KR20240015995A - Oxide containing a hydroxyl group prepared through a hydrothermal synthesis process - Google Patents

Abstract

The present invention relates to an oxide containing a hydroxyl group prepared through a hydrothermal synthesis process, and more specifically, to an oxide in which a hydroxyl group is directly doped rather than a hydroxyl group being substituted for an oxygen vacancy through hydrothermal synthesis.
The solvothermal direct doping technique of OH ions of the present invention is a new source technology that has not previously been reported, and by utilizing the developed technology, perovskite materials that were not previously considered hydrogen ion conductors can be newly discovered, It can also contribute to improving hydrogen ion conductivity by providing higher hydration power for materials such as BaZrO3, which has been widely used. In addition, the manufacturing method is simple and can be applied not only to perovskite materials but also to various ceramic materials, making it applicable to many applications.

Description

Oxide containing a hydroxyl group prepared through a hydrothermal synthesis process}

The present invention relates to an oxide containing a hydroxyl group prepared through a hydrothermal synthesis process, and more specifically, to an oxide in which a hydroxyl group is directly doped rather than a hydroxyl group being substituted for an oxygen vacancy through hydrothermal synthesis.

As policies for carbon neutrality are implemented around the world, a lot of investment is being made in related research to achieve zero carbon emissions by 2050. Hydrogen energy is considered the ultimate way to achieve zero carbon emissions, but the cost of producing green hydrogen, which can produce hydrogen without CO2 emissions, is still high and the energy conversion device that can convert hydrogen into other energy is still high. Much research and development is underway to improve these aspects due to low efficiency and durability.

A fuel cell is a representative energy conversion device that can convert chemical energy into electrical energy. It produces electricity when hydrogen is used as a fuel and produces water as a by-product. Conversely, electrolytic cells that apply electricity can produce hydrogen by decomposing water, so they can be considered an essential energy conversion device to achieve zero carbon emissions. In particular, solid oxide fuel/electrolytic cells are the 3rd generation fuel/electrolytic cells following the 1st generation alkaline fuel/electrolytic cells and the 2nd generation polymer fuel/electrolytic cells. They operate at high temperatures and can not only utilize cheap transition metals as catalysts, but also use heat energy as a catalyst. When used, it shows energy efficiency of close to 90% and is considered a next-generation fuel/electrolytic cell.

Unlike the oxygen ion conduction type, the hydrogen ion conduction type solid oxide fuel/electrolytic cell can be operated at a relatively low medium temperature of 450-600℃, and when the electrolytic cell is operated, hydrogen is produced at the electrode opposite to the electrode supplied with water. Therefore, it has the advantage of being able to produce high purity hydrogen. The core material of this type of solid oxide fuel/electrolytic cell is a hydrogen ion conductor used as an electrolyte and is mainly composed of oxides with a perovskite structure.

Perovskite material is an oxide with the chemical formula ABO3 and shows various properties depending on the type of ion present in the A-site and B-site. Since it has strong resistance to oxidation/reduction, it is used in many fields including electrolyte materials. It is being used in. Since the conductivity of a hydrogen ion conductor is proportional to the hydration characteristics of the material, improving hydration power is very important. Likewise, in perovskite hydrogen ion conductors, hydrogen ion conductivity depends on the concentration of hydroxide in the structure, and the existing method of increasing the concentration of hydroxide is to dope the B-site with a transition metal ion with a low oxidation number to force oxygen ion vacancies. is to form.

2B ^x _B +O ^x _O +M ₂ O ₃ =2M _B ^′ +V ^‥ _O +2BO ₂

Forming oxygen vacancies by doping, which is an existing technology, is an efficient method, but there are limits to the formation of oxygen vacancies because most perovskite materials have low solubility of doping ions or are not doped at all. In other words, low oxygen ion vacancy concentration is accompanied by low hydration power, and as a result, there is a limit to the improvement of hydrogen ion conductivity.

Republic of Korea Patent No. 10-2215719

In order to solve the above problems, the purpose of the present invention is to provide an oxide directly doped with a hydroxyl group.

Another object is to provide a method for producing an oxide directly doped with the hydroxyl group.

In order to achieve the above object, the present invention provides a high-temperature ceramic hydrogen ion conductor doped with hydroxide represented by the following formula (1):

[Formula 1]

A _1-x B _z O _3-y C _2y

In Formula 1,

A and B are each independently a metal cation,

C is a monovalent anion,

x, y and z are 0<x≤1, 0<y≤2, 0<z≤1, respectively.

