Sodium alginate membrane material with stable energy storage performance and preparation method thereof
By combining sodium alginate with pyrazolazobenzene quaternary ammonium salt compounds, stable sodium alginate film materials are prepared, which solves the problems of low energy storage density and unstable phase state of existing photoenergy storage materials, achieves efficient photoenergy storage and heat release, and expands the application range of photoenergy storage materials.
Patent Information
- Application Number
- CN202510596857.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-09
- Publication Date
- 2025-08-08
AI Technical Summary
The existing photoenergy storage materials have problems such as low energy storage density, difficulty in light energy storage, and unstable phase transition of materials, which limit their practical application in the field of photoenergy storage.
Sodium alginate and pyrazolazobenzene quaternary ammonium salt compounds are used to prepare stable sodium alginate film materials through electrostatic combination, and ultraviolet light storage and visible light release thermal energy to achieve stable storage and efficient conversion of light energy.
It has achieved high energy storage density, stable light energy storage and thermal energy release, stable material phase state, and energy storage period is up to more than 40 days, simplifying the preparation process.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of light energy storage and biomass materials, and mainly relates to a sodium alginate film material with stable energy storage performance and a preparation method thereof. Background Art
[0002] Light energy has the advantages of being renewable and pollution-free, making efficient conversion of light energy into other energy forms of great significance. Currently, the storage and utilization of light energy is primarily based on the development of electrochemical technologies, which still lack efficiency in terms of energy conversion. In contrast, molecular switch-based photothermal conversion materials can achieve stable storage of light energy and efficient conversion to thermal energy. In recent years, the design and synthesis of molecular switch-based photothermal conversion materials have attracted continuous attention in the field of energy chemistry.
[0003] Molecular switch-based photothermal conversion materials are primarily based on azo compounds, storing and converting light energy into heat through the photoisomerization of azo groups. Taking azobenzene as an example, the low-energy stable trans-azobenzene can be transformed into the high-energy metastable cis-azobenzene by absorbing ultraviolet light, storing the light energy. Under visible light stimulation, the cis-azobenzene reconverts to trans-azobenzene, releasing the stored light energy as heat. This photothermal conversion based on the photoisomerization of azo groups is a closed-loop energy conversion process, enabling ultra-high efficiency in converting light energy into heat. However, azobenzene materials suffer from relatively low energy storage density and difficulty in storing energy under illumination. Researchers have discovered that by covalently bonding azobenzene to carbon materials such as graphene or carbon nanotubes, non-photoinduced phase change energy storage materials can be prepared. By enhancing the intermolecular forces between azobenzene groups, the energy storage density of azobenzene materials can be significantly improved. However, this type of azobenzene attached to a carbon material is difficult to store directly through UV light. It typically requires dissolving it in an organic solvent for light-induced energy storage, after which the solvent is removed to produce a material that can release thermal energy. The complex photothermal conversion process and the short energy storage cycle of azobenzene-based materials make them unsuitable for practical applications in the field of solar energy storage.
[0004] Compared with azobenzene materials, pyrazole azobenzene materials have the advantages of high energy storage density and good energy storage stability. The pyrazole azobenzene energy storage materials currently under development are mainly organic small molecule compounds. Such materials can simultaneously undergo structural isomerization of molecular conformation and transformation of material phase under ultraviolet light irradiation, thereby improving energy storage density by storing light energy and low-temperature thermal energy at the same time. Although such materials achieve the simultaneous utilization of light energy and low-temperature thermal energy, the material phase transformation during the energy conversion process brings inconsistencies to certain application scenarios, such as the risk of material leakage or uneven material distribution when the material forms a liquid. The preparation of pyrazole azobenzene materials into non-photoinduced phase change energy storage materials will be able to expand the application range of azo energy storage materials.
[0005] Sodium alginate has the advantages of being abundant in nature, low cost, and renewable. It is one of the ideal raw materials for preparing non-photoinduced phase change energy storage materials to replace carbon materials such as graphene and carbon nanotubes. By utilizing the large amount of negative charge carried by sodium alginate molecules and electrostatically connecting pyrazoloazobenzene molecules to sodium alginate molecules, a structurally stable and lightweight membrane material is prepared, which is expected to achieve light energy storage of pyrazoloazobenzene molecules in a solid state. At the same time, this type of material will also have the advantages of good energy storage stability, low preparation cost, and simple synthesis. Therefore, combining sodium alginate and pyrazoloazobenzene molecules through electrostatic forces to develop photothermal conversion membrane materials with simple energy storage methods, high energy storage density, and phase stability is of great significance for expanding the application of sodium alginate materials and molecular switch materials in basic scientific research and new energy storage fields. Summary of the Invention
[0006] In view of this, the object of the present invention is to provide a sodium alginate membrane material with stable energy storage performance and a preparation method thereof.
