CN112499965B - Transparent phosphate proton conductor and preparation method thereof - Google Patents

Transparent phosphate proton conductor and preparation method thereof Download PDF

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CN112499965B
CN112499965B CN202011272097.3A CN202011272097A CN112499965B CN 112499965 B CN112499965 B CN 112499965B CN 202011272097 A CN202011272097 A CN 202011272097A CN 112499965 B CN112499965 B CN 112499965B
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proton conductor
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CN112499965A (en
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任洋
刘萍
刘荣欣
贺海燕
赵高扬
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Xian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/253—Silica-free oxide glass compositions containing germanium
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • 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
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Abstract

The invention relates to a preparation method of a transparent phosphate proton conductor, which comprises the following steps: step 1, preparing transparent phosphate glass; step 2, slicing the cylindrical transparent phosphate glass obtained in the step 1, and polishing one section by using sand paper; step 3, placing the polished slices into an ultrasonic cleaning machine for cleaning for 30min, and then plating platinum on all polished surfaces; and 4, putting the platinum-plated slice into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen to be 3-6 ml/min, then lapping an aluminum sheet on the platinum, carrying out solid electrochemical displacement reaction in the graphite crucible by taking molten tin or graphite powder as a bottom electrode, controlling the temperature to be 310-350 ℃, taking out after the reaction is carried out for 5 hours, and grinding and polishing to obtain the transparent phosphate proton conductor. The method has controllable process. Also provides a transparent phosphate proton conductor prepared by the method.

Description

Transparent phosphate proton conductor and preparation method thereof
Technical Field
The invention belongs to the technical field of proton conductor preparation methods, and particularly relates to a transparent phosphate proton conductor and a preparation method thereof.
Background
Proton conductors are solid electrolytes capable of conducting hydrogen ions, and have attracted much attention in fuel cells, hydrogen sensors, catalytic hydrogenation and dehydrogenation of organic substances, normal pressure synthesis of ammonia, and the like because of their room temperature conductivity. Through years of research, development and research of proton conductors are greatly advanced, but most of the currently known solid proton conductors are opaque or semitransparent materials (transparent proton conductors require that the average visible light transmittance of the conductors is over 75 percent, and the room is filled with the conductorsThe temperature proton conductivity reaches 10 -5 S/cm), which limits the application of proton conductors in optical devices, such as electrochromic glazing, which is composed of a transparent conductive layer, an electrochromic layer and an electrolyte layer, both the transparent conductive layer and the electrochromic layer (in a faded state) can achieve a light transmittance of more than 75%, but no transparent inorganic solid electrolyte (the light transmittance needs to be more than 75%) is used as a suitable type selection, so that the optical device cannot be used as an energy-saving window. Currently, electrochromic glass devices, which have been commercialized, use liquid Li + Or H + The solution is an electrolyte layer, so that the encapsulation of the device is greatly limited, and the device is often scrapped due to leakage. The number of all-solid-state optical devices developed today is small, and in such limited devices, li is included + Or H + Mainly a mechanical mixture of inorganic salts and organic matrix to replace the liquid electrolyte in the optical device. Although the light transmittance and proton conductivity of the proton conductor meet the electrolyte requirement required by electrochromic glass devices, and the problem of device packaging is solved, the proton conductor takes organic materials as a matrix, and the organic materials are easy to age after being influenced by illumination, heat and the like, so that the commercial application of the all-solid-state optical device is difficult to effectively popularize. Therefore, it is highly desirable to develop an inorganic solid-state transparent proton conductor suitable for optical devices.
Disclosure of Invention
The object of the present invention is to provide a transparent phosphate proton conductor having a high electrical conductivity.
The second purpose of the invention is to provide a preparation method of the transparent phosphate proton conductor, which can be used for preparing a large amount of proton conductors and has controllable process.
