WO2020258605A1 - Polyacid-based electrolyte conductor material and preparation method and application thereof - Google Patents

Polyacid-based electrolyte conductor material and preparation method and application thereof Download PDF

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WO2020258605A1
WO2020258605A1 PCT/CN2019/112054 CN2019112054W WO2020258605A1 WO 2020258605 A1 WO2020258605 A1 WO 2020258605A1 CN 2019112054 W CN2019112054 W CN 2019112054W WO 2020258605 A1 WO2020258605 A1 WO 2020258605A1
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polyacid
conductor material
based electrolyte
electrolyte conductor
polymer
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PCT/CN2019/112054
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French (fr)
Chinese (zh)
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郑昭
蔡林坤
殷盼超
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华南理工大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the field of battery materials, and particularly relates to a polyacid-based electrolyte conductor material and a preparation method and application thereof.
  • Polyoxometallates also known as polyacids, are nano-scale pre-transition metal-oxygen molecular clusters, and their low effective surface charge density gives them strong proton transport capabilities.
  • Keggin-type polyacids for example, H 3 PW 12 O 40 , H 4 SiW 12 O 40
  • H 3 PW 12 O 40 , H 4 SiW 12 O 40 have high proton conductivity comparable to Nafions under high humidity. Protons are transferred between polyacids through the hydrogen bond network formed by crystal water. Therefore, the conductivity is greatly affected by humidity, and its application is limited.
  • the primary purpose of the present invention is to provide a polyacid-based electrolyte conductor material.
  • the polyacid and the polymer form a three-dimensional network for transferring protons through hydrogen bonding, and the effective transfer of protons is realized through the movement of polymer chains.
  • the electrolyte conductor material has good proton conduction efficiency in a medium and low temperature environment, as well as good processability, safety and chemical stability.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polyacid-based electrolyte conductor material.
  • Another object of the present invention is to provide the application of the above-mentioned polyacid-based electrolyte conductor material.
  • a method for preparing a polyacid-based electrolyte conductor material includes the following steps: mixing polyacid and polymer melt to obtain a blend, heating and stirring the blend to react, and cooling to room temperature after the reaction is complete, and then preparing the blend The polyacid-based electrolyte conductor material.
  • the mass ratio of the polyacid to the polymer melt is 1:9-7:3.
  • the heating and stirring time is 5 to 48 hours, more preferably 12 hours; the heating and stirring temperature is 60 to 80° C.; the heating and stirring speed is 100 to 700 rpm.
  • the room temperature is 25-35°C.
  • the type of the polyacid is one of Keggin-type polyacid, Dawson-type polyacid and Preyssler-type polyacid.
  • the polymer is a polymer with one or more of hydroxyl group, carboxylic acid group and amino group.
  • the polymer with one or more of hydroxyl group, carboxylic acid group and amino group is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol and chitosan, more preferably polyethylene Glycol (PEG).
  • PEG polyethylene Glycol
  • the molecular weight of the polyethylene glycol is one of an average molecular weight of 400 to 300,000, more preferably a polyethylene glycol with an average molecular weight of 400, 4000 and a six-arm star polyethylene glycol with an average molecular weight of 2400. Two or more.
  • a preparation method of a polyacid-based electrolyte conductor material comprising the following steps: adding a polymer to a solvent to obtain a polymer solution; adding a polyacid to the solvent to obtain a polyacid solution; mixing a polyacid solution and a polymer solution to obtain The blend is heated and stirred to react, and after the reaction is completed, the polyacid-based electrolyte conductor material is prepared after the solvent is completely volatilized.
  • the polymer is added to the solvent to obtain a polymer solution, and the concentration of the polymer solution ranges from 0.1 g/ml to 1 g/ml.
  • the polyacid is added to the solvent to obtain a polyacid solution, and the concentration of the polyacid solution ranges from 0.1 g/ml to 1 g/ml.
  • the volume ratio of the polyacid solution to the polymer solution is 1:9-7:3.
  • the heating and stirring time is 5 to 48 hours, more preferably 12 hours; the heating and stirring temperature is 40 to 60°C; and the heating and stirring speed is 100 to 700 rpm.
  • the solvent is water or tetrahydrofuran, more preferably tetrahydrofuran.
  • the type of the polyacid is one or more of Keggin-type polyacid, Dawson-type polyacid and Preyssler-type polyacid.
  • the polymer is a polymer with one or more of hydroxyl group, carboxylic acid group and amino group.
  • the polymer with one or more of hydroxyl group, carboxylic acid group and amino group is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol and chitosan, more preferably poly Ethylene glycol.
  • the molecular weight of the polyethylene glycol is an average molecular weight, and the molecular weight ranges from 400 to 300,000, more preferably polyethylene glycol with an average molecular weight of 400 and 4000 and a six-arm star polyethylene glycol with an average molecular weight of 2400. One or more than two.
  • a polyacid-base electrolyte conductor material prepared by the above-mentioned preparation method of a polyacid-base electrolyte conductor material prepared by the above-mentioned preparation method of a polyacid-base electrolyte conductor material.
  • the present invention has the following advantages and beneficial effects:
  • the polyacid-based electrolyte conductor material of the present invention has a high proton conduction efficiency ( ⁇ 1.01 ⁇ 10 -2 S cm -1 ) in a medium and low temperature environment (80° C.).
  • the preparation method of the present invention is simple, the reaction conditions are mild, it is easy to prepare in large quantities, and the cost is low.
  • polyethylene glycol can be combined with polyacids through hydrogen bonds, which greatly improves the proton conduction efficiency, and the viscosity of the sample up to 273 Pa ⁇ s ensures its safety when used as an electrolyte Sex.
  • the polyacid-based electrolyte conductor material prepared by the present invention has obvious shear thinning behavior, so that the sample has good processability.
  • Figure 1 is the small-angle scattering spectra of the electrolyte conductor materials prepared in Examples 1-7.
  • Figure 2 is a schematic diagram of the structure and proton conduction of an electrolyte conductor material prepared in an embodiment of the present invention.
  • Figure 3 is a Nyquist diagram of the PEG400 electrolyte conductor material prepared in Comparative Example 1 at 25°C, 50°C and 80°C.
  • Figure 4 is a Nyquist diagram of the PEG400-10% PW 12 electrolyte conductor material prepared in Example 1 at 25°C, 50°C and 80°C.
  • Fig. 5 is a Nyquist diagram of the PEG400-20% PW 12 electrolyte conductor material prepared in Example 2 at 25°C, 50°C, and 80°C.
  • Figure 6 is a Nyquist diagram of the PEG400-50% PW 12 electrolyte conductor material prepared in Example 5 at 25°C, 50°C and 80°C.
  • Fig. 7 is a Nyquist diagram of the PEG400-70% PW 12 electrolyte conductor material prepared in Example 7 at 25°C, 50°C and 80°C.
