CN112151842A - 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 PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 91
- 239000004020 conductor Substances 0.000 title claims abstract description 89
- 239000003792 electrolyte Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 58
- 239000002202 Polyethylene glycol Substances 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 101000651178 Homo sapiens Striated muscle preferentially expressed protein kinase Proteins 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- 102100027659 Striated muscle preferentially expressed protein kinase Human genes 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229910020628 SiW12O40 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
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- 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
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Abstract
The invention discloses a polyacid-based electrolyte conductor material, a preparation method and application thereof, and specifically discloses two preparation methods: solid-state melt processes and solvent processes. In the polyacid-based electrolyte conductor material prepared by the invention, polyacid and polymer form a three-dimensional network through hydrogen bond action, and effective transfer of protons is realized. When the mass ratio of the polyacid is 70%, the conductivity of the conductor material can reach 1.01 multiplied by 10‑2S cm‑1(. about.80 ℃ C.). In terms of the mechanical properties of the composite material,the viscosity of the sample is 273 pas, so that the safety of the sample as an electrolyte is ensured. The shear thinning behavior, in turn, enables good processability of the polyacid-based electrolyte conductor material.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a polyacid-based electrolyte conductor material as well as a preparation method and application thereof.
Background
Improving the proton conductivity of polymer electrolytes is key to improving the efficiency of fuel cells and secondary batteries. Currently, the proton conductor material that has been commercialized in proton exchange membrane fuel cells is perfluorosulfonic acid (Nafions). Nafions at high humidity (RH 100%) and low temperature ((RH 100))<373K) Having extremely high proton conductivity under the conditions of (>10-2S cm-1). However, Nafions are expensive and have poor stability and mechanical properties. Therefore, the development of a conductive material that can replace Nafions is an urgent problem to be solved. The development of the electrolyte conductor material with good conductivity, mechanical property and processability simultaneously has profound significance for the development of batteries and capacitors.
Polyoxometalates (POMs), also known as polyacids, are nanoscale early transition metal-oxygen molecular clusters with low effective surface charge density that provide them with strong proton transport capability. Indeed, Keggin-type polyacids (e.g., H)3PW12O40，H4SiW12O40) Has high proton conductivity comparable to that of Nafions under high humidity. Protons are transferred between polyacids through a hydrogen bond network formed by crystal water, and therefore, the conductivity is greatly affected by humidity, and the application thereof is limited.
The polyacid can be combined with different organisms to form organic-inorganic hybrid materials with novel functional characteristics. Therefore, researchers blend polyacids with polymers to produce a range of conductor materials with improved stability, but the conductivity is far from the commercial conductor materials, and how to produce electrolyte conductor materials with ultra-high conductivity is a challenge.
Disclosure of Invention
In view of the shortcomings and drawbacks of the prior art, a primary object of the present invention is to provide a polyacid-based electrolyte conductor material. In the prepared polyacid-based electrolyte conductor material, polyacid and polymer form a three-dimensional network for transferring protons through the action of hydrogen bonds, and the effective transfer of protons is realized through the movement of a polymer chain. The electrolyte conductor material has good proton conduction efficiency in medium and low temperature environment, and has good processability, safety and chemical stability.
Another object of the present invention is to provide a method for preparing the polyacid-based electrolyte conductor material.
Still another object of the present invention is to provide the use of the above polyacid-based electrolyte conductor material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a polyacid-based electrolyte conductor material comprises the following steps: mixing the polyacid and the polymer melt to obtain a blend, heating and stirring the blend for reaction, and cooling to room temperature after the reaction is finished to obtain the polyacid-based electrolyte conductor material.
Preferably, the mass ratio of the polyacid to the polymer melt is 1: 9-7: 3.
Preferably, the heating and stirring time is 5-48 h, and more preferably 12 h; the heating and stirring temperature is 60-80 ℃; the heating and stirring speed is 100-700 rpm.
Preferably, the room temperature is 25-35 ℃.
Preferably, the polyacid type is one of Keggin type polyacid, Dawson type polyacid and Preyssler type polyacid.
