WO2020258605A1 - 一种多酸基电解质导体材料及其制备方法和应用 - Google Patents

一种多酸基电解质导体材料及其制备方法和应用 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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French (fr)
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郑昭
蔡林坤
殷盼超
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South China University of Technology SCUT
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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, LIGHT-SENSITIVE OR TEMPERATURE-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. in situ polymerisation or in situ 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 ).

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Abstract

一种多酸基电解质导体材料及其制备方法和应用，具体包括了两种制备方法：固态熔融法和溶剂法。所制备的多酸基电解质导体材料，通过多酸与聚合物的氢键作用形成三维网络，实现了质子的有效传递。在多酸质量比为70％时，导体材料电导率可达1.01×10 -2S cm -1(～80℃)。在力学性能方面，样品粘度为273Pa·s，保证了其作为电解质的安全性。剪切变稀行为，又使得该多酸基电解质导体材料具有良好的可加工性。

Description

一种多酸基电解质导体材料及其制备方法和应用 技术领域
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。
背景技术
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。
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。
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。
发明内容
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。
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。
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。
本发明的目的通过以下技术方案实现：
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。
优选的，所述多酸和聚合物熔体的质量比为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。
优选的，所述室温为25～35℃。
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。
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。
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)。
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)。
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。
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)。
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。
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。
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。
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。
优选的，所述多酸溶液和聚合物溶液的体积比为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。
优选的，所述溶剂为水或四氢呋喃，更优选为四氢呋喃。
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。
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。
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)。
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)。
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。
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。
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。
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。
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。
与现有技术相比，本发明具有以下优点和有益效果：
(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)。
(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。
(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。
(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。
附图说明
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
具体实施方式
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。
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。
实施例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。
实施例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。
实施例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。
实施例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。
实施例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。
实施例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。
实施例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。
实施例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。
实施例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。
实施例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。
对比例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。
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。
表1电导率测试结果一览图
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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。
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)。
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。

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。
  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。
  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。
  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。
  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；
    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。
  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，
    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；
    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；
    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。
  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。
  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。
  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。
  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。
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