  • Fig. 8 is a Nyquist diagram of the PEG4000-60% PW 12 electrolyte conductor material prepared in Example 8 at 25°C, 50°C and 80°C.
  • Figure 9 is a Nyquist diagram of the PEG4000-70% PW 12 electrolyte conductor material prepared in Example 9 at 25°C, 50°C and 80°C.
  • Fig. 10 is a Nyquist diagram of the SPEG2400-70% PW 12 electrolyte conductor material prepared in Example 10 at 25°C, 50°C, and 80°C.
  • FIG. 11 is a flow chart of the electrolyte conductor materials prepared in Examples 1-7 and the electrolyte conductor material prepared in Comparative Example 1.
  • FIG. 11 is a flow chart of the electrolyte conductor materials prepared in Examples 1-7 and the electrolyte conductor material prepared in Comparative Example 1.
  • the room temperature in the examples is 27°C
  • the polyacid is Keggin-type polyacid H 3 PW 12 O 40
  • the stirring rate is 300 rpm.
  • PEG400 a transparent PEG400 electrolyte conductor material
  • Table 1 shows the electrolyte conductor materials prepared in Example 1, Example 2, Example 5, Example 7, Example 8, Example 9 and Example 10, and Comparative Example 1 at 25°C, 50°C and 80°C Under the conditions (relative humidity is 45%) conductivity test results.
  • R b represents the impedance value, L represents the distance between the two platinum plate electrodes, and A is the area of the two electrode plates.
  • the conductivity values of the electrolyte conductor materials prepared in each embodiment can be obtained. It can be seen that the conductivity of each sample increases with the increase of temperature; as the content of polyacid increases, the conductivity of the prepared electrolyte conductor material The rate has increased by three orders of magnitude. Among them, the conductivity of the PEG400-70% PW 12 sample can reach 1.01 ⁇ 10 -2 S cm -1 at 80°C; the blending of high molecular weight polyethylene glycol and polyacid can also achieve high Electrolyte conductor material with proton conduction efficiency; SPEG2400-70%PW 12 samples prepared by solvent method also have higher conductivity.
  • Figure 1 is the small-angle scattering spectra of the electrolyte conductor materials prepared in Examples 1-7. It can be seen from Figure 1 that there is no obvious crystal diffraction peak in the small-angle spectrum of the prepared PEG400-PW 12 nanocomposite. It shows that in the electrolyte conductor material prepared by the present invention, the polyacid is uniformly dispersed in the polymer substrate to realize the nano-level dispersion of the polyacid and ensure the structural stability of the sample.
  • FIG. 2 is a schematic diagram of the structure and proton conduction of the electrolyte conductor material prepared in the embodiment of the present invention, in which the island-like structure represents the hydrogen bonding between phosphotungstic acid and its polymer components.
  • the intermitted solid line represents the polymer chain of polyethylene glycol, and H + represents the proton. It can be seen from Figure 2 that polyethylene glycol and polyacid form a three-dimensional network through hydrogen bonding, and the effective transfer of protons is realized by the movement of polymer chains.
  • Figure 3 is a Nyquist diagram of the PEG400 electrolyte conductor material prepared in Comparative Example 1 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
  • Figure 4 is a Nyquist diagram of the PEG400-10% PW 12 electrolyte conductor material prepared in Example 1 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
  • Fig. 5 is a Nyquist diagram of the PEG400-20% PW 12 electrolyte conductor material prepared in Example 2 at 25°C, 50°C, and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
  • Figure 6 is a Nyquist diagram of the PEG400-50% PW 12 electrolyte conductor material prepared in Example 5 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
  • Fig. 7 is a Nyquist diagram of the PEG400-70% PW 12 electrolyte conductor material prepared in Example 7 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
  • Fig. 8 is a Nyquist diagram of the PEG4000-60% PW 12 electrolyte conductor material prepared in Example 8 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
  • Figure 9 is a Nyquist diagram of the PEG4000-70% PW 12 electrolyte conductor material prepared in Example 9 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
  • Fig. 10 is a Nyquist diagram of the SPEG2400-70% PW 12 electrolyte conductor material prepared in Example 10 at 25°C, 50°C and 80°C.
  • the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram. It can be seen from Figure 10 that the polyacid-based electrolyte conductor material prepared by the solvent method also has higher conductivity.
  • Figure 11 is a flow curve diagram of the electrolyte conductor material prepared in Examples 1-7 and the electrolyte conductor material prepared in Comparative Example 1. It can be seen from Figure 11 that the viscosity of the PEG400-70%PW 12 sample at room temperature is as high as 273 Pa ⁇ s, to ensure the safety of the sample when used as an electrolyte. In addition, the obvious shear thinning behavior of the samples makes the samples have good processability.
  • the polyacid-based electrolyte conductor material prepared by the present invention has a temperature range of 25°C to 80°C and a relative humidity of 45%. The rise has been greatly improved.
  • samples with a polyacid mass ratio of 70% can achieve high proton conductivity (at 80°C, the conductivity of PEG400-70% PW 12 is 1.01 ⁇ 10 -2 S cm -1 , The conductivity of PEG4000-70% PW 12 is 1.64 ⁇ 10 -2 S cm -1 , and the conductivity of SPEG2400-70% PW 12 is 8.8 ⁇ 10 -3 S cm -1 ).

Abstract

A polyacid-based electrolyte conductor material and a preparation method and application thereof, specifically including two preparation methods: a solid-state melting method and a solvent method. The prepared polyacid-based electrolyte conductor material forms a three-dimensional network by means of hydrogen-bond interaction between the polyacid and the polymer, thereby realizing effective proton transfer. When the mass ratio of the polyacid is 70%, the conductivity of the conductor material may reach 1.01 × 10 -2 S cm -1 (- 80°C). In terms of mechanical properties, the viscosity of a sample is 273 Pa. s, guaranteeing the safety thereof as an electrolyte. The shear thinning behavior enables the polyacid-based electrolyte conductor material to have good processability.

Description

一种多酸基电解质导体材料及其制备方法和应用Polyacid-based electrolyte conductor material and preparation method and application thereof 技术领域Technical field
本发明属于电池材料领域，尤其涉及一种多酸基电解质导体材料及其制备方法和应用。The invention belongs to the field of battery materials, and particularly relates to a polyacid-based electrolyte conductor material and a preparation method and application thereof.
