CA3145331A1 - Polyoxometalate-based electrolyte conductor material and preparation method and application thereof - Google Patents

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

Info

Publication number
CA3145331A1
CA3145331A1 CA3145331A CA3145331A CA3145331A1 CA 3145331 A1 CA3145331 A1 CA 3145331A1 CA 3145331 A CA3145331 A CA 3145331A CA 3145331 A CA3145331 A CA 3145331A CA 3145331 A1 CA3145331 A1 CA 3145331A1
Authority
CA
Canada
Prior art keywords
pom
conductor material
based electrolyte
electrolyte conductor
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CA3145331A
Other languages
French (fr)
Inventor
Zhao ZHENG
Linkun CAI
Panchao YIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Publication of CA3145331A1 publication Critical patent/CA3145331A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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. 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fuel Cell (AREA)

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

POLYOXOMETALATE-BASED ELECTROLYTE CONDUCTOR MATERIAL
AND PREPARATION METHOD AND APPLICATION THEREOF
Field of the Invention The present invention belongs to the field of battery materials, and particularly relates to a polyoxometalate-based electrolyte conductor material and a preparation method and application thereof.
Back2round of the Invention Improving the proton conductivity of 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), which has extremely high proton conductivity (>
10-2 S cm-1) at a condition of high humidity (RH 100%) and low/medium temperature (<373 K). However, Nafions are expensive and have poor stability and mechanical property. Therefore, it is an urgent problem to be solved to research and prepare conductor materials that can replace Nafions. The development of electrolyte conductor materials with good conductivity, mechanical property, and processability has a profound significance for the development of fuel cells, batteries, and capacitors.
Polyoxometalates (POMs) are nanoscale early transition metal-oxygen molecule clusters with a lower effective surface charge density, which endow them with very strong proton transmitting capability. In fact, Keggin-type POMs (e.g., and H4SiW12040) exhibit high proton conductivities comparable to Nafions at high humidity. Protons are transferred between POMs through the hydrogen-bond network formed by their crystal water. Therefore, the conductivity is greatly affected by humidity which limits the application of POMs as conductors.
POMs can form organic-inorganic hybrid materials with new functional performance in combination with different organic components. Therefore, researchers blend POMs with polymers to prepare a series of conductor materials with Date Recue/Date Received 2021-12-24 somewhat improved stability, but there is a very great gap between them and the commercial conductor materials in conductivity. How to prepare electrolyte conductor materials with ultra-high conductivity is still a big challenge for researchers.
Summary of the Invention Aiming at the defects and deficiencies in the prior art, a primary objective of the present invention is to provide a POM-based electrolyte conductor material. In the prepared POM-based electrolyte conductor material, a three-dimensional network for transferring protons is formed by means of hydrogen-bond interaction between the POM and the polymer, thereby realizing effective transfer of protons by means of the movement of the polymer chains. This electrolyte conductor material has good proton conduction efficiency in low and medium temperature environments, and meanwhile, has superior processability, safety, and chemical stability.
Another objective of the present invention is to provide a preparation method of the above-described POM-based electrolyte conductor material.
Still another objective of the present invention is to provide an application of the above-described POM-based electrolyte conductor material.
The objectives of the present invention are achieved by the following technical solutions.
A preparation method of a POM-based electrolyte conductor material includes the following steps: mixing a POM with a polymer melt to obtain a blend, subjecting the blend to reacting under heating and stirring, then cooling to room temperature after the end of the reaction to prepare the POM-based electrolyte conductor material.
Preferably, a mass ratio of the POM to the polymer melt is 1: 9 to 7: 3.
Preferably, the heating and stirring is performed for a time of 5 to 48 hours, more preferably 12 hours, at a temperature of 60 to 80 C and a stirring rate of 100 to 700 rpm.
2 Date Recue/Date Received 2021-12-24 Preferably, the room temperature is 25 to 35 C.
Preferably, the type of the POM is one of Keggin type POMs, Dawson type POMs, and Preyssler type POMs.
Preferably, a general chemical formula of the Keggin type POMs is HnXM12040 (M=Mo, W, or V; and X=P or As, and n=3; X=Si or Ge, and n=4; X=B or Al, and n=5;
or X=Cu or Co, and n=6), and more preferably H3PW12040.
Preferably, a general chemical formula of the Dawson type POMs is HnX2Mt8062 (M=Mo or W; X=P, As, S or V; and n=6).
Preferably, a general chemical formula of the Preyssler type POMs is HnYX5M300110 (X=P; Y=Bi, Na, Ca, Eu or U; M=W; and n=12).
Preferably, the polymer is a polymer with one or more of hydroxyl, carboxylic acid group, and amino.
Preferably, the polymer with one or more of hydroxyl, carboxylic acid group, and amino is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol, and chitosan, and more preferably polyethylene glycol (PEG).
Preferably, the molecular weight of the polyethylene glycol is an average molecular weight of 400 to 300,000, and more preferably the polyethylene glycol is one or more of polyethylene glycol having an average molecular weight of 400 or 4,000 and six-arm star-shaped polyethylene glycol having an average molecular weight of 2,400.
A preparation method of a POM-based electrolyte conductor material includes the following steps: adding a polymer into a solvent to obtain a polymer solution;
adding a POM into the solvent to obtain a POM solution; mixing the POM
solution with the polymer solution to obtain a blend, subjecting the blend to reacting under heating and stirring, and after the end of the reaction, completely volatilizing the
3 Date Recue/Date Received 2021-12-24 solvent to prepare the POM-based electrolyte conductor material.
Preferably, the polymer is added into the solvent to obtain the polymer solution, and a concentration range of the polymer solution is 0.1 g/mL to 1 g/mL.