[0007] The technical solutions of the present invention are as follows:
[0008] The invention provides a sodium alginate membrane material with stable energy storage performance. The raw materials for preparing the sodium alginate membrane material include sodium alginate, a pyrazole azobenzene quaternary ammonium salt compound and calcium chloride.
[0009] In the present invention, the sodium alginate is a mixture of polysaccharide polymers with a molecular formula of (C6H7O6Na)n.
[0010] In the present invention, the pyrazoloazobenzene quaternary ammonium salt compound is any one of N,N,N-trimethyl-4-(4-(4-(1-methyl)-pyrazolyldiazenyl)phenoxy)n-butylammonium bromide and N,N,N-trimethyl-8-(4-(4-(1-methyl)-pyrazolyldiazenyl)phenoxy)n-octylammonium bromide.
[0011] In the present invention, the method for preparing the sodium alginate membrane material with stable energy storage performance comprises:
[0012] Under room temperature conditions, an aqueous solution of sodium alginate and an aqueous solution of a quaternary ammonium salt compound of a pyrazoloazobenzene are mixed, the obtained suspension is applied to a smooth surface of a glass plate, the suspension applied to the surface of the glass plate is naturally dried at room temperature to remove moisture to obtain an ion complex of sodium alginate and the quaternary ammonium salt compound of the pyrazoloazobenzene, the glass plate carrying the ion complex of sodium alginate and the quaternary ammonium salt compound of the pyrazoloazobenzene is immersed in a calcium chloride solution to obtain a membrane material, the obtained membrane material is washed three times with water for purification, and finally the obtained membrane material is peeled off the glass plate and naturally dried at room temperature to obtain the sodium alginate membrane material with stable energy storage performance of the present invention.
[0013] In the present invention, in the preparation method of the sodium alginate membrane material with stable energy storage performance, the concentration of the aqueous solution of sodium alginate is 20 to 30 mmol / L, based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na, the concentration of the aqueous solution of sodium alginate is 2 to 5 mmol / L, the mass concentration of the aqueous solution of the pyrazole azobenzene quaternary ammonium salt compound is 2 to 5 mmol / L, and the mass concentration of the calcium chloride solution is 1 to 3%.
[0014] In the present invention, in the method for preparing the sodium alginate membrane material with stable energy storage performance, in the suspension obtained by mixing the aqueous solution of sodium alginate with the aqueous solution of the pyrazoloazobenzene quaternary ammonium salt compound, the sodium alginate is calculated as C6H7O6Na in terms of the repeating monosaccharide unit of sodium alginate, and the molar ratio of the sodium alginate to the pyrazoloazobenzene quaternary ammonium salt compound is 3:1 to 5:1.
[0015] In the present invention, in the method for preparing the sodium alginate film material with stable energy storage performance, the suspension coated on the surface of the glass plate is naturally dried to remove moisture at room temperature (20-30°C) and a relative humidity of 70% or less for 24 hours; the glass plate carrying the ionic complex of sodium alginate and a pyrazoloazobenzene quaternary ammonium salt compound is immersed in a calcium chloride solution for 10 minutes; and the obtained film material is peeled off from the glass plate and then naturally dried at room temperature (20-30°C) and a relative humidity of 70% or less for 12 hours.
[0016] In the present invention, after the sodium alginate membrane material with stable energy storage performance is prepared, the process further includes storing energy under ultraviolet light irradiation and releasing heat under visible light irradiation of the sodium alginate membrane material with stable energy storage performance at room temperature.
[0017] In the present invention, the sodium alginate film material with stable energy storage performance is subjected to energy storage under ultraviolet irradiation: the ultraviolet irradiation conditions are: wavelength 365nm, intensity 20-50mW / cm 2 , time 10 minutes; the sodium alginate film material having stable energy storage performance releases heat energy under visible light irradiation: the visible light irradiation conditions are a wavelength of 520nm, an intensity of 50 to 100mW / cm 2 , time 15 minutes.