背景技术Background technique
改善聚合物电解质的质子传导性能是提高燃料电池和二次电池效率的关键。目前，质子交换膜燃料电池中已经商业化的质子导体材料是全氟磺酸(Nafions)。Nafions在高湿度(RH 100％)和低温(<373K)条件下具有极高的质子传导率(>10 -2S cm -1)。然而，Nafions的价格昂贵，稳定性和力学性能也较差。因此，研制可以替代Nafions的导体材料是一个急需解决的问题。开发同时具有良好传导性能、力学性能和加工性能的电解质导体材料，对于电池和电容器的发展，具有深远的意义。 Improving the proton conductivity of polymer electrolytes is the key to improving the efficiency of fuel cells and secondary batteries. At present, the proton conductor material that has been commercialized in proton exchange membrane fuel cells is perfluorosulfonic acid (Nafions). Nafions has extremely high proton conductivity (>10 -2 S cm -1 ) under high humidity (RH 100%) and low temperature (<373K) conditions. However, Nafions is expensive, and its stability and mechanical properties are also poor. Therefore, the development of conductive materials that can replace Nafions is an urgent problem to be solved. The development of electrolyte conductor materials with good conductivity, mechanical properties and processing properties at the same time has far-reaching significance for the development of batteries and capacitors.
多金属氧酸盐(POMs)，又称多酸，是一种纳米级的前过渡金属-氧分子簇，较低的有效表面电荷密度，使其具有很强的质子传输能力。事实上，Keggin型多酸(例如，H 3PW 12O 40，H 4SiW 12O 40)在高湿度下具备与Nafions相当的高质子传导率。质子在多酸间是通过结晶水形成的氢键网络进行传递的，因此，传导率受湿度的影响较大，其应用受到限制。 Polyoxometallates (POMs), also known as polyacids, are nano-scale pre-transition metal-oxygen molecular clusters, and their low effective surface charge density gives them strong proton transport capabilities. In fact, Keggin-type polyacids (for example, H 3 PW 12 O 40 , H 4 SiW 12 O 40 ) have high proton conductivity comparable to Nafions under high humidity. Protons are transferred between polyacids through the hydrogen bond network formed by crystal water. Therefore, the conductivity is greatly affected by humidity, and its application is limited.
多酸与不同有机体结合，可形成具有新型功能特性的有机-无机杂化材料。因此，研究人员将多酸与聚合物共混，制备了一系列导体材料，其稳定性有所提高，但传导率与商业化导体材料还有很大的差距，如何制备具有超高传导率的电解质导体材料是研究人员面临的一大挑战。The combination of polyacids with different organisms can form organic-inorganic hybrid materials with new functional properties. Therefore, the researchers blended polyacids and polymers to prepare a series of conductive materials with improved stability, but there is still a big gap between the conductivity and commercial conductive materials. How to prepare ultra-high conductivity Electrolyte conductor materials are a major challenge facing researchers.
发明内容Summary of the invention
针对现有技术中的缺陷和不足，本发明的首要目的为提供一种多酸基电解质导体材料。所制备的多酸基电解质导体料中，多酸与聚合物通过氢键作用，形成传递质子的三维网络，通过聚合物链的运动实现质子的有效传递。此电解质导体材料在中低温环境下具有良好的质子传导效率，同时具有较好的可加工 性、安全性和化学稳定性。In view of the defects and deficiencies in the prior art, the primary purpose of the present invention is to provide a polyacid-based electrolyte conductor material. In the prepared polyacid-based electrolyte conductor material, the polyacid and the polymer form a three-dimensional network for transferring protons through hydrogen bonding, and the effective transfer of protons is realized through the movement of polymer chains. The electrolyte conductor material has good proton conduction efficiency in a medium and low temperature environment, as well as good processability, safety and chemical stability.
本发明的另一目的在于提供上述多酸基电解质导体材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned polyacid-based electrolyte conductor material.
本发明的再一目的在于提供上述多酸基电解质导体材料的应用。Another object of the present invention is to provide the application of the above-mentioned polyacid-based electrolyte conductor material.
本发明的目的通过以下技术方案实现：The purpose of the present invention is achieved through the following technical solutions:
一种多酸基电解质导体材料的制备方法，包括以下步骤：将多酸和聚合物熔体混合得到共混物，将共混物加热搅拌反应，反应结束后冷却至室温，即可制备得到所述多酸基电解质导体材料。A method for preparing a polyacid-based electrolyte conductor material includes the following steps: mixing polyacid and polymer melt to obtain a blend, heating and stirring the blend to react, and cooling to room temperature after the reaction is complete, and then preparing the blend The polyacid-based electrolyte conductor material.
优选的，所述多酸和聚合物熔体的质量比为1:9～7:3。Preferably, the mass ratio of the polyacid to the polymer melt is 1:9-7:3.
优选的，所述加热搅拌的时间为5～48h，更优选为12h；所述加热搅拌的温度为60～80℃；所述加热搅拌的速率为100～700rpm。Preferably, the heating and stirring time is 5 to 48 hours, more preferably 12 hours; the heating and stirring temperature is 60 to 80° C.; the heating and stirring speed is 100 to 700 rpm.
优选的，所述室温为25～35℃。Preferably, the room temperature is 25-35°C.
优选的，所述多酸的类型为Keggin型多酸、Dawson型多酸和Preyssler型多酸中的一种。Preferably, the type of the polyacid is one of Keggin-type polyacid, Dawson-type polyacid and Preyssler-type polyacid.
优选的，所述Keggin型多酸的化学通式为H nXM 12O 40(M＝Mo，W，和V；X＝P，As，n＝3；X＝Si，Ge，n＝4；X＝B，Al，n＝5；X＝Cu，Co，n＝6)，更优选的为H 3PW 12O 40。 Preferably, the general chemical formula of the Keggin-type polyacid is H n XM 12 O 40 (M=Mo, W, and V; X=P, As, n=3; X=Si, Ge, n=4; X=B, Al, n=5; X=Cu, Co, n=6), more preferably H 3 PW 12 O 40 .
优选的，所述Dawson型多酸的化学通式为H nX 2M 18O 62(M＝Mo，W；X＝P，As，S，V；n＝6)。 Preferably, the general chemical formula of the Dawson-type polyacid is H n X 2 M 18 O 62 (M=Mo, W; X=P, As, S, V; n=6).
优选的，所述Preyssler型多酸的化学通式为H nYX 5M 30O 110(X＝P；Y＝Bi，Na，Ca，Eu，U；M＝W；n＝12)。 Preferably, the general chemical formula of the Preyssler type polyacid is H n YX 5 M 30 O 110 (X=P; Y=Bi, Na, Ca, Eu, U; M=W; n=12).
优选的，所述聚合物为带有羟基、羧酸基和氨基中的一种或两种以上的聚合物。Preferably, the polymer is a polymer with one or more of hydroxyl group, carboxylic acid group and amino group.
优选的，所述带有羟基、羧酸基和氨基中的一种或两种以上的聚合物为聚乙二醇、聚丙烯酸、聚乙烯醇和壳聚糖中一种，更优选的为聚乙二醇(PEG)。Preferably, the polymer with one or more of hydroxyl group, carboxylic acid group and amino group is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol and chitosan, more preferably polyethylene Glycol (PEG).
优选的，所述聚乙二醇的分子量为平均分子量为400～300000，更优选为平均分子量400、4000的聚乙二醇和平均分子量为2400的六臂星型聚乙二醇中的一种或两种以上。Preferably, the molecular weight of the polyethylene glycol is one of an average molecular weight of 400 to 300,000, more preferably a polyethylene glycol with an average molecular weight of 400, 4000 and a six-arm star polyethylene glycol with an average molecular weight of 2400. Two or more.