Preferably, the POM is added into the solvent to obtain the POM solution, and a concentration range of the POM solution is 0.1 g/mL to 1 g/mL.
Preferably, a volume ratio of the POM solution to the polymer solution is 1: 9 to 7: 3.
Preferably, the heating and stirring is performed for a time of 5 to 48 hours, more preferably 12 hours, at a temperature of 40 to 60 C and a stirring rate of 100 to 700 rpm.
Preferably, the solvent is water or tetrahydrofuran, and more preferably tetrahydrofuran.
Preferably, the type of the POM is one or more of Keggin type POMs, Dawson type POMs, and Preyssler type POMs.
Preferably, a general chemical formula of the Keggin type POMs is HnXM12040 (M=Mo, W or V; and X=P or As, and n=3; X=Si or Ge, and n=4; X=B or Al, and n=5;
or X=Cu or Co, and n=6), and more preferably H3PW12040.
Preferably, a general chemical formula of the Dawson type POMs is HnX2M18062 (M=Mo or W; X=P, As, S or V; and n=6).
Preferably, a general chemical formula of the Preyssler type POMs is HnYX5M300110 (X=P; Y=Bi, Na, Ca, Eu or U; M=W; and n=12).
Preferably, the polymer is a polymer with one or more of hydroxyl, a carboxylic acid group, and amino.
4 Date Recue/Date Received 2021-12-24 Preferably, the polymer with one or more of hydroxyl, a carboxylic acid group, and amino is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol, and chitosan, and more preferably polyethylene glycol.
Preferably, the molecular weight of the polyethylene glycol is an average molecular weight in a range of 400 to 300,000, and more preferably the polyethylene glycol is one or more of polyethylene glycol having an average molecular weight of 400 and 4,000 and six-arm star-shaped polyethylene glycol having an average molecular weight of 2,400.
A POM-based electrolyte conductor material is prepared by the preparation method of the POM-based electrolyte conductor material described above.
The POM-based electrolyte conductor material is applied in the fields of fuel cells, batteries, and super capacitors.
Compared with the prior art, the present invention has the following advantages and beneficial effects:
(1) the POM-based electrolyte conductor material of the present invention has very high proton conduction efficiency (to 1.01x102 S cm') in low/medium temperature environments (80 C).
(2) the preparation methods of the present invention are simple, have mild reaction conditions, are suitable for mass production, and have low cost.
(3) in the systems of the preparation methods of the present invention, the polyethylene glycol can combine with the POM through the hydrogen bond, thereby greatly increasing the proton conduction efficiency, and meanwhile, the viscosity of the sample is as high as 273 Pa's, which guarantees the safety of the sample while used as an electrolyte.
(4) the POM-based electrolyte conductor material of the present invention has an obvious shear thinning behavior which ensures the good processability of the sample.
Date Recue/Date Received 2021-12-24 Brief Description of the Drawin2s Fig. 1 is small angle X-ray scattering curves of electrolyte conductor materials prepared by Examples 1 to 7.
Fig. 2 is a schematic diagram of the structure and proton conduction of an electrolyte conductor material prepared by an example of the present invention.
Fig. 3 is a Nyquist diagram of a PEG400 electrolyte conductor material prepared by Comparative example 1 at conditions of 25 C, 50 C, and 80 C.
Fig. 4 is a Nyquist diagram of a PEG400-10%PW12 electrolyte conductor material prepared by Example 1 at conditions of 25 C, 50 C, and 80 C.
Fig. 5 is a Nyquist diagram of a PEG400-20%PW12 electrolyte conductor material prepared by Example 2 at conditions of 25 C, 50 C, and 80 C.
Fig. 6 is a Nyquist diagram of a PEG400-50%PW12 electrolyte conductor material prepared by Example 5 at conditions of 25 C, 50 C, and 80 C.
Fig. 7 is a Nyquist diagram of a PEG400-70%PW12 electrolyte conductor material prepared by Example 7 at conditions of 25 C, 50 C, and 80 C.
Fig. 8 is a Nyquist diagram of a PEG4000-60%PW12 electrolyte conductor material prepared by Example 8 at conditions of 25 C, 50 C, and 80 C.
Fig. 9 is a Nyquist diagram of a PEG4000-70%PW12 electrolyte conductor material prepared by Example 9 at conditions of 25 C, 50 C, and 80 C.
Fig. 10 is a Nyquist diagram of a SPEG2400-70%PW12 electrolyte conductor material prepared by Example 10 at conditions of 25 C, 50 C, and 80 C.
Fig. 11 is a flowing graph of the electrolyte conductor materials prepared by Date Recue/Date Received 2021-12-24 Examples 1 to 7 and the electrolyte conductor material prepared by Comparative example 1.
Detailed Description of the Embodiments Specific embodiments of the present invention will be further described in detail below with reference to the figures and examples. It should be pointed out that for an ordinary person skilled in the present field, several modifications and improvements can be made on the premise of without departing from the concept of the present invention. All these modifications and improvements shall fall within the scope of protection of the present invention.
In examples, the room temperature is 27 C, the POM is a Keggin type POM
H3PW12040, and a stirring rate is 300 rpm.
Example 1 1.0 g of POM was dissolved in 9.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 400 at 67 C to obtain a blend A; the blend A was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG400-10%PW12.
Example 2 2.0 g of POM was dissolved in 8.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 400 at 67 C to obtain a blend A; the blend A was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG400-20%PW12.
Example 3 Date Recue/Date Received 2021-12-24 3.0 g of POM was dissolved in 7.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 400 at 67 C to obtain a blend A; the blend A was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG400-30%PW12.
Example 4 4.0 g of POM was dissolved in 6.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 400 at 67 C to obtain a blend A; the blend A was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG400-40%PW12.
Example 5
5.0 g of POM was dissolved in 5.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 400 at 67 C to obtain a blend A; the blend A was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG400-50%PW12.
Example 6
6.0 g of POM was dissolved in 4.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 400 at 67 C to obtain a blend A; the blend A was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG400-60%PW12.