[0018] The present invention provides a sodium alginate membrane material with stable energy storage performance and a preparation method thereof. The sodium alginate membrane material with stable energy storage performance and the preparation method thereof have the following characteristics:
[0019] 1. The sodium alginate membrane material with stable energy storage performance obtained by the present invention is a membrane material containing a pyrazole azobenzene quaternary ammonium salt compound formed by calcium ion cross-linking sodium alginate molecules.
[0020] 2. The sodium alginate film material with stable energy storage performance obtained by the present invention can store light energy through ultraviolet light irradiation and release heat energy through visible light irradiation at room temperature.
[0021] 3. The sodium alginate membrane material with stable energy storage performance obtained by the present invention can stably store energy for more than 40 days at room temperature and without light conditions after completing energy storage by ultraviolet light irradiation. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is the UV-visible absorption spectrum of the sodium alginate membrane material with stable energy storage performance described in Example 1 before UV irradiation, after UV irradiation, and after visible light irradiation.
[0023] Figure 2 This is the differential scanning calorimetry analysis spectrum of the sodium alginate membrane material with stable energy storage performance described in Example 1 before and after ultraviolet light irradiation.
[0024] Figure 3 The sodium alginate film material with stable energy storage performance described in Example 1, after completing energy storage by ultraviolet light irradiation, the sodium alginate film material with stable energy storage performance is under light-free conditions, and the ultraviolet-visible absorption intensity of the sodium alginate film material with stable energy storage performance at 360nm at temperatures of 80°C, 85°C and 90°C changes. DETAILED DESCRIPTION
[0025] The present invention provides a sodium alginate membrane material with stable energy storage performance and a preparation method thereof. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve the desired effect. It should be noted that all similar replacements and modifications are obvious to those skilled in the art and are considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments. Relevant personnel can obviously modify or appropriately change and combine the methods and applications herein without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.
[0026] The present invention will be further described below in conjunction with the embodiments:
[0027] Example 1:
[0028] At room temperature, 1.0 mL of a 30 mmol / L sodium alginate aqueous solution (based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na) and 2.0 mL of a 5 mmol / L N,N,N-trimethyl-4-(4-(4-(1-methyl)-pyrazolyldiazenyl)phenoxy)n-butylammonium bromide aqueous solution were mixed, and the resulting suspension was applied to a smooth glass plate surface. The suspension applied to the glass plate surface was naturally dried at 20°C and a relative humidity of 50%. The method comprises the steps of: drying the obtained ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt for 24 hours to obtain an ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt compound; immersing the obtained ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt compound in a 2% by mass calcium chloride solution for 10 minutes to obtain a membrane material; washing the obtained membrane material three times with water for purification; and finally peeling the obtained membrane material from the glass plate and naturally drying it at 25° C. and a relative humidity of 50% for 12 hours to obtain the sodium alginate membrane material with stable energy storage performance of the present invention.
[0029] The UV-visible absorption spectra of the prepared sodium alginate membrane material with stable energy storage performance before UV irradiation, after UV irradiation for 10 minutes, and after visible light irradiation for 15 minutes are as follows: Figure 1 As shown, according to Figure 1 It was concluded that the prepared sodium alginate membrane material with stable energy storage performance contained N,N,N-trimethyl-4-(4-(4-(1-methyl)-pyrazolyldiazenyl)phenoxy)n-butylammonium, which underwent photoisomerization after both ultraviolet light irradiation and visible light irradiation.
[0030] The prepared sodium alginate membrane material with stable energy storage performance can maintain the solid phase of the membrane material unchanged after being irradiated with ultraviolet light for 10 minutes and after being irradiated with visible light for 15 minutes.
[0031] The prepared sodium alginate membrane material with stable energy storage performance has differential scanning calorimetry analysis patterns before and after ultraviolet irradiation for 10 minutes, as shown in FIG. Figure 2 As shown, according to Figure 2 The results show that the prepared sodium alginate membrane material with stable energy storage performance can achieve an energy storage density of 495.7 J / g under ultraviolet light irradiation. The energy stored in the prepared sodium alginate membrane material with stable energy storage performance can be released as heat energy under visible light irradiation.
