阅读说明：本技术 一种固体氧化物电池的制备方法以及由此得到的固体氧化物电池 (Preparation method of solid oxide battery and solid oxide battery obtained by preparation method ) 是由 王建强 林逍 杨军鹏 孔芳弟 杨云 张林娟 解春雨 于 2020-12-25 设计创作，主要内容包括：本发明涉及一种固体氧化物电池的制备方法,其包括在分别制备氢电极层、电解质层、阻隔层和氧电极层后将其依次组装得到固体氧化物电池,该电解质层为无孔致密电解质薄膜,该无孔致密电解质薄膜的制备包括如下步骤：形成含孔致密电解质薄膜；将含孔致密电解质薄膜置于过渡金属盐溶液中进行原位热解纳米粒子处理,得到的纳米粒子沉积于含孔致密电解质薄膜的微孔结构中以制备无孔致密电解质薄膜。本发明还涉及一种根据上述制备方法得到的固体氧化物电池。根据本发明的固体氧化物电池的制备方法,可以得到无孔致密电解质薄膜,该致密性提高的电解质层稳定地隔绝了氢氧两侧电极气体,提高了电池器件的稳定性。(The invention relates to a preparation method of a solid oxide battery, which comprises the steps of preparing a hydrogen electrode layer, an electrolyte layer, a barrier layer and an oxygen electrode layer respectively, and then assembling the hydrogen electrode layer, the electrolyte layer, the barrier layer and the oxygen electrode layer in sequence to obtain the solid oxide battery, wherein the electrolyte layer is a nonporous compact electrolyte film, and the preparation of the nonporous compact electrolyte film comprises the following steps: forming a porous dense electrolyte film; and (3) placing the porous compact electrolyte film into a transition metal salt solution for in-situ pyrolysis nano particle treatment, and depositing the obtained nano particles in a microporous structure of the porous compact electrolyte film to prepare the nonporous compact electrolyte film. The invention also relates to a solid oxide battery obtained according to the preparation method. According to the preparation method of the solid oxide battery, the nonporous compact electrolyte film can be obtained, the electrolyte layer with improved compactness stably isolates electrode gases at two sides of hydrogen and oxygen, and the stability of a battery device is improved.)

1. A preparation method of a solid oxide battery comprises the steps of preparing a hydrogen electrode layer, an electrolyte layer, a barrier layer and an oxygen electrode layer respectively, and then assembling the hydrogen electrode layer, the electrolyte layer, the barrier layer and the oxygen electrode layer in sequence to obtain the solid oxide battery, wherein the electrolyte layer is a nonporous compact electrolyte film, and the preparation of the nonporous compact electrolyte film comprises the following steps:

s1, forming a porous dense electrolyte film;

s2, placing the porous dense electrolyte film in a transition metal salt solution for in-situ pyrolysis nanoparticle treatment, and depositing the obtained nanoparticles in micropores of the porous dense electrolyte film to prepare the nonporous dense electrolyte film.

2. The production method according to claim 1, wherein the pore-containing dense electrolyte membrane is a membrane containing 5 to 10% by volume of micropores.

3. The method according to claim 1, wherein step S1 includes: preparing electrolyte slurry, uniformly depositing the electrolyte slurry by adopting a screen printing method, removing glue, and sintering to obtain the porous compact electrolyte film.

4. The method according to claim 1, wherein the solute of the transition metal salt solution is at least one of a soluble chloride, nitrate and organic complex of the transition metal, and the solvent of the transition metal salt solution is at least one of water, ethanol and propanol.

5. The method according to claim 4, wherein the transition metal is Y, Ce, Zr and/or Ba.

6. The method according to claim 4, wherein the transition metal salt solution is a mixed solution of different transition metal salts.

7. The method according to claim 4, wherein the transition metal salt solution is a mixed aqueous solution of at least two of yttrium chloride, yttrium nitrate, yttrium isopropoxide, zirconium chloride, zirconium nitrate, zirconium acetate, and zirconium n-butoxide.

8. The method of claim 1, wherein the nanoparticles are oxide nanoparticles.

9. The method according to claim 1, wherein step S2 includes: the porous compact electrolyte film is put into a transition metal salt solution with the solubility of 0.5-5M, and the nano particles are pyrolyzed in situ for 0.5-24h at the temperature of 60-90 ℃.