In order to achieve the above other object, the present invention includes adding a first precursor containing at least one of nitrate, chloride, or acetate, a second precursor containing an alkoxide, and a mineralizer to a solvent. A first step of conducting a synthesis reaction by stirring;

A method for producing a ceramic hydrogen ion conductor is provided, which includes a second step of cooling to room temperature after the synthesis reaction and separating it from the supernatant.

The solvothermal direct doping technique of OH ions of the present invention is a new source technology that has not previously been reported, and by utilizing the developed technology, perovskite materials that were not previously considered hydrogen ion conductors can be newly discovered, It can also contribute to improving hydrogen ion conductivity by providing higher hydration power for materials such as BaZrO ₃ , which has been widely used. In addition, the manufacturing method is simple and can be applied not only to perovskite materials but also to various ceramic materials, making it applicable to many applications.

The developed hydrogen ion conductor can be used as an electrolyte for solid oxide fuel/electrolytic cells, and can be expanded to hydrogen separation membranes for high-purity hydrogen production, hydrogen sensors, and catalyst fields that require hydrogen ion conductivity. In addition, when ammonia, which has recently been in the spotlight as an alternative fuel, is directly applied to a fuel cell, the fuel can be used without diluting the product with water.

Figure 1 is an SEM image of Ca _1-x TiO _3-y (OH) _2y directly doped with hydroxide according to an embodiment of the present invention.
Figure 2 is a graph showing the mass reduction of three samples analyzed by TGA according to an embodiment of the present invention.
Figure 3 is a graph comparing the density analyzed by a gas pycnometer and the density calculated by neutron diffraction analysis according to an embodiment of the present invention.
Figure 4 is a graph showing hydrogen ion conductivity through impedance analysis according to an embodiment of the present invention.
Figure 5 shows a crystal structure containing deuterium, an isotope of hydrogen ion, by neutron diffraction analysis according to an embodiment of the present invention, (a) is CaTiO 3 (CaTiO ₃ synthesized by a general solid-phase method) (b) shows the neutron diffraction pattern of CTO(SS)), and (b) shows the neutron diffraction pattern of Ca _1-x TiO _3-y (OD) _2y (CTO(ST)) directly doped with deuterium. diffraction pattern). (c) shows that the distance between Ti ions and O ions increases in the c-axis direction and decreases the distance between Ti ions and O ions in the b-axis direction in the octahedral structure of the B-site by direct doping of deuterium. (d) is an image showing that the crystal structure is changed from CaTiO ₃ , which has an existing orthorhombic structure, to a tetragonal structure by direct doping with hydroxide due to the structural change in (c). (e) is an image showing the crystal structure of Ca _1-x TiO _3-y (OD) _2y (CTO(ST)) simulated based on neutron diffraction.
Figure 6 is a graph of Ca _1-x TiO _3-y (OD) _2y (CTO(ST)) directly doped with deuterium analyzed by TGA-mass according to an embodiment of the present invention.
Figure 7 shows the hydrogen ion conductivity of Ca _1-x TiO _3-y (OH) _2y and Ca _1-x TiO _3-y (OD) _2y directly doped with OH ions and OD ions according to an embodiment of the present invention. This is the graph that shows it.

Hereinafter, the present invention will be described in more detail.

According to one aspect of the present invention, a high-temperature ceramic hydrogen ion conductor doped with hydroxide represented by the following formula (1) is provided:

[Formula 1]

A _1-x B _z O _3-y C _2y

In Formula 1, A and B are each independently a metal cation, C is a monovalent anion, and x, y, and z are 0<x≤1, 0<y≤1, and 0<z≤1, respectively.

The A is preferably one or more cations selected from the group consisting of Group 1 metals, Group 2 metals, organic cations, and combinations thereof, and may be an alkaline earth metal or rare earth metal.

B is preferably at least one selected from the group consisting of Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Zn, Zr, Ce, Yb, Cr, Mn and Si.

C is preferably a hydroxyl group, and it is more preferable that the hydrogen of the hydroxyl group contains all isotopes of hydrogen.

The above chemical formula may include doping a hydroxyl group into the perovskite of ABO ₃ , but when x or z is 0, the chemical formula may include doping an oxide of AO or BO ₂ rather than ABO ₃ with a hydroxyl group.