[0032] The prepared sodium alginate film material with stable energy storage performance, after completing energy storage by ultraviolet light irradiation, the sodium alginate film material with stable energy storage performance has a change in ultraviolet-visible absorption intensity at 360nm at temperatures of 80°C, 85°C and 90°C under no light conditions, as shown in FIG. Figure 3 As shown, according to Figure 3 , it was concluded that the prepared sodium alginate membrane material with stable energy storage performance can stably store energy for 45 days at 25°C and without light after completing energy storage under ultraviolet light irradiation.
[0033] Example 2:
[0034] At room temperature, 1.0 mL of a 30 mmol / L sodium alginate aqueous solution (based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na) and 2.0 mL of a 5 mmol / L N,N,N-trimethyl-8-(4-(4-(1-methyl)-pyrazolyldiazenyl)phenoxy)-n-octylammonium bromide aqueous solution were mixed, and the resulting suspension was applied to a smooth glass plate surface. The suspension applied to the glass plate surface was naturally dried at 20°C and a relative humidity of 50%. The method comprises the steps of: drying the obtained ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt for 24 hours to obtain an ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt compound; immersing the obtained ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt compound in a 2% by mass calcium chloride solution for 10 minutes to obtain a membrane material; washing the obtained membrane material three times with water for purification; and finally peeling the obtained membrane material from the glass plate and naturally drying it at 25° C. and a relative humidity of 50% for 12 hours to obtain the sodium alginate membrane material with stable energy storage performance of the present invention.
[0035] The prepared sodium alginate membrane material with stable energy storage performance can maintain the solid phase of the membrane material unchanged after being irradiated with ultraviolet light for 10 minutes and after being irradiated with visible light for 15 minutes.
[0036] Example 3:
[0037] At room temperature, 1.0 mL of a 30 mmol / L sodium alginate aqueous solution (based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na) and 1.2 mL of a 5 mmol / L N,N,N-trimethyl-4-(4-(4-(1-methyl)-pyrazolyldiazenyl)phenoxy)n-butylammonium bromide aqueous solution were mixed, and the resulting suspension was applied to a smooth glass plate surface. The suspension applied to the glass plate surface was naturally dried at 20°C and a relative humidity of 50%. The method comprises the steps of: drying the obtained ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt for 24 hours to obtain an ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt compound; immersing the obtained ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt compound in a 2% by mass calcium chloride solution for 10 minutes to obtain a membrane material; washing the obtained membrane material three times with water for purification; and finally peeling the obtained membrane material from the glass plate and naturally drying it at 25° C. and a relative humidity of 50% for 12 hours to obtain the sodium alginate membrane material with stable energy storage performance of the present invention.
[0038] The prepared sodium alginate membrane material with stable energy storage performance can maintain the solid phase of the membrane material unchanged after being irradiated with ultraviolet light for 5 minutes and after being irradiated with visible light for 15 minutes.
[0039] Comparative Example 1:
[0040] At room temperature, 1.0 mL of a 30 mmol / L sodium alginate aqueous solution (based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na) and 2.0 mL of a 5 mmol / L N,N-dimethyl-N-(4-(4-((4-n-octyloxyphenyl)diazenyl)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide aqueous solution were mixed, and the resulting suspension was applied to a smooth glass plate surface. The suspension applied to the glass plate surface was naturally dried at 20°C and a relative humidity of 50% for 24 hours to obtain sodium alginate and N,N-dimethyl-N-(4-(4-((4-n-octyloxyphenyl)diazenyl)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide. The invention relates to an ion complex of sodium alginate and N,N-dimethyl-N-(4-(4-((4-n-octyloxyphenyl)diazenyl)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide, and a glass plate loaded with the obtained sodium alginate and the ion complex of N,N-dimethyl-N-(4-(4-((4-n-octyloxyphenyl)diazenyl)phenoxy)n-butyl)-3,6,9,12-tetraoxatridecylammonium bromide is immersed in a calcium chloride solution with a mass concentration of 2% for 10 minutes to obtain a membrane material, and the obtained membrane material is purified by washing with water three times. Finally, the obtained membrane material is peeled off from the glass plate and naturally dried at 25° C. and a relative humidity of 50% for 12 hours to obtain a sodium alginate ion complex membrane material.
[0041] The sodium alginate ion complex membrane material prepared in Comparative Example 1 was tested and found to be transformed into a liquid state after being irradiated with ultraviolet light for 10 minutes.