10. A solid oxide cell obtained by the production method according to any one of claims 1 to 9, wherein the solid oxide cell is a solid oxide fuel cell or a solid oxide fuel electrolysis cell.

Technical Field

The present invention relates to a battery device, and more particularly, to a method of manufacturing a solid oxide battery and a solid oxide battery obtained thereby.

Background

The high-temperature solid oxide cell device has bidirectional functionalization, on one hand, chemical energy of fuel can be directly converted into electric energy through electrochemical reaction, and the high-temperature solid oxide cell device is expressed as a solid oxide fuel cell and has the characteristics of high energy conversion efficiency and small environmental pollution; on the other hand, waste heat and waste electricity can be utilized to realize the preparation of high-purity hydrogen by electrolyzing water, and the electrolytic cell is represented as a solid oxide electrolytic cell and has the characteristics of low energy consumption and high hydrogen production purity. Among them, the solid oxide cell is considered as a core reaction device with great application prospect because it does not need to use noble metal catalyst or catalytic component and can be compatible with the conversion reaction of hydrogen and various carbon-containing gases and coal gasification energy.

The core component of the solid oxide battery device generally consists of three layers of porous films, namely a hydrogen electrode layer, an oxygen electrode layer and a barrier layer, and a dense non-porous electrolyte layer. The electrolyte layer is formed by sintering solid particles with a certain size at high temperature, and the porosity of the porous hydrogen electrode supporting layer and the porous active layer is easily reduced due to overhigh sintering temperature, so that the performance of a battery device is influenced. The sintering temperature is moderate, a small amount of pinholes are easy to exist, partial leakage and air leakage are caused, the ohmic impedance of the battery is increased, and the stability of the solid oxide battery in long-term operation and the energy conversion efficiency are directly influenced. Therefore, the dense non-porous structure of the electrolyte thin film is critical to the performance and stability of the solid oxide cell. In the prior art, a screen printing method is usually adopted to prepare a high-temperature solid oxide electrolyte film, and the preparation method has the problems of unsatisfactory compactness of film formation by one-time sintering and small amount of open pores and closed pores. In addition, since the core components of the high-temperature solid oxide fuel cell are mainly oxide ceramic materials, the uniformity of the particle size is large, interface and pore resistance are easy to generate in the processing process, and the commercial development of the cell is limited.

Disclosure of Invention

In order to solve the problems of unsatisfactory compactness of a thin film and the like in the prior art, the invention provides a preparation method of a solid oxide battery and the solid oxide battery obtained by the preparation method.

The preparation method of the solid oxide battery comprises the steps of preparing a hydrogen electrode layer, an electrolyte layer, a barrier layer and an oxygen electrode layer respectively, and then assembling the hydrogen electrode layer, the electrolyte layer, the barrier layer and the oxygen electrode layer in sequence to obtain the solid oxide battery, wherein the electrolyte layer is a nonporous compact electrolyte film, and the preparation of the nonporous compact electrolyte film comprises the following steps: s1, forming a porous dense electrolyte film; s2, placing the porous dense electrolyte film in a transition metal salt solution for in-situ pyrolysis nanoparticle treatment, and depositing the obtained nanoparticles in micropores of the porous dense electrolyte film to prepare the nonporous dense electrolyte film.

Preferably, the pore-containing dense electrolyte membrane is a membrane containing 5 to 10% by volume of micropores.

Preferably, step S1 includes: preparing electrolyte slurry, uniformly depositing the electrolyte slurry by adopting a screen printing method, removing glue, and sintering to obtain the porous compact electrolyte film.

Preferably, the solute of the transition metal salt solution is at least one of a soluble chloride, a nitrate and an organic complex of the transition metal, and the solvent of the transition metal salt solution is at least one of water, ethanol and propanol.

Preferably, the transition metal is Y, Ce, Zr and/or Ba.

Preferably, the transition metal salt solution is a mixed solution of different transition metal salts.

Preferably, the transition metal salt solution is a mixed aqueous solution of at least two of yttrium chloride, yttrium nitrate, yttrium isopropoxide, zirconium chloride, zirconium nitrate, zirconium acetate, and zirconium n-butoxide.