Date Recue/Date Received 2021-12-24 Example 7
7.0 g of POM was dissolved in 3.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 400 at 67 C to obtain a blend A; the blend A was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG400-70%PW12.
Example 8 6.0 g of POM was dissolved in 4.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 4,000 at 80 C to obtain a blend A; the blend A
was subjected to reacting for 12 hours under heating and stirring at 80 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG4000-60%PW12.
Example 9 7.0 g of POM was dissolved in 3.0 g of polyethylene glycol (PEG) melt having a relative molecular weight of 4,000 at 80 C to obtain a blend A; the blend A
was subjected to reacting for 12 hours under heating and stirring at 80 C, and after the reaction ended, the temperature was cooled to room temperature to prepare a transparent POM-based electrolyte conductor material, which was denoted as PEG4000-70%PW12.
Example 10 7.0 g of POM was dissolved in 7 mL of tetrahydrofuran to obtain a solution A;
3.0 g of six-arm star-shaped polyethylene glycol having an average molecular weight of 2,400 was dissolved in 3 mL of tetrahydrofuran to obtain a solution B; the solution A was mixed with the solution B, and the mixture was subjected to reacting for Date Recue/Date Received 2021-12-24 hours under heating and stirring at 50 C; and after the reaction ended, the solvent was volatilized to obtain a POM-based electrolyte conductor material, which was denoted as SPEG2400-70%PW12.
Comparative example 1 g of polyethylene glycol having a relative molecular weight of 400 was subjected to reacting for 12 hours under heating and stirring at 67 C, and after the reaction ended, the temperature was cooled to room temperature to obtain a transparent PEG400 electrolyte conductor material, which was denoted as PEG400.
Table 1 is test results for conductivity of the electrolyte conductor materials of Example 1, Example 2, Example 5, Example 7, Example 8, Example 9, Example 10, and Comparative example 1 at conditions of 25 C, 50 C, and 80 C (at a relative humidity of 45%). A CHI660E electrochemical workstation purchased from CH
Instruments, Inc. was used as a test instrument. During the tests, two platinum sheets were used as electrodes, a test frequency range was from 0.01 Hz to 100,000 Hz, EIS
was used for test, and the proton conductivity was calculated by a formula a =