The proton conductivity of the perovskite oxide of the present invention is preferably 2 X 10 ^-4 to 0.5 X 10 ^-5 Scm ^-1 . More preferably, the proton conductivity is 2 × 10 ^-4 to 1.5 × 10 ^-5 Scm ^-1 . In addition, A _1-x B _z O _3-y C _2y directly doped with the hydroxide of the present invention has a cube-shaped shape of about 300 to 700 nm (see Figure 1).

The density of the perovskite oxide of the present invention is preferably A _1-x B _z O _3-y C _2y (solvothermal): 3.7 to 4.01 g cm ^-3 , more preferably 3.8 to 4.0 g cm It could be ^-3 .

According to another aspect of the present invention, a first precursor containing at least one of nitrate, chloride, or acetate, a second precursor containing an alkoxide, and a mineralizer are added to the solvent and stirred. A first step of conducting a synthesis reaction; and a second step of cooling to room temperature after the synthesis reaction and separating it from the supernatant.

The first step synthesis method is preferably solvothermal synthesis or hydrothermal synthesis, and the first step solvent is preferably water or a polyhydric alcohol. In addition, the mineralizer in the first step is preferably a hydroxide, and more preferably one or more of NaOH, KOH, Ca(OH) ₂ , LiOH, RbOH, CsOH, and Mg(OH) ₂ can be used.

The present invention demonstrates that direct doping of hydroxide ions is possible when synthesizing perovskite (ABO3) material using the solvothermal method and ultimately involves the process of producing hydrated A _1-x B _z O _3-y C _2y . Includes.

The solvent can be used by a hydrothermal synthesis method using water, or by a solvothermal method using polyethylene glycol (PEG) as in the present invention. Ethanol, methanol, isopropyl alcohol, N, N-dimethylformamide, and deuterium oxide can be used alone or in combination with two or more of the above solvents. You can.

It is preferable to use a nitrate, chloride, or acetate-based precursor and an alkoxide-based precursor as the precursor, and more preferably, the alkoxide-based precursor is titanium isopropoxide or titanium ethoxide. and titanium butoxide, any one alkoxide may be used, but is not limited thereto.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary. And the terms used in this specification are for describing embodiments and are not intended to limit the present invention. In this specification, singular forms also include plural forms unless specifically stated in the phrase.

In this document, expressions such as “A or B,” “at least one of A or/and B,” or “one or more of A or/and B” may include all possible combinations of the items listed together. . For example, “A or B,” “at least one of A and B,” or “at least one of A or B” includes (1) at least one A, (2) at least one B, or (3) it may refer to all cases including both at least one A and at least one B.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

<Example>

reagent

Calcium nitrate tetrahydrate Ca(NO ₃ ) ₂ 4H ₂ O (Alfa Aesar, >99%), titanium(IV) isopropoxide (Aldrich, >97 %), polyethylene glycol 300 (20 mL, PEG- 300, Aldrich), calcium carbonate CaCO ₃ (Aldrich,>99.0%), titanium dioxide TiO ₂ (Alfa Aesar,>99.6%), sodium hydroxide NaOH (Sigma Aldrich), heavy water D ₂ O (Aldrich,>99.9%), Calcium oxide CaO (Aldrich, >99.9%), sodium deuterium oxide NaOD mineralizer (Aldrich, 40 wt. % in D ₂ O,99at.%D), acetic acid (Aldrich), dichloromethane (Sigma Aldrich, CH ₂ Cl ₂ , 1.33 gcm ^-3 ) was used, and all samples used in the following examples were commercially available reagents, and each reagent was used without separate purification.

<Example 1> Ca directly doped with hydroxide _1-x TiO _3-y (OH) _2y manufacturing

Ca _1-x TiO _3-y (OH) _2y particles were prepared by solvothermal synthesis. Specifically, fill 20 mL of PEG-300 in a 30 mL Teflon container and add titanium isopropoxide (0.005 mol), Ca(NO ₃ ) _2· 4H ₂ O (0.005 mol), and NaOH (0.7 g) to make 1 It was stirred for some time. After stirring, the Teflon container was placed in a SUS container, sealed, reacted in an oven at 190°C for 20 hours, and then cooled to room temperature. Next, the supernatant was separated by centrifugation at 3500 rpm for 10 minutes, washed once with diluted acetic acid and twice with DI-water, centrifuged, and dried in an oven at 80 °C for 1 day.