一种多酸基电解质导体材料的制备方法，包括以下步骤：将聚合物加入到溶剂中得到聚合物溶液；将多酸加入到溶剂中得到多酸溶液；将多酸溶液和聚合物溶液混合得到共混物，将共混物加热搅拌反应，反应结束后待溶剂挥发完全，即制备得到所述多酸基电解质导体材料。A preparation method of a polyacid-based electrolyte conductor material, comprising the following steps: adding a polymer to a solvent to obtain a polymer solution; adding a polyacid to the solvent to obtain a polyacid solution; mixing a polyacid solution and a polymer solution to obtain The blend is heated and stirred to react, and after the reaction is completed, the polyacid-based electrolyte conductor material is prepared after the solvent is completely volatilized.
优选的，将聚合物加入到溶剂中得到聚合物溶液，所述聚合物溶液的浓度范围为0.1g/ml～1g/ml。Preferably, the polymer is added to the solvent to obtain a polymer solution, and the concentration of the polymer solution ranges from 0.1 g/ml to 1 g/ml.
优选的，将多酸加入到溶剂中得到多酸溶液，所述多酸溶液的浓度范围为0.1g/ml～1g/ml。Preferably, the polyacid is added to the solvent to obtain a polyacid solution, and the concentration of the polyacid solution ranges from 0.1 g/ml to 1 g/ml.
优选的，所述多酸溶液和聚合物溶液的体积比为1:9～7:3。Preferably, the volume ratio of the polyacid solution to the polymer solution is 1:9-7:3.
优选的，所述加热搅拌的时间为5～48h，更优选为12h；所述加热搅拌的温度为40～60℃；所述加热搅拌的速率为100～700rpm。Preferably, the heating and stirring time is 5 to 48 hours, more preferably 12 hours; the heating and stirring temperature is 40 to 60°C; and the heating and stirring speed is 100 to 700 rpm.
优选的，所述溶剂为水或四氢呋喃，更优选为四氢呋喃。Preferably, the solvent is water or tetrahydrofuran, more preferably tetrahydrofuran.
优选的，所述多酸的类型Keggin型多酸、Dawson型多酸和Preyssler型多酸中的一种或两种以上。Preferably, the type of the polyacid is one or more of Keggin-type polyacid, Dawson-type polyacid and Preyssler-type polyacid.
优选的，所述Keggin型多酸的化学通式为H nXM 12O 40(M＝Mo，W或V；X＝P或As，n＝3；或X＝Si或Ge，n＝4；或X＝B或Al，n＝5；或X＝Cu或Co，n＝6)，更优选的为H 3PW 12O 40。 Preferably, the general chemical formula of the Keggin-type polyacid is H n XM 12 O 40 (M=Mo, W or V; X=P or As, n=3; or X=Si or Ge, n=4; Or X=B or Al, n=5; or X=Cu or Co, n=6), more preferably H 3 PW 12 O 40 .
优选的，所述Dawson型多酸的化学通式为H nX 2M 18O 62(M＝Mo或W；X＝P，As，S或V；n＝6)。 Preferably, the general chemical formula of the Dawson-type polyacid is H n X 2 M 18 O 62 (M=Mo or W; X=P, As, S or V; n=6).
优选的，所述Preyssler型多酸的化学通式为H nYX 5M 30O 110(X＝P；Y＝Bi，Na，Ca，Eu或U；M＝W；n＝12)。 Preferably, the general chemical formula of the Preyssler polyacid is H n YX 5 M 30 O 110 (X=P; Y=Bi, Na, Ca, Eu or U; M=W; n=12).
优选的，所述聚合物为带有羟基、羧酸基和氨基中的一种或两种以上的聚合物。Preferably, the polymer is a polymer with one or more of hydroxyl group, carboxylic acid group and amino group.
优选的，所述带有羟基、羧酸基和氨基中的一种或两种以上的聚合物为聚乙二醇、聚丙烯酸、聚乙烯醇和壳聚糖中一种，更有选的为聚乙二醇。Preferably, the polymer with one or more of hydroxyl group, carboxylic acid group and amino group is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol and chitosan, more preferably poly Ethylene glycol.
优选的，所述聚乙二醇的分子量为平均分子量，分子量大小范围为400～300000，更优选为平均分子量400、4000的聚乙二醇和平均分子量为2400的六臂星型聚乙二醇中的一种或两种以上。Preferably, the molecular weight of the polyethylene glycol is an average molecular weight, and the molecular weight ranges from 400 to 300,000, more preferably polyethylene glycol with an average molecular weight of 400 and 4000 and a six-arm star polyethylene glycol with an average molecular weight of 2400. One or more than two.
上述一种多酸基电解质导体材料的制备方法制备得到的多酸基电解质导体材料。A polyacid-base electrolyte conductor material prepared by the above-mentioned preparation method of a polyacid-base electrolyte conductor material.
上述多酸基电解质导体材料在燃料电池、锂离子电池和超级电容器相关领域中的应用。The application of the above-mentioned polyacid-based electrolyte conductor materials in the related fields of fuel cells, lithium ion batteries and supercapacitors.
与现有技术相比，本发明具有以下优点和有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
(1)本发明所述多酸基电解质导体材料在中低温环境下(80℃)具有很高的质子传导效率(～1.01×10 -2S cm -1)。 (1) The polyacid-based electrolyte conductor material of the present invention has a high proton conduction efficiency (~1.01×10 -2 S cm -1 ) in a medium and low temperature environment (80° C.).
(2)本发明制备方法简单，反应条件温和，易于大量制备，且成本低。(2) The preparation method of the present invention is simple, the reaction conditions are mild, it is easy to prepare in large quantities, and the cost is low.
(3)本发明所制备方法体系中，聚乙二醇能够通过氢键与多酸相结合，在大大提高质子传导效率的同时，样品高达273Pa·s的粘度保证了其作为电解质使用时的安全性。(3) In the preparation method system of the present invention, polyethylene glycol can be combined with polyacids through hydrogen bonds, which greatly improves the proton conduction efficiency, and the viscosity of the sample up to 273 Pa·s ensures its safety when used as an electrolyte Sex.
(4)本发明所制备的多酸基电解质导体材料，存在明显的剪切变稀行为，使得样品具有良好的可加工性。(4) The polyacid-based electrolyte conductor material prepared by the present invention has obvious shear thinning behavior, so that the sample has good processability.
附图说明Description of the drawings
图1为实施例1～7制得的电解质导体材料的小角散射谱图。Figure 1 is the small-angle scattering spectra of the electrolyte conductor materials prepared in Examples 1-7.
图2为本发明实施例制得的电解质导体材料的结构和质子传导示意图。Figure 2 is a schematic diagram of the structure and proton conduction of an electrolyte conductor material prepared in an embodiment of the present invention.