L/(ARb). Rb represented a resistance value, L represented a distance between the two platinum sheet electrodes, and A represented an area of the two electrodes.
Table 1 General chart of test results for conductivity Sample 25 C_ 50 C_ 80 C_ conductivity / S conductivity / S conductivity / S

cm cm cm1 PEG400 7.4x106 1.3 x 10-5 2.9x105 PEG400-10%PW12 6.5x10-5 1.8x 10-4 4.2 x10-4 PEG400-20%PW12 1.4 x10-4 4.2x 10-4 1.0x10-3 PEG400-50%PW12 4.0 x10-4 1.2x 10-3 3.5x10-3 PEG400-70%PW12 1.4x10-3 3.6x 10-3 1.0x10-2 PEG4000-60%PW12 1.8 x 10-3 5.3 x 10-3 1.2 x 10-2 PEG4000-70%PW12 1.6 x 10-3 6.5 x 10-3 1.6 x 10-2 Date Recue/Date Received 2021-12-24 SPEG2400-70%PW12 6.1 x 10-4 2.4x 10-3 8.8x 10-3 Conductivity values of the electrolyte conductor materials prepared by various examples are listed in Table 1, and it can be seen that: the conductivities of various samples increase as the temperature is increased; with the increase of the content of the POM, the conductivity of the prepared electrolyte conductor material is increased by three orders of magnitude, wherein the conductivity of the PEG400-70%PW12 sample can reach 1.01x 10-2 S cm-1 at 80 C; an electrolyte conductor material with very high proton conduction efficiency can also be obtained by blending a higher molecular weight polyethylene glycol with a POM; and the SPEG2400-70%PW12 sample prepared by the solvent method also has higher conductivity.
Fig. 1 shows small angle X-ray scattering curves of the electrolyte conductor materials prepared by Examples 1 to 7. It can be seen from Fig. 1 that: the prepared PEG400-PW12 nanocomposite material has no obvious crystal diffraction peak in the small angle X-ray scattering spectrum. It indicates that in the electrolyte conductor materials of the present invention, the POM clusters are unifounly dispersed in the polymer substrate, which achieves the nanoscale dispersion of the POM, and guarantees the structural stability of the sample.
Fig. 2 is schematic diagram for the structure and proton conduction of the electrolyte conductor material prepared by the example of the present invention.
Wherein, islet shaped structures represent phosphotungstic acids and hydrogen-bond interaction between the phosphotungstic acids and the polymer components, solid lines connecting different islet structures represent the polymer chains of polyethylene glycol, and I-1+ represents protons. It can be seen from Fig. 2 that: the polyethylene glycol and the POM form a three-dimensional network through hydrogen bonds, and the protons are effectively transferred in virtue of the movement of the polymer chain.
Fig. 3 is a Nyquist diagram of the PEG400 electrolyte conductor material prepared by Comparative example 1 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the intercept of the Nyquist plot with the real axis.