Preferably, the nanoparticles are oxide nanoparticles. More preferably, the nanoparticles are nano-doped oxide particles.

Preferably, step S2 includes: the porous compact electrolyte film is put into a transition metal salt solution with the solubility of 0.5-5M, and the nano particles are pyrolyzed in situ for 0.5-24h at the temperature of 60-90 ℃. More preferably, the solubility of the transition metal salt solution is 2-4M, and the porous compact electrolyte film is subjected to in-situ pyrolysis nano particle treatment for 10-12h at 70-80 ℃.

The solid oxide cell obtained by the above preparation method according to the present invention is a solid oxide fuel cell or a solid oxide fuel electrolysis cell.

According to the preparation method of the solid oxide battery, the nonporous compact electrolyte film can be obtained, the electrolyte layer with improved compactness stably isolates electrode gases at two sides of hydrogen and oxygen, and the stability of a battery device is improved. In addition, due to the deposition of the nano particles, the grain boundaries among the large particles of the original electrolyte layer can be better contacted through the deposited nano particles, and the grain boundary contact surface among the solid particles is improved, so that the ohmic resistance and the polarization resistance of the electrolyte layer are reduced, the possibility of gas mixing at the two electrode sides of hydrogen and oxygen is avoided, and the energy conversion efficiency and the stability of the solid oxide battery are improved.

Drawings

Fig. 1 is a surface scanning electron micrograph of a dense electrolyte thin film containing pores according to comparative example 1 of the present invention;

fig. 2 is a surface scanning electron micrograph of a nonporous dense electrolyte thin film according to example 1 of the present invention;

fig. 3 is a surface scanning electron micrograph of a nonporous dense electrolyte thin film according to example 2 of the present invention;

fig. 4 is a surface scanning electron micrograph of a nonporous dense electrolyte thin film according to example 3 of the present invention;

fig. 5 is an open circuit voltage of a solid oxide cell assembled with a dense electrolyte membrane containing pores and no pores according to the present invention.

Detailed Description

The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

The method for manufacturing a solid oxide cell according to the present invention includes manufacturing a hydrogen electrode layer by casting. The hydrogen electrode layer is a porous sintered film and comprises a supporting layer and an active layer, wherein the supporting layer is located below the active layer, the supporting layer is composed of nickel oxide and 3 wt% of zirconia-based electrolyte, and the active layer is composed of nickel oxide and 8 wt% of zirconia-based electrolyte. In a preferred embodiment, the zirconia-based electrolyte is an electrolyte material of an oxygen ion conductor such as zirconia-based yttria, zirconia-based scandia, or zirconia-based ceria, and a proton-conducting electrolyte material such as barium zirconium cerium yttrium. In a preferred embodiment, the zirconia-based electrolyte is YSZ (yttria-stabilized zirconia). In a preferred embodiment, the thickness of the hydrogen electrode layer is 200 to 500 μm.

The preparation method of the solid oxide battery comprises the step of forming a hole-containing dense electrolyte film by screen printing, wherein the hole-containing dense electrolyte film is a dense electrolyte film containing a small number of micropores (also called pinholes). In a preferred embodiment, the pore-containing dense electrolyte membrane is a membrane containing 5-10% by volume of pinholes. Specifically, electrolyte slurry (such as zirconia-based electrolyte slurry or cerium-based electrolyte slurry) is prepared, the electrolyte slurry is uniformly deposited by a screen printing method, and the electrolyte slurry is sintered after glue discharge to obtain the porous compact electrolyte film. In a preferred embodiment, the gel is discharged at 500-700 ℃ for 1-3h, for example, at 600 ℃ for 2 h. In a preferred embodiment 1300 ℃ and 1400 ℃ are sintered for 3-5h, for example 1350 ℃ for 4 h. In a preferred embodiment, the electrolyte layer is 8YSZ (yttria stabilized zirconia). In a preferred embodiment, the thickness of the porous dense electrolyte membrane is 8 to 15 μm.