图3为对比例1制得的PEG400电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。Figure 3 is a Nyquist diagram of the PEG400 electrolyte conductor material prepared in Comparative Example 1 at 25°C, 50°C and 80°C.
图4为实施例1制得的PEG400-10％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。 Figure 4 is a Nyquist diagram of the PEG400-10% PW 12 electrolyte conductor material prepared in Example 1 at 25°C, 50°C and 80°C.
图5为实施例2制得的PEG400-20％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。 Fig. 5 is a Nyquist diagram of the PEG400-20% PW 12 electrolyte conductor material prepared in Example 2 at 25°C, 50°C, and 80°C.
图6为实施例5制得的PEG400-50％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。 Figure 6 is a Nyquist diagram of the PEG400-50% PW 12 electrolyte conductor material prepared in Example 5 at 25°C, 50°C and 80°C.
图7为实施例7制得的PEG400-70％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。 Fig. 7 is a Nyquist diagram of the PEG400-70% PW 12 electrolyte conductor material prepared in Example 7 at 25°C, 50°C and 80°C.
图8为实施例8制得的PEG4000-60％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。 Fig. 8 is a Nyquist diagram of the PEG4000-60% PW 12 electrolyte conductor material prepared in Example 8 at 25°C, 50°C and 80°C.
图9为实施例9制得的PEG4000-70％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。 Figure 9 is a Nyquist diagram of the PEG4000-70% PW 12 electrolyte conductor material prepared in Example 9 at 25°C, 50°C and 80°C.
图10是实施例10制得的SPEG2400-70％PW 12电解质导体材料在25℃、50℃和80℃的Nyquist图。 Fig. 10 is a Nyquist diagram of the SPEG2400-70% PW 12 electrolyte conductor material prepared in Example 10 at 25°C, 50°C, and 80°C.
图11是实施例1～7制备的电解质导体材料和对比例1制得的电解质导体材料的流动曲线图。11 is a flow chart of the electrolyte conductor materials prepared in Examples 1-7 and the electrolyte conductor material prepared in Comparative Example 1. FIG.
具体实施方式Detailed ways
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。应 当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这都属于本发明的保护范围。The specific embodiments of the present invention will be described in further detail below in conjunction with the drawings and embodiments. It should be pointed out that for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention. All these belong to the protection scope of the present invention.
实施例所述室温为27℃，所述多酸为Keggin型多酸H 3PW 12O 40，所述搅拌的速率为300rpm。 The room temperature in the examples is 27°C, the polyacid is Keggin-type polyacid H 3 PW 12 O 40 , and the stirring rate is 300 rpm.
实施例1Example 1
将1.0g多酸溶解于9.0g相对分子量为400的聚乙二醇(PEG)在67℃下熔体中，得到共混物A；将共混物A在67℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG400-10％PW 12。 Dissolve 1.0 g of polyacid in 9.0 g of polyethylene glycol (PEG) with a relative molecular weight of 400 in the melt at 67°C to obtain blend A; heat and stir the blend A at 67°C to react for 12 hours. After cooling down to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG400-10%PW 12 .
实施例2Example 2
将2.0g多酸溶解于8.0g相对分子量为400的聚乙二醇(PEG)在67℃下熔体中，得到共混物A；将共混物A在67℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG400-20％PW 12。 Dissolve 2.0 g of polyacid in 8.0 g of polyethylene glycol (PEG) with a relative molecular weight of 400 in the melt at 67°C to obtain blend A; heat and stir the blend A at 67°C for 12 hours, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG400-20%PW 12 .
实施例3Example 3
将3.0g多酸溶解于7.0g相对分子量为400的聚乙二醇(PEG)在67℃下熔体中，得到共混物A；将共混物A在67℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG400-30％PW 12。 Dissolve 3.0 g of polyacid in 7.0 g of polyethylene glycol (PEG) with a relative molecular weight of 400 in the melt at 67°C to obtain blend A; heat and stir the blend A at 67°C for 12 hours, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG400-30%PW 12 .
实施例4Example 4
将4.0g多酸溶解于6.0g相对分子量为400的聚乙二醇(PEG)在67℃下熔体中，得到共混物A；将共混物A在67℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG400-40％PW 12。 Dissolve 4.0 g of polyacid in 6.0 g of polyethylene glycol (PEG) with a relative molecular weight of 400 in the melt at 67°C to obtain blend A; heat and stir the blend A at 67°C for 12h, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG400-40%PW 12 .
实施例5Example 5
将5.0g多酸溶解于5.0g相对分子量为400的聚乙二醇(PEG)在67℃下熔体中，得到共混物A；将共混物A在67℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG400-50％PW 12。 Dissolve 5.0 g of polyacid in 5.0 g of polyethylene glycol (PEG) with a relative molecular weight of 400 in the melt at 67°C to obtain blend A; heat and stir the blend A at 67°C for 12h, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG400-50%PW 12 .
实施例6Example 6
将6.0g多酸溶解于4.0g相对分子量为400的聚乙二醇(PEG)在67℃下 熔体中，得到共混物A；将共混物A在67℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG400-60％PW 12。 Dissolve 6.0 g of polyacid in 4.0 g of polyethylene glycol (PEG) with a relative molecular weight of 400 in the melt at 67°C to obtain blend A; heat and stir the blend A at 67°C for 12h, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG400-60%PW 12 .
实施例7Example 7
将7.0g多酸溶解于3.0g相对分子量为400的聚乙二醇(PEG)在67℃下熔体中，得到共混物A；将共混物A在67℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG400-70％PW 12。 Dissolve 7.0g of polyacid in 3.0g of polyethylene glycol (PEG) with a relative molecular weight of 400 in the melt at 67°C to obtain blend A; heat and stir the blend A at 67°C for 12h, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG400-70% PW 12 .
实施例8Example 8
将6.0g多酸溶解于4.0g相对分子量为4000的聚乙二醇(PEG)在80℃下熔体中，得到共混物A；将共混物A在80℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG4000-60％PW 12。 Dissolve 6.0 g of polyacid in 4.0 g of polyethylene glycol (PEG) with a relative molecular weight of 4000 in the melt at 80°C to obtain blend A; heat and stir the blend A at 80°C for 12h, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG4000-60%PW 12 .
实施例9Example 9
将7.0g多酸溶解于3.0g相对分子量为4000的聚乙二醇(PEG)在80℃下熔体中，得到共混物A；将共混物A在80℃下加热搅拌反应12h，反应结束后冷却至室温，即制备得到透明的所述的多酸基电解质导体材料，记作PEG4000-70％PW 12。 Dissolve 7.0g of polyacid in 3.0g of polyethylene glycol (PEG) with a relative molecular weight of 4000 in the melt at 80°C to obtain blend A; heat and stir the blend A at 80°C for 12h, and react After cooling to room temperature, the transparent polyacid-based electrolyte conductor material is prepared, which is recorded as PEG4000-70%PW 12 .