Preferably, the chemical general formula of the Keggin type polyacid is HnXM12O40(M ═ Mo, W, and V ═ P, As, n ═ 3; X ═ Si, Ge, n ═ 4; X ═ B, Al, n ═ 5; X ═ Cu, Co, n ═ 6), more preferably H3PW12O40。
Preferably, the chemical formula of the Dawson type polyacid is HnX2M18O62(M＝Mo，W；X＝P， As，S，V；n＝6)。
Preferably, the chemical formula of the Preyssler type polyacid is HnYX5M30O110(X＝P；Y＝Bi， Na，Ca，Eu，U；M＝W；n＝12)。
Preferably, the polymer is a polymer having one or more of a hydroxyl group, a carboxylic acid group, and an amino group.
Preferably, the polymer having one or two or more of a hydroxyl group, a carboxylic acid group and an amino group is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol and chitosan, and more preferably polyethylene glycol (PEG).
Preferably, the polyethylene glycol has a molecular weight of 400-300000, more preferably 400-4000, and 2400.
A preparation method of a polyacid-based electrolyte conductor material comprises the following steps: adding a polymer into a solvent to obtain a polymer solution; adding a polyacid into a solvent to obtain a polyacid solution; and mixing the polyacid solution and the polymer solution to obtain a blend, heating and stirring the blend for reaction, and after the reaction is finished, completely volatilizing the solvent to obtain the polyacid-based electrolyte conductor material.
Preferably, the polymer is added to the solvent to obtain a polymer solution having a concentration ranging from 0.1g/ml to 1 g/ml.
Preferably, the polyacid is added to the solvent to obtain a polyacid solution, the concentration of the polyacid solution being in the range of 0.1g/ml to 1 g/ml.
Preferably, the volume ratio of the polyacid solution to the polymer solution is 1: 9-7: 3.
Preferably, the heating and stirring time is 5-48 h, and more preferably 12 h; the heating and stirring temperature is 40-60 ℃; the heating and stirring speed is 100-700 rpm.
Preferably, the solvent is water or tetrahydrofuran, more preferably tetrahydrofuran.
Preferably, the polyacid is one or more of Keggin-type polyacid, Dawson-type polyacid and Preyssler-type polyacid.
Preferably, the chemical general formula of the Keggin type polyacid is HnXM12O40(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 H3PW12O40。
Preferably, the chemical formula of the Dawson type polyacid is HnX2M18O62(M ═ Mo or W; X ═ P, As, S or V; n ═ 6).
Preferably, the chemical formula of the Preyssler type polyacid is HnYX5M30O110(X ═ P; Y ═ Bi, Na, Ca, Eu or U; M ═ W; n ═ 12).
Preferably, the polymer is a polymer having one or more of a hydroxyl group, a carboxylic acid group, and an amino group.
Preferably, the polymer having one or more of a hydroxyl group, a carboxylic acid group and an amino group is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol and chitosan, and more preferably polyethylene glycol.
Preferably, the polyethylene glycol has a molecular weight of 400-300000, more preferably 400-4000, and more preferably 2400.
The polyacid-based electrolyte conductor material prepared by the preparation method of the polyacid-based electrolyte conductor material is provided.
The polyacid-based electrolyte conductor material is applied to the related fields of fuel cells, lithium ion batteries and supercapacitors.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the polyacid-based electrolyte conductor material has high proton conduction efficiency (1.01 multiplied by 10) under the medium-low temperature environment (80℃)-2S cm-1)。
(2) The preparation method is simple, mild in reaction condition, easy for mass preparation and low in cost.
(3) In the preparation method system, the polyethylene glycol can be combined with polyacid through hydrogen bonds, so that the proton conduction efficiency is greatly improved, and the safety of the sample when the sample is used as an electrolyte is ensured by the viscosity of 273Pa & s.
(4) The polyacid-based electrolyte conductor material prepared by the invention has obvious shear thinning behavior, so that a sample has good processability.
Drawings
FIG. 1 is a small-angle scattering spectrum of the electrolyte conductor materials prepared in examples 1 to 7.
Fig. 2 is a schematic view showing the structure and proton conduction of the electrolyte conductor material prepared in the example of the present invention.
FIG. 3 is a Nyquist plot of the PEG400 electrolyte conductor material prepared in comparative example 1 at 25 deg.C, 50 deg.C, and 80 deg.C.