<Example 2> Conventional CaTiO ₃ and hydrated CaTiO ₃ (hydrated) manufacturing

Existing CaTiO ₃ was manufactured by a solid-phase method. 50 mL of acetone was filled in a 100 mL beaker, CaCO3 (0.005 mol) and TiO2 (0.005 mol) were added, and the mixture was stirred until all acetone was volatilized. The stirred powder was transferred to an alumina crucible and calcinated at 1100°C using an electric furnace. The calcined powder was pressed into pellets with a diameter of 13 mm and then sintered at 1350°C for 12 hours. Hydrated CaTiO ₃ (hydrated) was prepared by crushing the pellets, placing them in a hydrothermal synthesis vessel with DI-water, and hydrating them at 200°C for 24 hours.

<Example 3> Deuterium-doped Ca _1-x TiO _3-y (OD) _2y manufacturing

20 mL of PEG-300 was filled in a 30 mL Teflon container, 0.005 mol of titanium isopropoxide, 0.005 mol of dried CaO, and 0.7 g of sodium deuterium (NaOD) were added and stirred for 1 hour. After stirring, the Teflon container was placed in a SUS container, sealed, reacted in an oven at 190°C for 20 hours, and then cooled to room temperature. Next, the supernatant was separated by centrifugation at 3500 rpm for 10 minutes, washed once with diluted acetic acid and twice with D ₂ O, centrifuged, and dried in an oven at 80°C for 1 day.

<Example 4> Sample preparation for measuring hydrogen ion conductivity

Hydrated CaTiO ₃ (hydrated) and Ca _1-x TiO _3-y (OH) _2y powder directly doped with hydroxide were each added with 10 wt.% of PTFE and stirred. Each powder was pressed and molded into a 13 mm pellet shape, and Ag paste was applied to both sides in a circle with a diameter of 1 cm to be used as an electrode.

<Experimental Example 1> Hydration degree analysis

TGA analysis used Stanton Redcroft TG1000M: TGA equipment and analyzed OH ions in the perovskite structure in a dry air atmosphere. After raising the temperature from room temperature to 100°C, a process was performed to remove moisture adsorbed to the surface for 30 minutes. Afterwards, the temperature was raised to 900°C at 5°C per minute, and the temperature range and mass over which OH ions present in the crystal structure were removed were analyzed.

Figure 2 is a graph showing the mass reduction of three samples analyzed by TGA according to an embodiment of the present invention. As explained with reference to FIG. 2, CTO is a CaTiO3 perovskite material synthesized by a general solid-state method and without any treatment. CTO (hydrated) is a material obtained by hydrating the CaTiO3 material synthesized by the solid phase method above at 200 degrees. CTO(ST) is a Ca _1-x TiO _3-y (OH) _2y material directly doped with hydroxide by the solvothermal method of the present invention. The mass loss is due to the evaporation of hydroxide ions in the perovskite structure, and it was found that the material directly doped with hydroxide of the present invention contains about 10 times more hydroxide ions compared to existing materials, which means The decreasing mass of OH ions can be confirmed by the molar ratio.

It was confirmed that mass loss occurred between 200 and 500 ℃ as OH ions in the crystal structure were removed. It was confirmed that 0.15 OH ions were removed from the material directly doped with hydroxide of the present invention, whereas 0.015 OH ions were removed from the existing materials. As a result, it was possible to improve the hydration power by about 10 times by direct hydroxide doping.

<Experimental Example 2> Density analysis

Density analysis was performed using a pycnometer flask. After washing and completely drying the pycnometer, existing CaTiO ₃ , hydroxide-doped Ca _1-x TiO _3-y (OH) _2y powder and dichloromethane (CH ₂ Cl ₂ , 1.33gcm ^-3 ) The density was calculated using the formula below.

[Equation 1]

ρ _s = m _s / V _s

ρ _s : Density of sample (g cm ^-3 )

m _s : mass of sample (g)

V _s : volume of sample (cm ³ )

[Equation 2]

V _s = V ₀ - V _w

V ₀ : Volume of empty pycnometer (cm ³ )

V _w : Volume of working fluid (cm ³ )

[Equation 3]

V _w = {( m ₀ + m _s + m _w )-( m ₀ + m _s )}/ ρ _s

m ₀ : Mass of empty pycnometer (g)

m _w : mass of working fluid (g)

ρ _s : Density of working fluid (1.33 g cm ^-3 )

The data analyzed by neutron diffraction were interpreted by modification using GASAII software and the density was calculated.