实施例10Example 10
将7.0g多酸溶解于7ml四氢呋喃中，得到溶液A；将3.0g平均分子量为2400的六臂星型聚乙二醇溶于3ml四氢呋喃中，得到溶液B；将A与B混合，在50℃加热搅拌反应12h；反应结束后挥发掉溶剂，得到所述多酸基电解质导体材料，记作SPEG2400-70％PW 12。 Dissolve 7.0g of polyacid in 7ml of tetrahydrofuran to obtain solution A; Dissolve 3.0g of six-arm star polyethylene glycol with an average molecular weight of 2400 in 3ml of tetrahydrofuran to obtain solution B; Heat and stir the reaction for 12 hours; after the reaction, the solvent is volatilized to obtain the polyacid-based electrolyte conductor material, which is recorded as SPEG2400-70% PW 12 .
对比例1Comparative example 1
将10g相对分子量为400的聚乙二醇在67℃加热搅拌反应12h，反应结束后冷却至室温，得到透明的PEG400电解质导体材料，记作PEG400。10 g of polyethylene glycol with a relative molecular weight of 400 was heated and stirred at 67° C. for 12 hours, and cooled to room temperature after the reaction was completed, to obtain a transparent PEG400 electrolyte conductor material, which was denoted as PEG400.
表1是实施例1、实施例2、实施例5、实施例7、实施例8、实施例9和实施例10，以及对比例1制得的电解质导体材料在25℃、50℃和80℃条件下(相对湿度为45％)的电导率测试结果。测试仪器为辰华CHI660E电化学工作站。测试时，使用两个铂片为电极，测试频率范围为0.01Hz～100000Hz，用EIS测试，通过公式σ＝L/(AR b)，计算质子电导率。R b代表阻抗值，L代表两个铂片 电极之间的距离，A为两个电极片的面积。 Table 1 shows the electrolyte conductor materials prepared in Example 1, Example 2, Example 5, Example 7, Example 8, Example 9 and Example 10, and Comparative Example 1 at 25°C, 50°C and 80°C Under the conditions (relative humidity is 45%) conductivity test results. The test instrument is Chenhua CHI660E electrochemical workstation. During the test, two platinum plates are used as electrodes, the test frequency range is 0.01 Hz to 100000 Hz, and the EIS test is used to calculate the proton conductivity through the formula σ=L/(AR b ). R b represents the impedance value, L represents the distance between the two platinum plate electrodes, and A is the area of the two electrode plates.
表1电导率测试结果一览图Table 1 List of conductivity test results
Figure PCTCN2019112054-appb-000001
Figure PCTCN2019112054-appb-000001
由表1可得出各个实施例所制备电解质导体材料的电导率数值，可以看出：各个样品电导率随温度升高而升高；随着多酸含量的增高，所制备的电解质导体材料电导率提高了三个数量级，其中PEG400-70％PW 12样品电导率在80℃下可以达到1.01×10 -2S cm -1；高分子量聚乙二醇与多酸共混也可得到具有很高质子传导效率的电解质导体材料；由溶剂法所制备的SPEG2400-70％PW 12样品也具有较高的电导率。 From Table 1, the conductivity values of the electrolyte conductor materials prepared in each embodiment can be obtained. It can be seen that the conductivity of each sample increases with the increase of temperature; as the content of polyacid increases, the conductivity of the prepared electrolyte conductor material The rate has increased by three orders of magnitude. Among them, the conductivity of the PEG400-70% PW 12 sample can reach 1.01×10 -2 S cm -1 at 80°C; the blending of high molecular weight polyethylene glycol and polyacid can also achieve high Electrolyte conductor material with proton conduction efficiency; SPEG2400-70%PW 12 samples prepared by solvent method also have higher conductivity.
图1为实施例1～7制得的电解质导体材料的小角散射谱图。从图1可以看出：所制备的PEG400-PW 12纳米复合材料的小角谱图中没有明显的结晶衍射峰。说明本发明制备得到的电解质导体材料中，多酸均匀分散在聚合物基底中，实现了多酸的纳米级分散，确保了样品的结构稳定性。 Figure 1 is the small-angle scattering spectra of the electrolyte conductor materials prepared in Examples 1-7. It can be seen from Figure 1 that there is no obvious crystal diffraction peak in the small-angle spectrum of the prepared PEG400-PW 12 nanocomposite. It shows that in the electrolyte conductor material prepared by the present invention, the polyacid is uniformly dispersed in the polymer substrate to realize the nano-level dispersion of the polyacid and ensure the structural stability of the sample.
图2为本发明实施例制得的电解质导体材料的结构和质子传导示意图，其中，小岛状结构代表磷钨酸及其与聚合物组分之间的氢键作用，不同小岛状结构之间连接的实线代表聚乙二醇的聚合物链，H +代表质子。由图2可以看出：聚乙二醇与多酸通过氢键形成三维网络，借助聚合物链的运动实现质子的有效传递。 Figure 2 is a schematic diagram of the structure and proton conduction of the electrolyte conductor material prepared in the embodiment of the present invention, in which the island-like structure represents the hydrogen bonding between phosphotungstic acid and its polymer components. The intermitted solid line represents the polymer chain of polyethylene glycol, and H + represents the proton. It can be seen from Figure 2 that polyethylene glycol and polyacid form a three-dimensional network through hydrogen bonding, and the effective transfer of protons is realized by the movement of polymer chains.
图3为对比例1制得的PEG400电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。Figure 3 is a Nyquist diagram of the PEG400 electrolyte conductor material prepared in Comparative Example 1 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
图4为实施例1制得的PEG400-10％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。 Figure 4 is a Nyquist diagram of the PEG400-10% PW 12 electrolyte conductor material prepared in Example 1 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
图5为实施例2制得的PEG400-20％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。 Fig. 5 is a Nyquist diagram of the PEG400-20% PW 12 electrolyte conductor material prepared in Example 2 at 25°C, 50°C, and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
图6为实施例5制得的PEG400-50％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。 Figure 6 is a Nyquist diagram of the PEG400-50% PW 12 electrolyte conductor material prepared in Example 5 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
图7为实施例7制得的PEG400-70％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。 Fig. 7 is a Nyquist diagram of the PEG400-70% PW 12 electrolyte conductor material prepared in Example 7 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
从图4～7可以看出，多酸的加入使得聚乙二醇的电导率大大增大。同时也说明，随着温度升高到80℃，样品的电导率有明显的变大趋势。It can be seen from Figures 4-7 that the addition of polyacids greatly increases the conductivity of polyethylene glycol. It also shows that as the temperature rises to 80°C, the conductivity of the sample has a significant tendency to increase.
图8为实施例8制得的PEG4000-60％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。 Fig. 8 is a Nyquist diagram of the PEG4000-60% PW 12 electrolyte conductor material prepared in Example 8 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
图9为实施例9制得的PEG4000-70％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。 Figure 9 is a Nyquist diagram of the PEG4000-70% PW 12 electrolyte conductor material prepared in Example 9 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram.
