CN105226295B - A kind of dielectric film and method for producing oxygen through based on air oxygen - Google Patents
A kind of dielectric film and method for producing oxygen through based on air oxygen Download PDFInfo
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- CN105226295B CN105226295B CN201510575817.6A CN201510575817A CN105226295B CN 105226295 B CN105226295 B CN 105226295B CN 201510575817 A CN201510575817 A CN 201510575817A CN 105226295 B CN105226295 B CN 105226295B
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- oxygen
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of dielectric films based on air oxygen, including electrolyte layer and the cathode electrode as air side electrode layer positioned at electrolyte layer two sides and the anode electrode as oxygen side electrode layer；The cathode electrode is identical with the constituent of anode electrode.In addition, also disclosing the method for producing oxygen through and its oxygen product obtained using above-mentioned dielectric film.The ionic conductivity of dielectric film of the present invention has 100% selectivity, dielectric film is fine and close, pure oxygen can be easily and efficiently obtained, and device assembly production is simple, high yield rate, low energy consumption, to breach sophisticated industry to the technical bottleneck of high purity oxygen gas demand.
Description
Technical field
The present invention relates to solid-state ionics field more particularly to a kind of dielectric film based on air oxygen and oxygen sides processed
Method.
Background technique
Oxygen is a kind of important chemical products, in steel industry, health care, aerospace, oxygen-enriched combusting, fuel electricity
The fields such as pond and chemical engineering have important application.Current the manufacture of oxygen enterprise most in the world uses air liquefaction point
From method, principle is fractionated using each component boiling point difference in air, and this method is in the process compressed to air
In can consume a large amount of electric energy, oxygen cost processed is very high.The method efficiency for the pressure-variable adsorption separation air that developed recently gets up has
It is improved, but is limited by reaction principle, the oxygen of 93% or so purity only up to be obtained, product quality is lower, can only be applicable in
It is produced in general industry.Although and the oxygen permeation membrane oxygenerating technology theoretically available pure oxygen based on electronics, ion mixed conductor,
But it needs to extract oxygen from pure oxygen side using vacuum pump, then repressurization obtains atmospheric oxygen.Vacuum pump, booster pump and preheating
System can expend big energy, and due in air partial pressure of oxygen there was only 0.21, oxygen permeation membrane two sides need to bear 5 times or more of pressure
Strong poor just achievable oxygen efficiently separates.This proposes very high requirement, but oxygen flow film strength and thickness to oxygen flow film strength
Spend proportional, and oxygen permeating amount and thickness are in inverse ratio, and the reconciliation of the two is very difficult, causes oxygen permeation membrane yields low, it is difficult to
Realize industrialization.In addition, electrolysis water or vapor oxygen are also a kind of method possible in theory, but electrolytic process energy consumption is huge
Greatly, the hydrogen storage and transportation and as one of product is difficult, and usage amount and use environment and oxygen mismatch, and constrains electrolysis water system
The development of oxygen.
Summary of the invention
It is efficient and convenient based on air oxygen that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of oxygen processed
Dielectric film improve the application level of oxygen to obtain purity is high, the stable oxygen of supply, extend the application range of oxygen,
To break through sophisticated industry to the technical bottleneck of high purity oxygen gas demand.Another object of the present invention is to provide use above-mentioned electrolysis
The method for producing oxygen through of plasma membrane and its oxygen product obtained.
The purpose of the present invention is achieved by the following technical programs:
A kind of dielectric film based on air oxygen provided by the invention, including electrolyte layer and be located at electrolyte layer
The cathode electrode as air side electrode layer and the anode electrode as oxygen side electrode layer of two sides；The cathode electrode and sun
The constituent of pole electrode is identical.
Further, the ingredient of electrolyte layer of the present invention is one kind or combinations thereof of following substance:
Yttrium stable zirconium oxide (YSZ) (Y2O3)x(ZrO2)1-x, x=0.03~0.08,
Scandium stabilizing zirconia (ScSZ) (Sc2O3)x(ZrO2)1-x, x=0.08~0.11,
Gd doped cerium oxide (GDC) GdxCe1-xO2-0.5x, x=0.1~0.4,
Sm doped cerium oxide (SDC) SmxCe1-xO2-0.5x, x=0.1~0.4,
Lanthanum gallate (LSGM) La of Sr and Mg codope0.8Sr0.2Ga0.9Mg0.1O3、
Er adulterates bismuth oxide (ESB) (Er2O3)x(Bi2O3)1-x, x=0.1~0.3.
Further, the ingredient of cathode electrode/anode electrode of the present invention is one kind or combinations thereof of following substance:
(LSM)La1-xSrxMnO3, x=0.2~0.4,
(LSC)La1-xSrxCoO3, x=0.2~0.4,
(LSF)La1-xSrxFeO3, x=0.2~0.4,
(LSN)La1-xSrxNiO3, x=0.2~0.4,
(NN)Nd2NiO4、
(SFM)Sr2Fe1.5Mo0.5O6, x=0.2~0.4.
In above scheme, the relative density of electrolyte layer of the present invention is greater than 96%.The electrolyte layer with a thickness of 5
~200 μm, the thickness of cathode electrode and anode electrode be respectively 20~200 μm.
