 4

[0089] High-strength energy storage heating glass for industrial plants

[0090] 1) Preparation of modified carbon black:

[0091] Nine kg of conductive carbon black with a particle size of 20-40 nm was added to 45 L of a 6% (w / w) aqueous solution prepared from silane coupling agent KH590 and deionized water. The mixture was placed in an ultrasonic disperser, and ultrasonically dispersed for 50 min at a power of 900 W and a frequency of 28 kHz to form a uniform suspension. The suspension was then transferred to a vacuum oven and dried at 85 °C and -0.095 MPa for 3.5 h to obtain modified carbon black particles.

[0092] 2) Preparation of carbon black photothermal conversion layer:

[0093] The modified carbon black and EVA / POE composite granules (EVA / POE mass ratio = 8:2) were mixed at a mass ratio of 1:14 and added to a high-speed shear mill. The mixture was sheared at 1300 r / min for 25 min, and then homogenized three times under a high-pressure homogenizer at 90 MPa pressure to ensure that the carbon black was uniformly dispersed in the mixture, thus obtaining the photothermal conversion adhesive. The adhesive was then coated onto the surface of the first adhesive layer (EVA / POE composite film, 0.5 mm thick) using a roller coating process, with the coating thickness controlled at 70 μm, forming a composite structure of carbon black photothermal conversion layer and first adhesive layer.

[0094] 3) Phase change energy storage layer preparation:

[0095] Paraffin wax and stearic acid were weighed at a mass ratio of 8:2, heated to 70℃ to completely melt and stirred evenly to obtain a composite phase change material. This material was added to a 10% (w / w) melamine-formaldehyde resin solution, stirred at high speed to form an emulsion, and then 5% (w / w) of ammonium chloride catalyst was added. The mixture was reacted at 60℃ for 90 min to obtain a microencapsulated paraffin wax-stearic acid composite phase change material with a particle size of 1-3 μm and an encapsulation efficiency of 85%. Using a porous silica carrier with a pore size of 60-120 nm, the microencapsulated composite phase change material was mixed evenly with the porous silica carrier at a mass ratio of 3.5:1 and compacted under 12 MPa pressure to form a 2.5 mm thick phase change energy storage layer with a latent heat of phase change of 115 J / g and a phase change temperature range of 20-32℃.

[0096] 4) Lamination assembly:

[0097] Two tempered laminated glass sheets, each measuring 1000mm × 700mm × 8mm, were selected as the first and second substrates. They were stacked in the following order: first substrate glass - first adhesive layer (including photothermal conversion layer) - phase change energy storage layer - second adhesive layer (EVA / POE composite film, 0.5mm thick) - second substrate glass, and then placed in a vacuum laminator. The laminator's process parameters were set as follows: vacuuming time 35 min, preheating temperature 75℃, preheating time 30 min, hot pressing temperature 135℃, hot pressing pressure 1.2 MPa, and holding time 45 min. The glass was then allowed to cool naturally to room temperature to obtain the finished energy storage and heating glass product.

[0098] The core performance test data of the energy storage heating glass product prepared in this embodiment are as follows: photothermal conversion efficiency 73% (GB / T 39759-2021 standard test); after storing energy at 25℃ for 1.5h, it can maintain a surface temperature of 25~30℃ for 5h, and the energy storage density reaches 125kJ / m³. 2With a visible light transmittance of 60%, it meets the lighting needs of industrial plants while also providing good privacy protection.

[0099] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A sandwich-type energy storage and heating glass containing carbon black, characterized in that, It includes a first substrate glass, a first adhesive layer, a carbon black photothermal conversion layer, a phase change energy storage layer, a second adhesive layer, and a second substrate glass, which are stacked sequentially. The carbon black photothermal conversion layer contains carbon black modified with a silane coupling agent; The phase change energy storage layer comprises a microencapsulated composite phase change material and a porous silica carrier, wherein the phase change material in the microencapsulated composite phase change material includes paraffin and stearic acid.

2. The laminated energy storage and heating glass according to claim 1, characterized in that, The silane coupling agent modified carbon black is made from carbon black raw material after being modified by a silane coupling agent; the carbon black raw material is ordinary carbon black and / or conductive carbon black; the particle size of the carbon black raw material is 5~50nm; the grade of the silane coupling agent is one or more of KH550, KH560, KH570 and KH590.

3. The laminated energy storage heating glass according to claim 1, characterized in that, The carbon black photothermal conversion layer also contains a binder.

4. The laminated energy storage heating glass according to claim 3, characterized in that, The adhesive is one or more of ethylene-vinyl acetate copolymer, polyvinyl butyral and polyolefin elastomer; the mass ratio of silane coupling agent modified carbon black in the carbon black photothermal conversion layer to the adhesive is 1:(10~20).

5. The laminated energy storage heating glass according to claim 1, characterized in that, The thickness of the carbon black photothermal conversion layer is 30~150μm.

6. The laminated energy storage heating glass according to claim 1, characterized in that, The paraffin wax accounts for 50-90 wt% of the total mass of paraffin wax and stearic acid.

7. The laminated energy storage heating glass according to claim 1, characterized in that, The phase change material also includes palmitic acid; the content of palmitic acid in the phase change material is 10~30wt%.

8. The laminated energy storage heating glass according to claim 1, characterized in that, The particle size of the microencapsulated composite phase change material is 0.5~5μm.

9. The laminated energy storage heating glass according to claim 1, characterized in that, The mass ratio of the microencapsulated composite phase change material to the porous silica carrier in the phase change energy storage layer is (1~5):

1.

10. The laminated energy storage heating glass according to claim 1, characterized in that, The thickness of the phase change energy storage layer is 1~5mm.