The technical scheme adopted by the invention is that the preparation method of the transparent phosphate proton conductor comprises the following specific steps:
step 1, preparing transparent phosphate glass;
step 1.1, weighing a certain amount of Na 2 CO 3 、La 2 O 3 、GeO 2 And H 3 PO 4 Placing the crucible in a platinum crucible, then placing the crucible in a heating furnace, heating the crucible to 800 ℃ at the speed of 10 ℃/min without covering a cover of the platinum crucible, and then preserving heat for 1-2 hours;
step 1.2, covering a platinum crucible with a cover, and continuously heating to 1250-1450 ℃ at the speed of 7-10 ℃/min;
step 1.3, taking out the platinum crucible, uniformly shaking the platinum crucible, then putting the platinum crucible into a heating furnace, keeping the temperature for 1 to 2 hours, then taking out the platinum crucible, uniformly shaking the platinum crucible, and then continuously putting the platinum crucible into the heating furnace for heating for 1 to 2 hours;
step 1.4, taking out the crucible in the step 1.3, and pouring substances in the crucible into a circular mold to form cylindrical glass;
step 1.5, taking out the cylindrical glass, putting the cylindrical glass into a heating furnace, preserving the heat for 1 to 2 hours at the temperature of 440 to 460 ℃, and then cooling the cylindrical glass to room temperature for 12 hours to obtain transparent phosphate glass;
step 2, slicing the cylindrical transparent phosphate glass obtained in the step 1, and polishing one section by using sand paper;
step 3, placing the polished slices into an ultrasonic cleaning machine for cleaning for 30min, and then plating platinum on all polished surfaces;
and 4, putting the platinum-plated slice into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen to be 3-6 ml/min, then lapping an aluminum sheet on the platinum, carrying out solid electrochemical displacement reaction in the graphite crucible by taking molten tin or graphite powder as a bottom electrode, controlling the temperature to be 310-350 ℃, taking out after the reaction is carried out for 5 hours, and grinding and polishing to obtain the transparent phosphate proton conductor.
The present invention is also characterized in that,
in step 1.1, na 2 CO 3 ：H 3 PO 4 ：La 2 O 3 ：GeO 2 Is 25:63: 10-2: 2 to 10.
In the step 2, the thickness of the phosphate glass slice is 1mm, the diameter of the circular cross section of the phosphate glass slice is 1cm, and the sand paper after polishing treatment is 1000 meshes.
And 3, plating platinum with the thickness of 50nm on the polished surface of the slice.
The second technical scheme adopted by the invention is that the transparent phosphate proton conductor is prepared by adopting the preparation method.
The invention has the beneficial effects that:
(1) The transparent phosphate proton conductor is a solid electrolyte suitable for optical use, uses phosphate glass as a raw material, and injects a large amount of hydrogen ions into the phosphate glass to form a disk-shaped proton conductor, and the transparency and the electric conductivity of the proton conductor are greatly improved.
(2) The transparent phosphate proton conductor of the invention adopts common inorganic salt as raw material, does not need modifier and stabilizer, has simple formula and low cost, and has strong market competitiveness in the aspect of economy.
(3) The preparation method of the transparent phosphate proton conductor is a solid electrochemical technology, can prepare the proton conductor with higher transparency, has more excellent performance and higher transparency compared with the proton conductor on the market, and the electrochemical method adopted for preparing the proton conductor can be used for preparing a large amount of proton conductors, has controllable process, lays the foundation for realizing industrialized mass production, and has great practical significance.
Drawings
FIG. 1 is a flow chart of a method for preparing a transparent phosphate proton conductor according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a transparent phosphate proton conductor, which comprises the following specific steps as shown in figure 1:
step 1, preparing transparent phosphate glass;
step 1.1, weighing a certain amount of Na 2 CO 3 、La 2 O 3 、GeO 2 And H 3 PO 4 Placing it in platinum crucible, placing the crucible in heating furnace, and making it have no need of covering platinumHeating the cover of the gold crucible to 800 ℃ at the speed of 10 ℃/min, and then preserving heat for 1-2 hours;
in step 1.1, na 2 CO 3 ：H 3 PO 4 ：La 2 O 3 ：GeO 2 The ratio of the amounts of substances of (a) to (b) is 25:63:10 to 2:2 to 10.