FIG. 4 shows 400-10% PW for PEG prepared in example 112Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C.
FIG. 5 shows PEG 400-20% PW obtained in example 212Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C.
FIG. 6 shows PEG 400-50% PW obtained in example 512Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C.
FIG. 7 shows PEG 400-70% PW obtained in example 712Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C.
FIG. 8 shows PEG 4000-60% PW obtained in example 812Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C.
FIG. 9 shows PEG 4000-70% PW obtained in example 912Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C.
FIG. 10 is a graph showing SPEG 2400-70% PW obtained in example 1012Nyquist plots of the electrolyte conductor material at 25 deg.C, 50 deg.C, and 80 deg.C.
FIG. 11 is a flow chart of the electrolyte conductor materials prepared in examples 1 to 7 and the electrolyte conductor material prepared in comparative example 1.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
In the examples, the room temperature was 27 ℃ and the polyacid was Keggin type polyacid H3PW12O40The stirring rate was 300 rpm.
Example 1
Dissolving 1.0g of polyacid in 9.0g of polyethylene glycol (PEG) with the relative molecular weight of 400 at the temperature of 67 ℃ to obtain a blend A; heating the blend A at 67 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 400-10% PW12。
Example 2
Dissolving 2.0g of polyacid in 8.0g of polyethylene glycol (PEG) with the relative molecular weight of 400 at the temperature of 67 ℃ to obtain a blend A; heating the blend A at 67 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 400-20% PW12。
Example 3
Dissolving 3.0g of polyacid in 7.0g of polyethylene glycol (PEG) with the relative molecular weight of 400 in a melt at 67 ℃ to obtain a blend A; heating the blend A at 67 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 400-30% PW12。
Example 4
Dissolving 4.0g of polyacid in 6.0g of polyethylene glycol (PEG) with the relative molecular weight of 400 in a melt at 67 ℃ to obtain a blend A; heating the blend A at 67 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 400-40% PW12。
Example 5
Dissolving 5.0g of polyacid in 5.0g of polyethylene glycol (PEG) with the relative molecular weight of 400 in a melt at 67 ℃ to obtain a blend A; heating and stirring the blend A at 67 ℃ for 12 hours of reaction, and cooling to room temperature after the reaction is finished, namelyPreparing the transparent polyacid-based electrolyte conductor material, which is marked as PEG 400-50% PW12。
Example 6
6.0g of polyacid was dissolved in 4.0g of polyethylene glycol (PEG) having a relative molecular weight of 400 in a melt at 67 ℃ to give blend A; heating the blend A at 67 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 400-60% PW12。
Example 7
Dissolving 7.0g of polyacid in 3.0g of polyethylene glycol (PEG) with the relative molecular weight of 400 in a melt at 67 ℃ to obtain a blend A; heating the blend A at 67 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 400-70% PW12。
Example 8
Dissolving 6.0g of polyacid in 4.0g of polyethylene glycol (PEG) with the relative molecular weight of 4000 at a melt temperature of 80 ℃ to obtain a blend A; heating the blend A at 80 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 4000-60% PW12。
Example 9
Dissolving 7.0g of polyacid in 3.0g of polyethylene glycol (PEG) with the relative molecular weight of 4000 at a melt temperature of 80 ℃ to obtain a blend A; heating the blend A at 80 ℃, stirring and reacting for 12h, cooling to room temperature after the reaction is finished, and preparing the transparent polyacid-based electrolyte conductor material which is marked as PEG 4000-70% PW12。
Example 10
Dissolving 7.0g of polyacid in 7ml of tetrahydrofuran to obtain a solution A; dissolving 3.0g of six-arm star-shaped polyethylene glycol with the average molecular weight of 2400 in 3ml of tetrahydrofuran to obtain a solution B; mixing A and B, heating and stirring at 50 ℃ to react for 12 h; after the reaction is finished, the solvent is volatilized to obtain the polyacid-based electrolyte conductor material which is recorded as SPEG 2400-70% PW12。
Comparative example 1
10g of polyethylene glycol with the relative molecular weight of 400 is heated and stirred at 67 ℃ for reaction for 12h, and after the reaction is finished, the reaction product is cooled to room temperature to obtain a transparent PEG400 electrolyte conductor material, which is marked as PEG 400.