The preparation method of the solid oxide battery comprises the steps of placing the compact electrolyte film containing the holes in a transition metal salt solution for in-situ pyrolysis nano particle treatment, and depositing the obtained nano particles in the solution containing the holesThe dense electrolyte membrane is in the micropores to prepare a nonporous dense electrolyte membrane. In a preferred embodiment, the solute of the transition metal salt solution is at least one of a soluble chloride, nitrate and organic complex of a transition metal, the transition metal is Y, Ce, Zr and/or Ba, the solvent of the transition metal salt solution is at least one of water, ethanol and propanol, and the solute reacts with the solvent to generate the corresponding oxide nanoparticles in situ. Preferably, the transition metal salt solution is a mixed solution of different transition metal salts, mixed oxide nanoparticles of corresponding metals are generated in situ, and are deposited in micropores of the porous compact electrolyte film on a micro-nano scale, secondary micro-nano regulation treatment is performed on the electrolyte layer, and the compactness of the electrolyte layer is improved. In a preferred embodiment, the transition metal salt solution is a mixed aqueous solution of at least two of yttrium chloride, yttrium nitrate, yttrium isopropoxide, zirconium chloride, zirconium nitrate, zirconium acetate, and zirconium n-butoxide. In a preferred embodiment, the mixed solution is YCl₃And ZrCl₄To obtain nano-Y doped ZrO₂Particles to obtain nano-Y doped ZrO₂A modified nonporous dense electrolyte membrane. Specifically, the porous dense electrolyte film is put in a transition metal salt solution with the solubility of 0.5-5M at the temperature of 60-90 ℃ and is subjected to in-situ nanoparticle pyrolysis treatment for 0.5-24 h. In a preferred embodiment, the solubility of the transition metal salt solution is 2-4M, and the porous dense electrolyte film is subjected to in-situ pyrolysis nanoparticle treatment for 10-12h at 70-80 ℃.

The preparation method of the solid oxide battery comprises the step of forming the barrier layer through screen printing. The barrier layer is a porous sintered film. In a preferred embodiment, the porous barrier layer film is obtained by sintering at 1200 ℃. In a preferred embodiment, the barrier layer is GDC. Specifically, barrier slurry composed of gadolinium-doped cerium oxide is prepared, and a screen printing method is adopted to uniformly deposit the barrier slurry to form a barrier thin layer, so that a porous barrier layer is obtained. In a preferred embodiment, the thickness of the thin barrier layer is 3-5 μm and the thickness of the barrier layer is 10-15 μm.

The method for manufacturing a solid oxide cell according to the present invention includes forming an oxygen electrode layer by screen printing. The oxygen electrode layer is a porous sintered film. In a preferred embodiment, the porous oxygen electrode membrane is obtained by sintering at 1100 ℃. In a preferred embodiment, the oxygen electrode layer is LSCF (lanthanum cobaltate) -GDC. Specifically, preparing oxygen electrode paste consisting of LSFC or LSM (lanthanum manganate), uniformly depositing the oxygen electrode paste by a screen printing method to form an oxygen electrode layer, obtaining a porous oxygen electrode thin layer, and repeatedly performing operation according to the thickness of the oxygen electrode layer to prepare the oxygen electrode layer. In a preferred embodiment, the thickness of the oxygen electrode layer is 15-30 μm.

The preparation method of the solid oxide battery comprises the step of assembling the hydrogen electrode layer, the nonporous compact electrolyte film, the barrier layer and the oxygen electrode layer from bottom to top in sequence to obtain the solid oxide battery. It should be understood that the solid oxide cell may be a solid oxide fuel cell or a solid oxide fuel electrolytic cell, depending on the application.

Comparative example 1

The cells used were solid oxide cells supported by a hydrogen electrode (cell size 5 x 5 cm)²) The cell structure is NiO-YSZ//8YSZ// GDC// LSCF-GDC, and all preparation methods are routine operations which are verified by experiments.

Preparing a porous supporting layer and an active layer NiO-YSZ by a tape casting method, and sintering at 1400 ℃ to prepare the porous hydrogen electrode layer.