Step 1.2, covering a platinum crucible with a cover, and continuously heating to 1250-1450 ℃ at the speed of 7-10 ℃/min;
step 1.3, taking out the platinum crucible, uniformly shaking the platinum crucible, then putting the platinum crucible into a heating furnace, keeping the temperature for 1 to 2 hours, then taking out the platinum crucible, uniformly shaking the platinum crucible, and then continuously putting the platinum crucible into the heating furnace for heating for 1 to 2 hours;
step 1.4, taking out the crucible in the step 1.3, and pouring substances in the crucible into a circular mold to form cylindrical glass;
step 1.5, taking out the cylindrical glass, putting the cylindrical glass into a heating furnace, preserving heat for 1-2 hours at 440-460 ℃, and then cooling to room temperature for 12 hours to obtain transparent phosphate glass;
step 2, slicing the cylindrical transparent phosphate glass obtained in the step 1, and polishing one section by using sand paper;
in the step 2, the thickness of the phosphate glass slice is 1mm, the diameter of the circular cross section of the phosphate glass slice is 1cm, and the sand paper after polishing treatment is 1000 meshes.
Step 3, placing the polished slices into an ultrasonic cleaning machine for cleaning for 30min, and then plating platinum on all polished surfaces;
and 4, putting the platinum-plated slice into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen to be 3-6 ml/min, then lapping an aluminum sheet on the platinum, carrying out solid electrochemical displacement reaction in the graphite crucible by taking molten tin or graphite powder as a bottom electrode, controlling the temperature to be 310-350 ℃, taking out after the reaction is carried out for 5 hours, and grinding and polishing to obtain the transparent phosphate proton conductor.
In step 3, the polished surface of the slice is plated with 50nm thick platinum.
The invention also provides a transparent phosphate proton conductor prepared by the preparation method.
Example 1
A preparation method of a transparent phosphate proton conductor comprises the following specific steps:
3.90g of Na are weighed 2 CO 3 ，1.85g GeO 2 ，2.88g La 2 O 3 And 21.38g of H 3 PO 4 Putting the crucible into a platinum crucible, putting the crucible into a heating furnace (without covering the cover of the platinum crucible), heating to 800 ℃ at the speed of 7 ℃/min, preserving heat for 1 hour, covering the cover of the platinum crucible, continuously heating to 1250 ℃ at the speed of 7 ℃/min, taking out the platinum crucible, uniformly shaking, putting the platinum crucible into the heating furnace again, preserving heat for 1 hour, taking out the platinum crucible, uniformly shaking, continuously putting the platinum crucible into the heating furnace, heating for 1 hour, taking out the crucible, pouring substances in a circular mold to form cylindrical glass, taking out the cylindrical glass in the mold, putting the cylindrical glass into the heating furnace, preserving heat for 1 hour at 440 ℃, continuously cooling to room temperature for 12 hours, and obtaining the transparent phosphate glass.
The method comprises the steps of slicing cylindrical glass, polishing the sliced glass with the diameter of 1cm and the thickness of 1mm by using abrasive paper, cleaning the polished sliced glass in an ultrasonic cleaning machine for 30 mm, plating platinum on the polished surface, putting the sliced glass plated with the platinum into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, enabling the flow rate of the hydrogen to be 3ml/min, lapping an aluminum sheet on the platinum-plated surface of the sliced glass, performing solid electrochemical displacement reaction in the graphite crucible by using molten tin or graphite powder as a bottom electrode, controlling the temperature to be 310 ℃, taking out the sliced glass after the reaction is performed for 5 hours, and polishing to obtain the transparent phosphate proton conductor.
The conductivity of the transparent phosphate proton conductor was 9.0X 10 -5 s/m, transparency 88%.
Example 2
A preparation method of a transparent phosphate proton conductor comprises the following specific steps:
3.94g of Na are weighed out 2 CO 3 ，2.49g GeO 2 ，1.94g La 2 O 3 And 21.62g of H 3 PO 4 Placing the crucible in a platinum crucible, then placing the crucible in a heating furnace (without covering the cover of the platinum crucible), heating to 800 ℃ at the speed of 8 ℃/min, and then preserving heat for 1 hour; covering a cover of the platinum crucible, continuously heating to 1350 ℃ at the speed of 8 ℃/min, taking out the platinum crucible, uniformly shaking, then putting the platinum crucible into a heating furnace, preserving heat for 1 hour, then taking out the platinum crucible, uniformly shaking, then putting the platinum crucible into the heating furnace, and heating for 1 hour; taking out the crucible, pouring the substances in the crucible into a circular mold to form cylindrical glass, taking out the cylindrical glass in the mold, putting the cylindrical glass into a heating furnace, preserving the heat at 450 ℃ for 1 hour, and continuously cooling to room temperature for 12 hours to obtain the transparent phosphate glass.