Figure 3 is a graph comparing the density analyzed by a gas pycnometer and the density calculated by neutron diffraction analysis according to an embodiment of the present invention. Referring to FIG. 3, CTO(SS) represents CaTiO ₃ synthesized by a general solid-phase method, and CTO(ST) represents Ca _1-x TiO _3-y (OH) of the present invention directly doped with the hydroxide of the present invention. ) represents _2y . CNTO(ST) indicates that hydroxide and Ni ions are simultaneously doped. In the graph, the decrease in density when hydroxide is directly doped is explained by the formation of a vacancy in the place of the A-site Ca ion as the hydroxide ion is doped, as shown in the equation above. The density at this time was Ca _1-x TiO _3-y (OH) _2y (solvothermal): 3.914±0.02 g cm ^-3 CaTiO ₃ (solid-state): 4.005±0.03 g cm ^-3 .

<Experimental Example 3> Increase in grid volume

X-ray diffraction was analyzed at room temperature using a PANalytical Empyrean Diffractometer with filtered and monochromated CuKa1 radiation, and the analysis conditions were as follows. 2θ=10°~90°, 0.02° step size, and 1 hour collection time were set. The crystal structure and lattice volume of the materials were determined by refinement using WinXPow software and the results are shown in Table 1 below:

Table 1 above is a table showing the unit cell volume analyzed by XRD. CTO(SS) represents CaTiO ₃ synthesized by a general solid-state method, and CTO(ST) represents Ca _1-x TiO _3-y (OH) _2y of the present invention directly doped with hydroxide. Direct doping of hydroxide ions can be explained by the fact that the volume of the unit lattice increases as hydroxide ions are directly doped.

From Table 1, it can be seen that the lattice volume of the Ca _1-x TiO _3-y (OH) _2y material increases significantly compared to the existing CaTiO ₃ , and this is obtained as a result of direct doping of OH ions in the crystal structure.

<Experimental Example 4> Hydrogen ion conductivity analysis

0.03atm)를 흘려보내며 측정하였다.Hydrogen ion conductivity was analyzed in the frequency range of 1 Hz to 1 MHz using AC impedance spectroscopy (Solartron Analytical 1260A) connected to a Pt wire. A circular pellet with a diameter of 13 mm and a thickness of 1.5 mm was manufactured and a sample with electrodes coated with Ag paste on both sides was analyzed. Impedance was measured at intervals of 50°C from 150°C to 400°C using humidified Ar gas (p(H2O)).

It was measured while flowing 0.03 atm.

Figure 4 is a graph showing hydrogen ion conductivity through impedance analysis according to an embodiment of the present invention. When explained with reference to FIG. 4, CTO represents CaTiO ₃ synthesized by a general solid-phase method and has a hydrogen ion conductivity of 10 ^-6 Scm ^-1 . CTO(ST) represents Ca1-xTiO3-y(OH)2y directly doped with hydroxide and shows a hydrogen ion conductivity of 10 ^-4 Scm ^-1 , resulting in a hydrogen ion conductivity that is 2 orders of magnitude higher due to direct hydroxide doping. You can get it.

In Figure 4, conventional CaTiO ₃ showed a hydrogen ion conductivity of 1.4x10 ^-6 Scm ^-1 at 200℃, but Ca _1-x TiO _3-y (OH) _2y directly doped with hydroxide had 3.4x10 ^-5 Scm ^- It showed hydrogen ion conductivity that was about 2 orders of magnitude higher than ¹ .

Figure 7 is a graph showing the hydrogen ion conductivity of Ca _1-x TiO _3-y (OH) _2y and Ca _1-x TiO _3-y (OD) _2y directly doped with OH ions and OD ions. As explained with reference to FIG. 7, the conductivity of protons appears about 1.6 times faster than that of deuterons due to the difference in ionic mass between OH ions and OD. Therefore, it was found that direct doping of hydroxide ions within the crystal structure was possible.

<Experimental Example 5> Neutron diffraction analysis

Neutron diffraction was analyzed at room temperature using an ISIS time-of-flight high-resolution powder diffractometer (HRPD). A cylindrical vanadium can was used as a sample holder, and the overall intensity profile was recorded in the range d _hkl = 0.65 A to 2.6 A using a backscattering detector bank with a center of 2θ = 168°. Data was collected for 6 hours per sample, collected three times in total, integrated and corrected through adsorption correction. The HRPD pattern was refined through GSAS II software, and the crystal structure, lattice constant, location of deuterium, site occupancies, and atomic isotropic displacement factor were determined. For metering, the experimental background was determined using a Chebyshev polynomial model with 12 coefficients, and the diffraction peaks were fitted using a pseudo-Voigt profile. In Figure 5 (a) and (b), Rwp = 4.53% and goodnessoffit (GOF) = 2.94 were obtained for the existing CaTiO ₃ sample, and Rwp = ~6.12% and GOF = ~4.89 were obtained for the hydroxide directly doped Ca _{1- x} TiO _3-y (OH) _2y can be said to be reliable. The location of deuterium was estimated by performing a difference Fourier map.