Table 1 shows the results of the conductivity tests of 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 (relative humidity of 45%). The test instrument was Chenghua CHI660E electrochemical workstation. When in test, two platinum sheets are used as electrodes, the test frequency range is 0.01 Hz-100000 Hz, the EIS test is carried out, and the sigma is L/(AR)b) And calculating the proton conductivity. RbRepresenting the impedance value, L representing the distance between the two platinum sheet electrodes, and a being the area of the two electrode sheets.
Table 1 summary of conductivity test results
From table 1, the conductivity values of the electrolyte conductor materials prepared in the respective examples can be found that: the conductivity of each sample increases with increasing temperature; the conductivity of the prepared electrolyte conductor material is improved by three orders of magnitude along with the increase of the polyacid content, wherein PEG 400-70% PW12The conductivity of the sample can reach 1.01 multiplied by 10 at 80 DEG C-2S cm-1(ii) a The electrolyte conductor material with high proton conduction efficiency can also be obtained by blending the high molecular weight polyethylene glycol and the polyacid; SPEG 2400-70% PW prepared by solvent method12The sample also has a higher conductivity.
FIG. 1 is a small-angle scattering spectrum of the electrolyte conductor materials prepared in examples 1 to 7. As can be seen from fig. 1: prepared PEG400-PW12The small angle spectrum of the nano composite material has no obvious crystal diffraction peak. The electrolyte conductor material prepared by the invention has the advantages that the polyacid is uniformly dispersed in the polymer substrate, the nanoscale dispersion of the polyacid is realized, and the structural stability of a sample is ensured。
FIG. 2 is a schematic diagram showing the structure and proton conduction of the electrolyte conductor material prepared in the example of the present invention, in which the island-like structures represent phosphotungstic acid and hydrogen bonding between phosphotungstic acid and polymer components, the solid lines connecting different island-like structures represent polymer chains of polyethylene glycol, and H represents+Represents a proton. As can be seen from fig. 2: the polyethylene glycol and the polyacid form a three-dimensional network through hydrogen bonds, and effective transfer of protons is realized by virtue of the movement of a polymer chain.
FIG. 3 is a Nyquist plot of the PEG400 electrolyte conductor material prepared in comparative example 1 at 25 deg.C, 50 deg.C, and 80 deg.C. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram.
FIG. 4 shows 400-10% PW for PEG prepared in example 112Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram.
FIG. 5 shows PEG 400-20% PW obtained in example 212Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram.
FIG. 6 shows PEG 400-50% PW obtained in example 512Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram.
FIG. 7 shows PEG 400-70% PW obtained in example 712Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram.
As can be seen from FIGS. 4 to 7, the addition of the polyacid greatly increases the conductivity of the polyethylene glycol. It also shows that the conductivity of the sample has a significantly higher tendency as the temperature is increased to 80 ℃.
FIG. 8 shows PEG 4000-60% PW obtained in example 812Electrolyte conductor materialNyquist plot at 25 ℃, 50 ℃ and 80 ℃. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram.
FIG. 9 shows PEG 4000-70% PW obtained in example 912Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram.
As can be seen from fig. 8 and 9, the conductivity of the sample has a significantly greater tendency as the temperature increases to 80 ℃.
FIG. 10 is a graph showing SPEG 2400-70% PW obtained in example 1012Nyquist plot of the electrolyte conductor material at 25 deg.C, 50 deg.C and 80 deg.C. Wherein the conductivity of the electrolyte conductor material can be obtained by the real intercept of the corresponding Nyquist diagram. As can be seen from fig. 10, the polyacid-based electrolyte conductor material prepared by the solvent method also has higher conductivity.
FIG. 11 is a flow chart of the electrolyte conductor materials prepared in examples 1 to 7 and the electrolyte conductor material prepared in comparative example 1, and it can be seen from FIG. 11 that: PEG 400-70% PW at room temperature12The viscosity of the sample is as high as 273 Pa.s, so that the safety of the sample when the sample is used as an electrolyte is ensured. Furthermore, the clear shear-thinning behavior of the samples allows good processability of the samples.