Slicing cylindrical glass, wherein the diameter of the circular cross section of the sliced piece is 1cm, the thickness of the sliced piece is 1mm, polishing the sliced piece by using abrasive paper, cleaning the polished sliced piece in an ultrasonic cleaning machine for 30 mm, plating platinum on the polished side, putting the sliced piece plated with the platinum into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen to be 5ml/min, plating an aluminum sheet on the side plated with the platinum of the sliced piece, performing solid electrochemical displacement reaction in the graphite crucible by using molten tin or graphite powder, controlling the temperature to be 330 ℃, taking out the sliced piece after the reaction is performed for 5 hours, and polishing the piece to obtain the transparent phosphate proton conductor.
The conductivity of the transparent phosphate proton conductor was 1.2X 10 -4 s/m, transparency 90%
Example 3
A preparation method of a transparent phosphate proton conductor comprises the following specific steps:
3.99g of Na are weighed 2 CO 3 ，3.15g GeO 2 ，0.98g La 2 O 3 And 21.88g of H 3 PO 4 Putting the crucible into a platinum crucible, putting the crucible into a heating furnace (without covering the cover of the platinum crucible), heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 1 hour, covering the cover of the platinum crucible, continuously heating to 1450 ℃ at the speed of 10 ℃/min, taking out the platinum crucible, uniformly shaking, putting the platinum crucible into the heating furnace, preserving heat for 1 hour, and then putting the platinum crucible into the heating furnaceTaking out, shaking uniformly, then continuously placing the glass in a heating furnace for heating for 1 hour, taking out the crucible, pouring the substances in the crucible into a circular mold to form cylindrical glass, taking out the cylindrical glass in the mold, placing the cylindrical glass in the heating furnace, keeping the temperature for 1 hour at 450 ℃, and continuously cooling to room temperature for 12 hours to obtain the transparent phosphate glass.
Slicing cylindrical glass, wherein the diameter of the circular cross section of the sliced piece is 1cm, the thickness of the sliced piece is 1mm, polishing the sliced piece by using sand paper, cleaning the polished sliced piece by 30 mm in an ultrasonic cleaner, and plating platinum on the polished surface; putting the slice plated with platinum into a cleaned graphite crucible, introducing hydrogen into the graphite crucible at the flow rate of 6ml/min, lapping an aluminum sheet on the side plated with platinum of the slice, carrying out solid electrochemical displacement reaction in the graphite crucible by using molten tin or graphite powder, controlling the temperature at 350 ℃, taking out after 5-hour reaction, and grinding and polishing to obtain the transparent phosphate proton conductor.
The conductivity of the transparent phosphate proton conductor was 8.7X 10 -5 s/m, transparency 91%.
Example 4
A preparation method of a transparent phosphate proton conductor comprises the following specific steps:
step 1, preparing transparent phosphate glass;
step 1.1, weighing a certain amount of Na 2 CO 3 、La 2 O 3 、GeO 2 And H 3 PO 4 Placing the crucible in a platinum crucible, then placing the crucible in a heating furnace, heating the crucible to 800 ℃ at the speed of 10 ℃/min without covering a cover of the platinum crucible, and then preserving heat for 1 hour;
in step 1.1, na 2 CO 3 ：H 3 PO 4 ：La 2 O 3 ：GeO 2 The ratio of the amounts of substances of (a) to (b) is 25:63:10:2.
step 1.2, covering a cover on the platinum crucible, and continuously heating to 1250 ℃ at the speed of 7 ℃/min;
step 1.3, taking out the platinum crucible, uniformly shaking the platinum crucible, then putting the platinum crucible into a heating furnace, preserving heat for 1 hour, then taking out the platinum crucible, uniformly shaking the platinum crucible, and then continuously putting the platinum crucible into the heating furnace for heating for 1 hour;
step 1.4, taking out the crucible in the step 1.3, and pouring the substances in the crucible into a circular mold to form cylindrical glass;
step 1.5, taking out the cylindrical glass, putting the cylindrical glass into a heating furnace, preserving the heat at 440 ℃ for 1 hour, and cooling the cylindrical glass to room temperature for 12 hours to obtain transparent phosphate glass;
step 2, slicing the cylindrical transparent phosphate glass obtained in the step 1, and polishing one section by using abrasive paper;
in the step 2, the thickness of the phosphate glass slice is 1mm, the diameter of the circular cross section of the phosphate glass slice is 1cm, and the sand paper after polishing treatment is 1000 meshes.