Figure 5 shows a crystal structure containing deuterium, an isotope of hydrogen ion, based on neutron diffraction analysis. Referring to Figure 5, (a) shows the neutron diffraction pattern of CaTiO ₃ (CTO(SS)) synthesized by a general solid-phase method, and (b) shows the neutron diffraction pattern of Ca _1-x TiO _3- directly doped with deuterium. _y (OD) _2y (shows the neutron diffraction pattern of CTO(ST). (c) is the distance between Ti ions and O ions in the c-axis direction in the octahedral structure of the B-site by direct doping of deuterium. increases and the distance between Ti ions and O ions decreases in the b-axis direction. (d) shows direct doping of hydroxide in CaTiO ₃ having an existing orthorhombic structure due to the structural change in (c) above. It shows that the crystal structure changes closer to the tetragonal structure. (e) shows the crystal structure of Ca _1-x TiO _3-y (OD) _2y (CTO(ST)) simulated based on neutron diffraction. As a result, the shortened distance between Ti ions and O ions facilitates intra-molecular proton transfer, and the A-site vacancy also facilitates inter-molecular proton transfer, resulting in an increase in hydrogen ion conductivity. appear.

Figure 6 is a graph of Ca _1-x TiO _3-y (OD) _2y (CTO(ST)) directly doped with deuterium analyzed by TGA-mass. When explained with reference to Figure 6, D, an isotope of H When doped, the ion current value for OH does not appear and the ion current value for OD appears in the mass reduction section, indicating that OD ions are doped directly within the crystal structure. Content of OD ions simulated by neutron diffraction The content of OD ions measured by TGA-mass analysis is shown in Table 2 below:

Therefore, in the oxide directly doped with a hydroxyl group according to the present invention, as the distance between the cation and oxygen is shortened, both intra-molecular and inter-molecular proton transfer are facilitated, and perovskite transfer is facilitated by the solid-state method. It was found that the Rwp value and GOF value increased compared to when synthesizing . In addition, it was confirmed that density, lattice volume, and hydrogen ion conductivity were improved compared to the prior art.

The foregoing has described, rather broadly, the features and technical advantages of the present invention to enable a better understanding of the claims described below. A person skilled in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing its technical idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the claims and their equivalent concepts should be construed as being included in the scope of the present invention.

Claims (9)

A high-temperature ceramic hydrogen ion conductor doped with hydroxide represented by the following formula (1):
[Formula 1]
A _1-x B _z O _3-y C _2y
In Formula 1,
A and B are each independently a metal cation,
C is a monovalent anion,
x, y and z are 0<x≤1, 0<y≤2, 0<z≤1, respectively.
According to claim 1,
A high-temperature ceramic hydrogen ion conductor doped with hydroxide, characterized in that the formula is one or more cations selected from the group consisting of Group 1 metals, Group 2 metals, rare earth metals, organic cations, and combinations thereof.
According to claim 2,
A is a hydroxide-doped high-temperature ceramic hydrogen ion conductor, characterized in that A is an alkaline earth metal or a rare earth metal.
According to claim 1,
wherein B is at least one selected from the group consisting of Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti, Zn, Zr, Ce, Yb, Cr, Mn and Si. type ceramic hydrogen ion conductor.
According to claim 1,
A high-temperature ceramic hydrogen ion conductor doped with hydroxide, wherein C is a hydroxyl group.
According to claim 5,
A high-temperature ceramic hydrogen ion conductor doped with hydroxide, wherein the hydrogen of the hydroxyl group contains all isotopes of hydrogen.
A first step of performing a synthesis reaction by adding a first precursor containing at least one of nitrate, chloride, or acetate, a second precursor containing an alkoxide, and a mineralizer to a solvent and stirring;
A method for manufacturing a ceramic hydrogen ion conductor comprising a second step of cooling to room temperature after the synthesis reaction and separating it from the supernatant.
According to claim 7,
A method of producing a ceramic hydrogen ion conductor, characterized in that the first step synthesis method is solvothermal synthesis or hydrothermal synthesis.
According to claim 8,
A method for manufacturing a ceramic hydrogen ion conductor, wherein the mineralizer in the first step is hydroxide.