从图8和图9可以看出，随着温度升高到80℃，样品的电导率有明显的变大趋势。It can be seen from Figure 8 and Figure 9 that as the temperature rises to 80°C, the conductivity of the sample has an obvious tendency to increase.
图10是实施例10制得的SPEG2400-70％PW 12电解质导体材料在25℃、50℃和80℃条件下的Nyquist图。其中，电解质导体材料的电导率可以通过对应的Nyquist图的实部截距得到。从图10可以看出，溶剂法制得的多酸基电解质导体材料也具有较高的电导率。 Fig. 10 is a Nyquist diagram of the SPEG2400-70% PW 12 electrolyte conductor material prepared in Example 10 at 25°C, 50°C and 80°C. Among them, the conductivity of the electrolyte conductor material can be obtained by the real part intercept of the corresponding Nyquist diagram. It can be seen from Figure 10 that the polyacid-based electrolyte conductor material prepared by the solvent method also has higher conductivity.
图11是实施例1～7制备的电解质导体材料和对比例1制得的电解质导体材料的流动曲线图，从图11可以看出：在室温下PEG400-70％PW 12样品的粘度高达273Pa·s，保证了样品作为电解质使用时的安全性。此外，样品明显的剪切变稀行为，使得样品具有良好的可加工性。 Figure 11 is a flow curve diagram of the electrolyte conductor material prepared in Examples 1-7 and the electrolyte conductor material prepared in Comparative Example 1. It can be seen from Figure 11 that the viscosity of the PEG400-70%PW 12 sample at room temperature is as high as 273 Pa· s, to ensure the safety of the sample when used as an electrolyte. In addition, the obvious shear thinning behavior of the samples makes the samples have good processability.
由上述内容对本发明实施例的详细描述，可以了解本发明所制备的多酸基 电解质导体材料，在温度区间25℃～80℃和相对湿度为45％的条件下，其导电率随着温度的上升有很大的提高。材料的制备过程中，多酸质量比为70％的样品，都可达到很高的质子导电率(80℃温度下，PEG400-70％PW 12电导率为1.01×10 -2S cm -1，PEG4000-70％PW 12电导率1.64×10 -2S cm -1，SPEG2400-70％PW 12电导率为8.8×10 -3S cm -1)。 From the above detailed description of the embodiments of the present invention, it can be understood that the polyacid-based electrolyte conductor material prepared by the present invention has a temperature range of 25°C to 80°C and a relative humidity of 45%. The rise has been greatly improved. In the preparation process of the material, samples with a polyacid mass ratio of 70% can achieve high proton conductivity (at 80°C, the conductivity of PEG400-70% PW 12 is 1.01×10 -2 S cm -1 , The conductivity of PEG4000-70% PW 12 is 1.64×10 -2 S cm -1 , and the conductivity of SPEG2400-70% PW 12 is 8.8×10 -3 S cm -1 ).
以上所述仅是本发明的优选实施方式，并不用于限制本发明。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变形，这些改进和变型也应视为本发明的保护范围，因此，凡是未脱离本发明专利方案的内容，依据本发明专利技术实质对上述实施例所做的任何简单修改、等同变化及修饰，均属于本发明专利保护的范围。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the technical principles of the present invention, several improvements and modifications can be made. These improvements and modifications should also be regarded as the protection scope of the present invention. Therefore, Any simple amendments, equivalent changes and modifications made to the above embodiments according to the technical essence of the patent of the present invention without departing from the content of the patent scheme of the present invention shall fall within the protection scope of the patent of the present invention.

Claims (10)

  1. 一种多酸基电解质导体材料的制备方法，其特征在于，包括以下步骤：将多酸和聚合物熔体按1:9～7:3的质量比混合得到共混物，将共混物加热搅拌反应，反应结束后冷却至室温，即制备得到所述多酸基电解质导体材料。A preparation method of a polyacid-based electrolyte conductor material is characterized in that it comprises the following steps: mixing polyacid and polymer melt at a mass ratio of 1:9-7:3 to obtain a blend, and heating the blend The reaction is stirred, and after the reaction is completed, it is cooled to room temperature to prepare the polyacid-based electrolyte conductor material.
  2. 根据权利要求1所述一种多酸基电解质导体材料的制备方法，其特征在于，所述加热搅拌的时间为5～48h；所述加热搅拌的温度为60～80℃；所述加热搅拌的速率为100～700rpm。The method for preparing a polyacid-based electrolyte conductor material according to claim 1, wherein the heating and stirring time is 5 to 48 hours; the heating and stirring temperature is 60 to 80°C; The speed is 100 to 700 rpm.
  3. 一种多酸基电解质导体材料的制备方法，其特征在于，包括以下步骤：将聚合物加入到溶剂中得到浓度为0.1g/mL～1g/mL的聚合物溶液；将多酸加入到溶剂中得到浓度为0.1g/mL～1g/mL的多酸溶液；将多酸溶液和聚合物溶液按1:9～7:3的体积比混合得到共混物，将共混物加热搅拌反应，反应结束后待溶剂挥发完全，即制备得到所述多酸基电解质导体材料。A preparation method of a polyacid-based electrolyte conductor material, which is characterized in that it comprises the following steps: adding a polymer to a solvent to obtain a polymer solution with a concentration of 0.1g/mL-1g/mL; adding a polyacid to the solvent A polyacid solution with a concentration of 0.1g/mL～1g/mL is obtained; the polyacid solution and the polymer solution are mixed in a volume ratio of 1:9～7:3 to obtain a blend, and the blend is heated and stirred to react and react After the completion of the solvent volatilization, the polyacid-based electrolyte conductor material is prepared.
  4. 根据权利要求3所述一种多酸基电解质导体材料的制备方法，其特征在于，所述加热搅拌的时间为5～48h；所述加热搅拌的温度为40～60℃；所述加热搅拌的速率为100～700rpm；所述聚合物溶液和多酸溶液的溶剂为水或四氢呋喃。The method for preparing a polyacid-based electrolyte conductor material according to claim 3, wherein the heating and stirring time is 5 to 48 hours; the heating and stirring temperature is 40 to 60°C; The speed is 100-700 rpm; the solvent of the polymer solution and the polyacid solution is water or tetrahydrofuran.
  5. 根据权利要求1或3所述一种多酸基电解质导体材料的制备方法，其特征在于，所述多酸为Keggin型多酸、Dawson型多酸和Preyssler型多酸中的一种或两种以上；The method for preparing a polyacid-based electrolyte conductor material according to claim 1 or 3, wherein the polyacid is one or two of Keggin-type polyacid, Dawson-type polyacid and Preyssler-type polyacid the above;
    所述聚合物为带有羟基、羧酸基和氨基中的一种或两种以上的聚合物。The polymer is a polymer with one or more of hydroxyl group, carboxylic acid group and amino group.