Step 3, placing the polished slices into an ultrasonic cleaning machine for cleaning for 30min, and then plating platinum on all polished surfaces;
and 4, putting the platinum-plated slice into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen at 3ml/min, then lapping an aluminum sheet on the platinum, carrying out solid electrochemical displacement reaction in the graphite crucible by taking molten tin or graphite powder as a bottom electrode, controlling the temperature at 310 ℃, taking out after the reaction is carried out for 5 hours, and grinding and polishing to obtain the transparent phosphate proton conductor.
In step 3, the polished surface of the slice is plated with 50nm thick platinum.
Example 5
A preparation method of a transparent phosphate proton conductor comprises the following specific steps:
step 1, preparing transparent phosphate glass;
step 1.1, weighing a certain amount of Na 2 CO 3 、La 2 O 3 、GeO 2 And H 3 PO 4 Placing the crucible in a platinum crucible, then placing the crucible in a heating furnace, heating the crucible to 800 ℃ at the speed of 10 ℃/min without covering the cover of the platinum crucible, and then preserving the heat for 2 hours;
in step 1.1, na 2 CO 3 ：H 3 PO 4 ：La 2 O 3 ：GeO 2 The ratio of the amounts of substances of (a) to (b) is 25:63:2:10.
step 1.2, covering a platinum crucible with a cover, and continuously heating to 1450 ℃ at a speed of 10 ℃/min;
step 1.3, taking out the platinum crucible, uniformly shaking the platinum crucible, then putting the platinum crucible into a heating furnace, preserving heat for 2 hours, then taking out the platinum crucible, uniformly shaking the platinum crucible, and then continuously putting the platinum crucible into the heating furnace for heating for 2 hours;
step 1.4, taking out the crucible in the step 1.3, and pouring the substances in the crucible into a circular mold to form cylindrical glass;
step 1.5, taking out the cylindrical glass, putting the cylindrical glass into a heating furnace, preserving the heat at 460 ℃ for 2 hours, and then cooling the cylindrical glass to room temperature for 12 hours to obtain transparent phosphate glass;
step 2, slicing the cylindrical transparent phosphate glass obtained in the step 1, and polishing one section by using abrasive paper;
in the step 2, the thickness of the phosphate glass slice is 1mm, the diameter of the circular cross section of the phosphate glass slice is 1cm, and the sand paper after polishing treatment is 1000 meshes.
Step 3, placing the polished slices into an ultrasonic cleaning machine for cleaning for 30min, and then plating platinum on all polished surfaces;
and 4, putting the platinum-plated slices into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen to be 6ml/min, then lapping an aluminum sheet on the platinum, carrying out solid electrochemical displacement reaction in the graphite crucible by taking molten tin or graphite powder as a bottom electrode, controlling the temperature to be 350 ℃, taking out after 5-hour reaction, and grinding and polishing to obtain the transparent phosphate proton conductor.
And 3, plating platinum with the thickness of 50nm on the polished surface of the slice.
Example 6
A preparation method of a transparent phosphate proton conductor comprises the following specific steps:
step 1, preparing transparent phosphate glass;
step 1.1, weighing a certain amount of Na 2 CO 3 、La 2 O 3 、GeO 2 And H 3 PO 4 Placing the crucible in a platinum crucible, then placing the crucible in a heating furnace, heating the crucible to 800 ℃ at the speed of 10 ℃/min without covering the cover of the platinum crucible, and then preserving the heat for 1.5 hours;
in step 1.1, na 2 CO 3 ：H 3 PO 4 ：La 2 O 3 ：GeO 2 The ratio of the amounts of substances of (a) to (b) is 25:63:5:7.