Preparing a YSZ electrolyte layer by a screen printing method, raising the temperature to 600 ℃/min at the heating rate of 1 ℃/min, keeping for 2 hours, raising the temperature to 1350 ℃/min at the heating rate of 1 ℃/min after organic substances in the slurry are completely volatilized, keeping for 8 hours, and lowering the temperature to room temperature at the cooling rate of 2 ℃/min to obtain the porous compact electrolyte film.

And (3) obtaining a porous electrode film with a certain thickness by screen printing of a GDC barrier layer and an LSCF oxygen electrode layer and high-temperature sintering, and assembling into a complete solid oxide battery.

Fig. 1 is a scanning electron micrograph of the surface of the pore-containing dense electrolyte thin film of this comparative example, which contains a small number of micropores. As shown in fig. 5, the open circuit voltage of 0.99V at 750 ℃ is larger than the theoretical value in the solid oxide cell assembled with the porous dense electrolyte thin film, indicating that the solid oxide cell has partial air leakage and self-loss.

Example 1

The preparation method of each layer was the same as in comparative example 1 except for the electrolyte layer.

Preparing a YSZ layer on the porous hydrogen electrode layer NiO-YSZ substrate by a screen printing method, raising the temperature to 600 ℃/min at the heating rate of 1 ℃/min, keeping for 2 hours, raising the temperature to 1350 ℃/min at the heating rate of 1 ℃/min after organic substances in the slurry are completely volatilized, keeping for 8 hours, and lowering the temperature to room temperature at the cooling rate of 2 ℃/min to obtain the porous compact electrolyte film. Then placing the membrane in a mixed aqueous solution of 0.5M yttrium nitrate and zirconium nitrate (the volume ratio is 8/92), and placing the membrane in a constant-temperature 80 ℃ oven for heat treatment for 10h to obtain a nano-particle secondary treatment electrolyte membrane, namely a nonporous compact electrolyte membrane.

Example 2

Preparing a YSZ layer on the porous hydrogen electrode layer NiO-YSZ substrate by a screen printing method, raising the temperature to 600 ℃/min at the heating rate of 1 ℃/min, keeping for 2 hours, raising the temperature to 1350 ℃/min at the heating rate of 1 ℃/min after organic substances in the slurry are completely volatilized, keeping for 8 hours, and lowering the temperature to room temperature at the cooling rate of 2 ℃/min to obtain the porous compact electrolyte film. Then placing the membrane in a mixed 75% ethanol solution of 2M yttrium chloride and zirconium chloride (volume ratio of 8/92), and placing the membrane in a constant-temperature 75 ℃ oven for heat treatment for 12h to obtain a nano-particle secondary treatment electrolyte membrane, namely a nonporous compact electrolyte membrane.

Example 3

Preparing a YSZ layer on the porous hydrogen electrode layer NiO-YSZ substrate by a screen printing method, raising the temperature to 600 ℃/min at the heating rate of 1 ℃/min, keeping for 2 hours, raising the temperature to 1350 ℃/min at the heating rate of 1 ℃/min after organic substances in the slurry are completely volatilized, keeping for 8 hours, and lowering the temperature to room temperature at the cooling rate of 2 ℃/min to obtain the porous compact electrolyte film. Then placing the membrane in 5M mixed isopropanol solution of yttrium isopropoxide and n-butyl zirconium (volume ratio 8/92), and placing the membrane in a constant temperature 80 ℃ oven for heat treatment for 24h to obtain the electrolyte membrane for secondary treatment of the nano particles, namely the nonporous compact electrolyte membrane.

Fig. 2 to 4 are scanning electron micrographs of the surfaces of the nonporous dense electrolyte thin films of examples 1 to 3, respectively, as can be seen by comparing with fig. 1: a large amount of nanoparticles are deposited between the electrolyte particles of the nonporous dense electrolyte membrane, so that the contact between the electrolyte particles is firmer.

As shown in FIG. 5, the solid oxide cell assembled with the nonporous dense electrolyte thin films of examples 1 to 3 was operated at 750 ℃ and 3% H₂After the side of the hydrogen electrode is stabilized, the open-circuit voltage values of the solid oxide battery device are respectively 1.03V, 1.07V and 1.10V, and are closer to the theoretical open-circuit voltage value, which shows that the assembled solid oxide battery is stable, and the electrolyte layer is compact and non-porous.

The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.