Date Recue/Date Received 2021-12-24 Fig. 4 is a Nyquist diagram of the PEG400-10%PW12 electrolyte conductor material prepared by Example 1 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the intercept of the Nyquist plot with the real axis.
Fig. 5 is a Nyquist diagram of the PEG400-20%PW12 electrolyte conductor material prepared by Example 2 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the intercept of the Nyquist plot with the real axis.
Fig. 6 is a Nyquist diagram of the PEG400-50%PW12 electrolyte conductor material prepared by Example 5 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the intercept of the Nyquist plot with the real axis.
Fig. 7 is a Nyquist diagram of the PEG400-70%PW12 electrolyte conductor material prepared by Example 7 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the intercept of the Nyquist plot with the real axis.
It can be seen from Fig. 4 to Fig. 7 that the conductivity of the conductor is greatly increased with the addition of the POM. Meanwhile, it indicates that as the temperature is increased to 80 C, the conductivity of the sample has an obvious rising tendency.
Fig. 8 is a Nyquist diagram of the PEG4000-60%PW12 electrolyte conductor material prepared by Example 8 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the intercept of the Nyquist plot with the real axis.
Fig. 9 is a Nyquist diagram of the PEG4000-70%PW12 electrolyte conductor material prepared by Example 9 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the Date Recue/Date Received 2021-12-24 intercept of the Nyquist plot with the real axis.
It can be seen from Fig. 8 and Fig. 9 that as the temperature is increased to 80 C, the conductivity of the sample has an obvious rising tendency.
Fig. 10 is a Nyquist diagram of the SPEG2400-70%PW12 electrolyte conductor material prepared by Example 10 at conditions of 25 C, 50 C, and 80 C.
Wherein, the conductivity of the electrolyte conductor material can be obtained from the intercept of the Nyquist plot with the real axis. It can be seen from Fig. 10 that the POM-based electrolyte conductor material prepared by the solvent method also exhibits relatively high conductivity.
Fig. 11 is a flow graph of the electrolyte conductor materials prepared by Examples 1 to 7 and the electrolyte conductor material of Comparative example 1. It can be seen from Fig. 11 that the viscosity of the PEG400-70%PW12 sample is as high as 273 Pa's at room temperature, which guarantees the safety of the sample used as an electrolyte. In addition, the obvious shear thinning behavior of the sample enables the sample to have good processability.
From the detailed description of the examples of the present invention with the above-described content, it can be understood that the conductivity of the POM-based electrolyte conductor material of the present invention is greatly increased as the temperature rises, under conditions of the temperature range of 25 C to 80 C
and a relative humidity of 45%. During the preparation of the materials, the samples with the POM in a mass ratio of 70% can all have very high conductivity (at a temperature of 80 C, the conductivity of PEG400-70%PW12 is 1.01 x 10-2 S cm-1, the conductivity of PEG4000-70%PW12 is 1.64x 10-2 S cm-1, and the conductivity of SPEG2400-70%PW12 is 8.8x 10-3 S cm').
What is described above are preferred embodiments of the present invention and not intended to limit the present invention. It should be pointed out that an ordinary person skilled in the present technical field can make several improvements and modifications on the premise of without departing from the technical principle of the present inventions, and these improvements and modifications shall also be deemed as Date Recue/Date Received 2021-12-24 falling within the scope of protection of the present invention. Therefore, the content of without departing from the patented solution of the present invention, any simple amendment, equivalent change, and modification made to the above examples according to the essence of the patented technology of the present invention shall fall within the scope of protection of the patent of the present invention.