step 1.2, covering a cover on the platinum crucible, and continuously heating to 1300 ℃ at the speed of 7-10 ℃/min;
step 1.3, taking out the platinum crucible, uniformly shaking the platinum crucible, then putting the platinum crucible into a heating furnace, preserving heat for 1.5 hours, then taking out the platinum crucible, uniformly shaking the platinum crucible, and then continuously putting the platinum crucible into the heating furnace for heating for 1.5 hours;
step 1.4, taking out the crucible in the step 1.3, and pouring the substances in the crucible into a circular mold to form cylindrical glass;
step 1.5, taking out the cylindrical glass, putting the cylindrical glass into a heating furnace, preserving the heat at 450 ℃ for 1.5 hours, and then cooling the cylindrical glass to room temperature for 12 hours to obtain transparent phosphate glass;
step 2, slicing the cylindrical transparent phosphate glass obtained in the step 1, and polishing one section by using sand paper;
in the step 2, the thickness of the phosphate glass slice is 1mm, the diameter of the circular cross section of the phosphate glass slice is 1cm, and the sand paper after polishing treatment is 1000 meshes.
Step 3, placing the polished slices into an ultrasonic cleaning machine for cleaning for 30min, and then plating platinum on all polished surfaces;
and 4, putting the platinum-plated slices into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen to be 4ml/min, then lapping an aluminum sheet on the platinum, carrying out solid electrochemical displacement reaction in the graphite crucible by taking molten tin or graphite powder as a bottom electrode, controlling the temperature to be 320 ℃, taking out after 5-hour reaction, and grinding and polishing to obtain the transparent phosphate proton conductor.
In step 3, the polished surface of the slice is plated with 50nm thick platinum.

Claims (4)

1. A preparation method of a transparent phosphate proton conductor is characterized by comprising the following specific steps:
step 1, preparing transparent phosphate glass;
step 1.1, weighing a certain amount of Na 2 CO 3 、La 2 O 3 、GeO 2 And H 3 PO 4 Placing the crucible in a platinum crucible, then placing the crucible in a heating furnace, heating to 800 ℃ at the speed of 10 ℃/min without covering the cover of the platinum crucible, and then preserving heat for 1-2 hours;
step 1.2, covering a platinum crucible with a cover, and continuously heating to 1250-1450 ℃ at the speed of 7-10 ℃/min;
step 1.3, taking out the platinum crucible, uniformly shaking the platinum crucible, then putting the platinum crucible into a heating furnace, keeping the temperature for 1 to 2 hours, then taking out the platinum crucible, uniformly shaking the platinum crucible, and then continuously putting the platinum crucible into the heating furnace for heating for 1 to 2 hours;
step 1.4, taking out the crucible in the step 1.3, and pouring the substances in the crucible into a circular mold to form cylindrical glass;
step 1.5, taking out the cylindrical glass, putting the cylindrical glass into a heating furnace, preserving the heat for 1 to 2 hours at the temperature of 440 to 460 ℃, and then cooling the cylindrical glass to room temperature for 12 hours to obtain transparent phosphate glass;
step 2, slicing the cylindrical transparent phosphate glass obtained in the step 1, and polishing one section by using sand paper;
step 3, placing the polished slices into an ultrasonic cleaning machine for cleaning for 30min, and then plating platinum on all polished surfaces;
step 4, putting the platinum-plated slices into a cleaned graphite crucible, introducing hydrogen into the graphite crucible, controlling the flow rate of the hydrogen to be 3-6 ml/min, then lapping aluminum sheets on the platinum, carrying out solid electrochemical displacement reaction in the graphite crucible by taking molten tin or graphite powder as a bottom electrode, controlling the temperature to be 310-350 ℃, taking out after the reaction is carried out for 5 hours, and grinding and polishing to obtain the transparent phosphate proton conductor;
in step 1, na 2 CO 3 ：H 3 PO 4 ：La 2 O 3 ：GeO 2 The ratio of the amounts of substances of (a) to (b) is 25:63: 10-2: 2 to 10.
2. The method of claim 1, wherein in the step 2, the thickness of the phosphate glass slice is 1mm, the diameter of the circular cross section of the phosphate glass slice is 1cm, and the polished sand paper is 1000 mesh.
3. The method according to claim 1, wherein in step 3, the polished surface of the cut piece is plated with platinum having a thickness of 50 nm.
4. A transparent phosphate proton conductor characterized by being produced by the production method according to any one of claims 1 to 3.
CN202011272097.3A 2020-11-13 2020-11-13 Transparent phosphate proton conductor and preparation method thereof Active CN112499965B (en)

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