  6. 根据权利要求5所述一种多酸基电解质导体材料的制备方法，其特征在于，The method for preparing a polyacid-based electrolyte conductor material according to claim 5, wherein:
    所述Keggin型多酸的化学通式为H nXM 12O 40，M＝Mo，W或V；X＝P或As，n＝3；或X＝Si或Ge，n＝4；或X＝B或Al，n＝5；或X＝Cu或Co，n＝6； The general chemical formula of the Keggin-type polyacid is H n XM 12 O 40 , M=Mo, W or V; X=P or As, n=3; or X=Si or Ge, n=4; or X= B or Al, n=5; or X=Cu or Co, n=6;
    所述Dawson型多酸的化学通式为H nX 2M 18O 62，M＝Mo或W；X＝P，As，S或V；n＝6； The general chemical formula of the Dawson-type polyacid is H n X 2 M 18 O 62 , M=Mo or W; X=P, As, S or V; n=6;
    所述Preyssler型多酸的化学通式为H nYX 5M 30O 110，X＝P；Y＝Bi，Na，Ca，Eu或U；M＝W；n＝12。 The general chemical formula of the Preyssler polyacid is H n YX 5 M 30 O 110 , X=P; Y=Bi, Na, Ca, Eu or U; M=W; n=12.
  7. 根据权利5所述一种多酸基电解质导体材料的制备方法，其特征在于，所述带有羟基、羧酸基和氨基中的一种或两种以上的聚合物为聚乙二醇、聚丙烯酸、聚乙烯醇和壳聚糖中的一种；所述Keggin型多酸为H 3PW 12O 40。 The method for preparing a polyacid-based electrolyte conductor material according to claim 5, wherein the polymer with one or more of hydroxyl group, carboxylic acid group and amino group is polyethylene glycol, poly One of acrylic acid, polyvinyl alcohol and chitosan; the Keggin type polyacid is H 3 PW 12 O 40 .
  8. 根据权利7所述一种多酸基电解质导体材料的制备方法，其特征在于，所述聚乙二醇的平均分子量为400～300000。The method for preparing a polyacid-based electrolyte conductor material according to claim 7, wherein the average molecular weight of the polyethylene glycol is 400 to 300,000.
  9. 权利要求1～8任一项所述一种多酸基电解质导体材料的制备方法制备得到的多酸基电解质导体材料。A polyacid-based electrolyte conductor material prepared by a method for preparing a polyacid-based electrolyte conductor material according to any one of claims 1 to 8.
  10. 权利要求9所述多酸基电解质导体材料在燃料电池、锂离子电池和超级电容器领域中的应用。The application of the polyacid-based electrolyte conductor material of claim 9 in the fields of fuel cells, lithium ion batteries and supercapacitors.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113717395A (en) * 2021-09-01 2021-11-30 哈尔滨师范大学 { P6Mo18O73Porous electrode material based on metal organic framework and preparation method and application thereof
CN114686914A (en) * 2022-03-31 2022-07-01 辽宁大学 Transparent polyoxometallate membrane electrode and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113013458B (en) * 2021-02-25 2022-07-26 华南理工大学 Microphase separated high-temperature anhydrous ion conductive nano composite material and preparation and application thereof
CN115735949B (en) * 2022-12-26 2023-07-21 河南大学 Polyoxometallate crosslinked polyethylene glycol modified chitosan sponge composite material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497728A (en) * 2008-01-31 2009-08-05 中国科学院福建物质结构研究所 Polyacid-polymer compound film, and preparation and use thereof
CN103145978A (en) * 2013-03-25 2013-06-12 南开大学 Pegylation polyoxometallate and preparation method thereof
CN109659601A (en) * 2018-12-12 2019-04-19 南京师范大学 A kind of polyacid/application of the high molecular polymer hybridized nanometer wire material as solid electrolyte
CN109850902A (en) * 2018-12-13 2019-06-07 华南理工大学 A kind of preparation method of silico-tungstic acid nanometer rods

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2428131C (en) * 2001-09-11 2010-11-16 Sekisui Chemical Co., Ltd. Membrane-electrode assembly, method of manufacturing the same, and polymer electrolyte fuel cell using the same
CN1207804C (en) * 2003-05-19 2005-06-22 清华大学 Method for preparing heat-resisting proton exchange film
CN101140991B (en) * 2006-09-08 2010-04-14 中国科学院大连化学物理研究所 Fuel batter with proton exchange film electric pole catalyze layer and producing thereof
CN102376961B (en) * 2010-08-18 2015-06-10 北京航空航天大学 High temperature proton exchange membrane for fuel cell, and preparation method thereof
CN104659395B (en) * 2013-11-20 2017-02-08 北京迈托科美科技有限公司 Organic-inorganic composite proton exchange membrane for proton exchange membrane fuel cell and preparation method thereof
EP3197906B1 (en) * 2014-09-26 2023-10-25 Mebius d.o.o. Processes for preparing polyoxometalate salts for use in proton exchange membranes and fuel cells
KR101977853B1 (en) * 2014-12-04 2019-05-13 주식회사 엘지화학 Polymer electrolyte membrane
JP6163509B2 (en) * 2015-03-13 2017-07-12 ニッポン高度紙工業株式会社 Fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497728A (en) * 2008-01-31 2009-08-05 中国科学院福建物质结构研究所 Polyacid-polymer compound film, and preparation and use thereof
CN103145978A (en) * 2013-03-25 2013-06-12 南开大学 Pegylation polyoxometallate and preparation method thereof
CN109659601A (en) * 2018-12-12 2019-04-19 南京师范大学 A kind of polyacid/application of the high molecular polymer hybridized nanometer wire material as solid electrolyte
CN109850902A (en) * 2018-12-13 2019-06-07 华南理工大学 A kind of preparation method of silico-tungstic acid nanometer rods

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LU, SHANFU ET AL.: "A Self-anchored Phosphotungstic Acid Hybrid Proton Exchange Membrane Achieved via One-step Synthesis", JOURNAL OF ADVANCED ENERGY MATERIALS, vol. 4, no. 17, 29 July 2014 (2014-07-29), XP055772966, ISSN: 1614-6832, DOI: 20200317103741X *
XU, XIN ET AL.: "A Phosphotungstic Acid Self-anchored Hybrid Proton Exchange Membrane for Direct Methanol Fuel Cells", JOURNAL OF RSC ADVANCES, vol. 6, no. 49, 26 April 2016 (2016-04-26), XP055772969, ISSN: 2046-2069, DOI: 00317X *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113717395A (en) * 2021-09-01 2021-11-30 哈尔滨师范大学 { P6Mo18O73Porous electrode material based on metal organic framework and preparation method and application thereof
CN114686914A (en) * 2022-03-31 2022-07-01 辽宁大学 Transparent polyoxometallate membrane electrode and preparation method thereof

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