Date Recue/Date Received 2021-12-24

Claims (10)

Claims
1. A preparation method of a POM-based electrolyte conductor material, characterized in that, it comprises the following steps: mixing a POM with a polymer melt in a mass ratio of 1 : 9 to 7 : 3 to obtain a blend, subjecting the blend to reacting under heating and stirring, then cooling to room temperature after the end of the reaction to prepare the POM-based electrolyte conductor material.
2. The preparation method of a POM-based electrolyte conductor material according to claim 1, characterized in that, the heating and stirring is performed for a time of 5 to 48 hours at a temperature of 60 to 80 C and a stirring rate of 100 to 700 rpm.
3. A preparation method of a POM-based electrolyte conductor material, characterized in that, it comprises the following steps: adding a polymer into a solvent to obtain a polymer solution at a concentration of 0.1 g/mL to 1 g/mL; adding a POM
into the solvent to obtain a POM solution at a concentration of 0.1 g/mL to 1 g/mL;
mixing the POM solution with the polymer solution in a volume ratio of 1 : 9 to 7 : 3 to obtain a blend, subjecting the blend to reacting under heating and stirring, and after the end of the reaction, completely volatilizing the solvent to prepare the POM-based electrolyte conductor material.
4. The preparation method of a POM-based electrolyte conductor material according to claim 3, characterized in that, the heating and stirring is performed for a time of 5 to 48 hours at a temperature of 40 to 60 C and a stirring rate of 100 to 700 rpm; and the solvent of the polymer solution and the POM solution is water or tetrahydrofuran.
5. The preparation method of the POM-based electrolyte conductor material according to claims 1 or 3, characterized in that, the POM is one or more of Keggin type POMs, Dawson type POMs, and Preyssler type POMs; and the polymer is a polymer with one or more of hydroxyl, carboxylic acid group, and amino.
Date Recue/Date Received 2021-12-24
6. The preparation method of the POM-based electrolyte conductor material according to claim 5, characterized in that, a general chemical formula of the Keggin type POMs is HnXM12040, where M=Mo, W or V; and X=P or As, and n=3; X=Si or Ge, and n=4; X=B or Al, and n=5;

or X=Cu or Co, and n=6;
a general chemical formula of the Dawson type POMs is HnX2M18062, where M=Mo or W; X=P, As, S or V; and n=6; and a general chemical formula of the Preyssler type POMs is HnYX5M3oOlio, where X=P; Y=Bi, Na, Ca, Eu or U; M=W; and n=12.
7. The preparation method of the POM-based electrolyte conductor material according to claim 5, characterized in that, the polymer with one or more of hydroxyl, carboxylic acid group, and amino is one of polyethylene glycol, polyacrylic acid, polyvinyl alcohol, and chitosan; and the Keggin type POM is H3PW1204o.
8. The preparation method of the POM-based electrolyte conductor material according to claim 7, characterized in that, the polyethylene glycol has an average molecular weight of 400 to 300,000.
9. A POM-based electrolyte conductor material prepared by the preparation method of the POM-based electrolyte conductor material according to any one of claims 1 to 8.
10. An application of the POM-based electrolyte conductor material according to claim 9 in the fields of fuel cells, lithium ion batteries, and supercapacitors.

Date Recue/Date Received 2021-12-24
CA3145331A 2019-06-27 2019-10-18 Polyoxometalate-based electrolyte conductor material and preparation method and application thereof Pending CA3145331A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201910566176.6A CN112151842A (en) 2019-06-27 2019-06-27 Polyacid-based electrolyte conductor material and preparation method and application thereof
CN201910566176.6 2019-06-27
PCT/CN2019/112054 WO2020258605A1 (en) 2019-06-27 2019-10-18 Polyacid-based electrolyte conductor material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CA3145331A1 true CA3145331A1 (en) 2020-12-30

Family

ID=73870093

Family Applications (1)

Application Number Title Priority Date Filing Date
CA3145331A Pending CA3145331A1 (en) 2019-06-27 2019-10-18 Polyoxometalate-based electrolyte conductor material and preparation method and application thereof

Country Status (3)

Country Link
CN (1) CN112151842A (en)
CA (1) CA3145331A1 (en)
WO (1) WO2020258605A1 (en)

Families Citing this family (4)

* 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
CN113717395B (en) * 2021-09-01 2023-02-24 哈尔滨师范大学 Porous electrode material with { P6Mo18O73} based 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
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

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100428549C (en) * 2001-09-11 2008-10-22 积水化学工业株式会社 Membrane electrode assembly, method of preparing 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
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
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
CN103145978B (en) * 2013-03-25 2015-05-13 南开大学 Pegylation polyoxometallate 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
WO2016045754A1 (en) * 2014-09-26 2016-03-31 Mebius D.O.O Polyoxometalate salts, proton exchange membranes and precursors, membrane-electrode assemblies, fuel cells and methods
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
CN109659601B (en) * 2018-12-12 2021-09-28 南京师范大学 Application of polyacid/high-molecular polymer hybrid nanowire material as solid electrolyte
CN109850902B (en) * 2018-12-13 2022-03-29 华南理工大学 Preparation method of silicotungstic acid nanorod