From the above detailed description of the embodiments of the present invention, it can be understood that the conductivity of the polyacid-based electrolyte conductor material prepared by the present invention is greatly improved along with the temperature rise under the conditions of the temperature range of 25 ℃ to 80 ℃ and the relative humidity of 45%. In the preparation process of the material, samples with the polyacid mass ratio of 70 percent can achieve very high proton conductivity (PEG 400-70 percent PW at the temperature of 80℃)12The conductivity was 1.01X 10-2S cm-1，PEG4000-70％PW12Conductivity 1.64X 10-2S cm-1， SPEG2400-70％PW12The conductivity was 8.8X 10-3S cm-1)。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that, for those skilled in the art, without departing from the technical principle of the present invention, several modifications and variations can be made, and these modifications and variations should be considered as the protection scope of the present invention, and therefore, any simple modification, equivalent change and modification made to the above-mentioned embodiments according to the technical essence of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a polyacid-based electrolyte conductor material is characterized by comprising the following steps: mixing polyacid and the polymer melt according to the mass ratio of 1: 9-7: 3 to obtain a blend, heating and stirring the blend for reaction, and cooling to room temperature after the reaction is finished to obtain the polyacid-based electrolyte conductor material.
2. The method for preparing the polyacid-based electrolyte conductor material according to claim 1, wherein the heating and stirring time is 5-48 h; the heating and stirring temperature is 60-80 ℃; the heating and stirring speed is 100-700 rpm.
3. A preparation method of a polyacid-based electrolyte conductor material is characterized by comprising the following steps: adding the polymer into a solvent to obtain a polymer solution with the concentration of 0.1 g/mL-1 g/mL; adding polyacid into the solvent to obtain a polyacid solution with the concentration of 0.1 g/mL-1 g/mL; mixing the polyacid solution and the polymer solution according to the volume ratio of 1: 9-7: 3 to obtain a blend, heating and stirring the blend for reaction, and after the reaction is finished, completely volatilizing the solvent to obtain the polyacid-based electrolyte conductor material.
4. The method for preparing the polyacid-based electrolyte conductor material according to claim 3, wherein the heating and stirring time is 5-48 h; the heating and stirring temperature is 40-60 ℃; the heating and stirring speed is 100-700 rpm; the solvent of the polymer solution and the polyacid solution is water or tetrahydrofuran.
5. The method for preparing a polyacid-based electrolyte conductor material according to claim 1 or 3, wherein the polyacid is one or more of a Keggin-type polyacid, a Dawson-type polyacid and a Preyssler-type polyacid;
the polymer is a polymer with one or more than two of hydroxyl, carboxylic acid group and amino group.
6. The method for preparing a polyacid-based electrolyte conductor material according to claim 5,
the chemical general formula of the Keggin type polyacid is HnXM12O40M ═ Mo, W or V; x is P or As, n is 3; or X ═ Si or Ge, n ═ 4; or X ═ B or Al, n ═ 5; or X ═ Cu or Co, n ═ 6;
the chemical general formula of the Dawson type polyacid is HnX2M18O62M ═ Mo or W; x ═ P, As, S, or V; n is 6;
the chemical general formula of the Preyssler type polyacid is HnYX5M30O110X ═ P; y ═ Bi, Na, Ca, Eu, or U; m is W; n is 12.
7. The method according to claim 5, wherein the polymer having one or more of a hydroxyl group, a carboxylic acid group, and an amino group is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol, and chitosan; the Keggin type polyacid is H3PW12O40。
8. The method for preparing a polyacid-based electrolyte conductor material according to claim 7, wherein the average molecular weight of the polyethylene glycol is 400-300000.
9. The polyacid-based electrolyte conductor material prepared by the method for preparing the polyacid-based electrolyte conductor material according to any one of claims 1 to 8.
10. Use 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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| PCT/CN2019/112054 WO2020258605A1 (en) | 2019-06-27 | 2019-10-18 | Polyacid-based electrolyte conductor material and preparation method and application thereof |
| CA3145331A CA3145331A1 (en) | 2019-06-27 | 2019-10-18 | Polyoxometalate-based electrolyte conductor material and preparation method and application thereof |
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| CN115735949A (en) * | 2022-12-26 | 2023-03-07 | 河南大学 | Polyoxometallate crosslinked polyethylene glycol modified chitosan sponge composite material and preparation method and application thereof |
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