[0042] Comparative Example 2:
[0043] At room temperature, 1.0 mL of a 30 mmol / L aqueous solution of sodium carboxymethyl cellulose (based on the repeating monosaccharide unit of sodium carboxymethyl cellulose being C6H7O2(OH)2OCH2COONa) and 2.0 mL of a 5 mmol / L aqueous solution of N,N,N-trimethyl-4-(4-(4-(1-methyl)-pyrazolyldiazenyl)phenoxy)n-butylammonium bromide were mixed, and the resulting suspension was applied to a smooth glass plate surface. The suspension applied to the glass plate surface was naturally dried at 20°C and a relative humidity of 50% for 24 hours to obtain an ionic complex of carboxymethyl cellulose and a quaternary ammonium salt compound of a pyrazoloazobenzene type. The glass plate carrying the obtained ionic complex of carboxymethyl cellulose and a quaternary ammonium salt compound of a pyrazoloazobenzene type was immersed in a 2% by mass calcium chloride solution for 10 minutes, but no membrane material was obtained.
[0044] The above are only preferred embodiments of the present invention. It should be pointed out that those skilled in the art can make several improvements without departing from the principles of the present invention, and these improvements should also be considered as within the scope of protection of the present invention.
Claims
1. A sodium alginate membrane material with stable energy storage performance, characterized in that: The preparation raw materials include sodium alginate, a pyrazolodiazobenzene quaternary ammonium salt compound and calcium chloride. The sodium alginate is a mixture of polysaccharide polymers with a molecular formula of (C6H7O6Na)n. The pyrazolodiazobenzene quaternary ammonium salt compound is any one of N,N,N-trimethyl-4-(4-(4-(1-methyl)-pyrazolodiazenyl)phenoxy)n-butylammonium bromide and N,N,N-trimethyl-8-(4-(4-(1-methyl)-pyrazolodiazenyl)phenoxy)n-octylammonium bromide.
2. The method for preparing a sodium alginate membrane material with stable energy storage performance according to claim 1, characterized in that: include: Under room temperature conditions, an aqueous solution of sodium alginate and an aqueous solution of a quaternary ammonium salt compound of a pyrazoloazobenzene are mixed, the obtained suspension is applied to a smooth surface of a glass plate, the suspension applied to the surface of the glass plate is naturally dried at room temperature to remove moisture to obtain an ion complex of sodium alginate and the quaternary ammonium salt compound of the pyrazoloazobenzene, the glass plate carrying the ion complex of sodium alginate and the quaternary ammonium salt compound of the pyrazoloazobenzene is immersed in a calcium chloride solution to obtain a membrane material, the obtained membrane material is washed three times with water for purification, and finally the obtained membrane material is peeled off the glass plate and naturally dried at room temperature to obtain the sodium alginate membrane material with stable energy storage performance of the present invention.
3. The method for preparing the sodium alginate membrane material with stable energy storage performance according to claim 2, characterized in that: The sodium alginate aqueous solution has a concentration of 20 to 30 mmol / L, based on the repeating monosaccharide unit of sodium alginate being C6H7O6Na; the concentration of the aqueous solution of the pyrazole azobenzene quaternary ammonium salt compound is 2 to 5 mmol / L; and the mass concentration of the calcium chloride solution is 1 to 3%.
4. The method for preparing the sodium alginate membrane material with stable energy storage performance according to claim 2, characterized in that: In the suspension obtained by mixing the aqueous solution of sodium alginate with the aqueous solution of the pyrazoloazobenzene quaternary ammonium salt compound, the sodium alginate is calculated as C6H7O6Na in terms of the repeating monosaccharide unit of sodium alginate, and the molar ratio of the sodium alginate to the pyrazoloazobenzene quaternary ammonium salt compound is 3:1 to 5:
1.
5. The method for preparing the sodium alginate membrane material with stable energy storage performance according to claim 2, characterized in that: The suspension applied to the surface of the glass plate is naturally dried to remove moisture at room temperature (20-30° C., relative humidity below 70%) for 24 hours; the glass plate carrying the ionic complex of sodium alginate and pyrazoloazobenzene quaternary ammonium salt compound is immersed in a calcium chloride solution for 10 minutes; and the obtained film material is peeled off from the glass plate and then naturally dried at room temperature (20-30° C., relative humidity below 70%) for 12 hours.