Also Published As

Publication number Publication date
CN112151842A (en) 2020-12-29
WO2020258605A1 (en) 2020-12-30

Similar Documents

Publication Publication Date Title
CA3145331A1 (en) Polyoxometalate-based electrolyte conductor material and preparation method and application thereof
Chen et al. Tunable multi-cations-crosslinked poly (arylene piperidinium)-based alkaline membranes with high ion conductivity and durability
Chen et al. Improved performance of lithium ion battery separator enabled by co-electrospinnig polyimide/poly (vinylidene fluoride-co-hexafluoropropylene) and the incorporation of TiO2-(2-hydroxyethyl methacrylate)
Yin et al. Polymer electrolytes based on dicationic polymeric ionic liquids: application in lithium metal batteries
CN102044702B (en) Composite polymer electrolyte for lithium ion battery and preparation method thereof
Gopi et al. Development of polyvinyl alcohol/chitosan blend anion exchange membrane with mono and di quaternizing agents for application in alkaline polymer electrolyte fuel cells
Das et al. A bionanocomposite based on 1, 4-diazabicyclo-[2.2. 2]-octane cellulose nanofiber cross-linked-quaternary polysulfone as an anion conducting membrane
Xu et al. Garnet-doped composite polymer electrolyte with high ionic conductivity for dendrite-free lithium batteries
Liu et al. Anion-exchange membranes derived from quaternized polysulfone and exfoliated layered double hydroxide for fuel cells
Li et al. Poly (aryl ether ketone)/polymeric ionic liquid with anisotropic swelling behavior for anion exchange membranes
CN107534153A (en) For improving dispersiveness and the low-resistance secondary battery cathode slurry of drop and including its negative pole
CN111525184A (en) Composite solid electrolyte film and preparation and application thereof
Li et al. A high-performance solid electrolyte assisted with hybrid biomaterials for lithium metal batteries
CN110504486B (en) Functionalized quantum dot composite solid electrolyte membrane and preparation method and application thereof
Hu et al. Hydroxyl-rich single-ion conductors enable solid hybrid polymer electrolytes with excellent compatibility for dendrite-free lithium metal batteries
CN101735589B (en) Polymer electrolyte, preparation method thereof and battery comprising polymer electrolyte
Liu et al. Preparation and characterization of high conductivity comb polymer anion exchange membranes
CN100513467C (en) Porous gel polyelectrolyte thin film and preparation method thereof
TW202320378A (en) Preparation method of all-solid composite polymer electrolyte film and all-solid lithium battery advantageous in having fast manufacturing process and excellent performance, and capable of being perfectly applied to all-solid lithium batteries with high voltage and high energy density
Zhang et al. Synergistically regulating the separator pore structure and surface property toward dendrite-free and high-performance aqueous zinc-ion batteries
CN104810549B (en) The porous gel method for preparing polymer electrolytes of doped compound nano particle
Pan et al. Enhanced mechanical strength and conductivity of PVFM based membrane and its supporting polymer electrolytes
CN101800338A (en) Modified alkaline polymer electrolyte film and preparation method thereof
Yao et al. Multifunctional polyzwitterion ionic liquid based solid-state electrolytes for enhancing the low-temperature performance of lithium-metal batteries
Salehi Artimani et al. Proton Conducting Nanocomposite Membranes Based on Poly Vinyl Alcohol (PVA)/Glutaraldehyde (GA) for Proton Exchange Membrane Fuel Cells

Legal Events

Date Code Title Description
EEER Examination request

Effective date: 20220209

EEER Examination request

Effective date: 20220209

EEER Examination request

Effective date: 20220209

EEER Examination request

Effective date: 20220209

EEER Examination request

Effective date: 20220209

EEER Examination request

Effective date: 20220209

EEER Examination request

Effective date: 20220209

EEER Examination request

Effective date: 20220209