Another object of the present invention is achieved by the following technical programs:
Method for producing oxygen through provided by the invention using above-mentioned dielectric film, by the one side of the cathode electrode of the dielectric film
It is placed in air side, applies cathode potential to it, the oxygen in air obtains electronics and becomes oxonium ion；The oxonium ion is through electricity
After solving plasma membrane arrival anode electrode, loses electronics and be oxidized to oxygen；The operating temperature of the dielectric film is 500~1000
DEG C, operating voltage is 50~300mV.
Using oxygen product made from above-mentioned method for producing oxygen through, the oxygen purity is 99.90~99.99%.
The invention has the following advantages:
(1) ionic conductivity of dielectric film of the present invention has 100% selectivity, and dielectric film is fine and close, in air
Nitrogen and other impurities cannot reach pure oxygen side through dielectric film, to easily and efficiently obtain pure oxygen, oxygen processed per hour
Amount is 83~125ml h-1cm-2。
(2) common oxygen permeation membrane (such as Ba is solved1-xSrxCoO3) problem that needs to bear 5 times or more pressure differences, make membrane material
The intensity requirement of material is greatly reduced, and the design difficulty of reaction unit is significantly reduced.
(3) due to can nernst voltage (theoretical voltage) less than 50mV, in addition the activity of device electrode at the working temperature is non-
Chang Gao, overpotential is small, and practical decomposition voltage (operating voltage) is less than 0.3V, and oxygen energy consumption processed significantly reduces.
(4) with electrolysis vapor reaction unit compared with, the present invention not only have the advantages that it is above-mentioned low energy consumption, but also not by
The limitation of hydrogen disposition.Moreover, both sides electrode material is in oxidizing atmosphere, the requirement to electrode material and electrolyte
Relax significantly.
(5) two lateral electrode of dielectric film is in oxidizing atmosphere, and there is no the danger such as burning, explosion, seals to device
Requirement be remarkably decreased.
(6) device assembly produces simple, high yield rate, advantageously reduces cost.
Detailed description of the invention
Below in conjunction with embodiment and attached drawing, the present invention is described in further detail:
Fig. 1 is the structural schematic diagram of dielectric film of the present invention.
In figure: electrolyte layer 1, cathode electrode 2, anode electrode 3
Specific embodiment
A kind of dielectric film based on air oxygen of the embodiment of the present invention, as shown in Figure 1, including electrolyte layer 1, Yi Jiwei
The cathode electrode 2 as air side electrode layer in electrolyte layer two sides and the anode electrode 3 as oxygen side electrode layer.Its
In, electrode layer its cathode electrode 2, the ingredient of anode electrode 3 are identical.
Its electrolyte layer of various embodiments of the present invention dielectric film and electrode layer at being grouped as shown in table 1.
1 its electrolyte layer of various embodiments of the present invention dielectric film of table and electrode layer at being grouped as
The wt% of each material composition is shared content in electrolyte layer/electrode layer.
The present invention is as follows using the method for producing oxygen through of above-described embodiment dielectric film: by the one side of the cathode electrode of dielectric film
It is placed in air side, applies cathode potential to it, the oxygen in air obtains electronics and becomes oxonium ion: O2+ 4e=2O2-；Oxygen from
After son is reached through dielectric film to electrode (anode electrode), loses electronics and be oxidized to oxygen: 2O2-- 4e=O2；Wherein,
Electrolyte layer be it is one or more layers, the overall thickness of electrolyte layer is 5~200 μm, the thickness of cathode electrode and anode electrode
Respectively 20~200 μm；The operating temperature of dielectric film is 500~1000 DEG C, and operating voltage is 50~300mV.
Its running parameter of various embodiments of the present invention method for producing oxygen through and oxygen effect processed are respectively as shown in table 2, table 3.
The technological parameter of 2 various embodiments of the present invention method for producing oxygen through of table
* electrode layers thickness is cathode electrode, the respective thickness of anode electrode.
The oxygen effect processed of 3 various embodiments of the present invention method for producing oxygen through of table
| Embodiment | Oxygen purity (%) | Oxygen making amount (mlh per hour-1cm-2) |
| Embodiment one | 99.95 | 105 |
| Embodiment two | 99.98 | 104.5 |
| Embodiment three | 99.91 | 105 |
| Example IV | 99.93 | 83 |
| Embodiment five | 99.96 | 105 |
| Embodiment six | 99.97 | 125 |
| Embodiment seven | 99.92 | 105 |
| Embodiment eight | 99.99 | 83 |
| Embodiment nine | 99.95 | 83 |
| Embodiment ten | 99.96 | 125 |
Claims (2)
1. a kind of dielectric film based on air oxygen, it is characterised in that: be plate armature, including electrolyte layer (1) and
It is electric positioned at the cathode electrode (2) as air side electrode layer of electrolyte layer (1) two sides and the anode as oxygen side electrode layer
Pole (3)；
The relative density of the electrolyte layer (1) is greater than 96%, and ingredient is one kind or combinations thereof of following substance:
Yttrium stable zirconium oxide (Y2O3) x (ZrO2)1-x ,x=0.03~0.08,
Scandium stabilizing zirconia (Sc2O3) x (ZrO2)1-x ,x=0.08~0.11,
Gd doped cerium oxide Gd x Ce1-xO2-0.5x,x=0.1~0.4,
Sm doped cerium oxide Sm xCe1-xO2-0.5x,x=0.1~0.4,
The lanthanum gallate La of Sr and Mg codope0.8Sr0.2Ga0.9Mg0.1O3、
Er adulterates bismuth oxide (Er2O3) x (Bi2O3)1-x ,x=0.1~0.3；
The cathode electrode (2) is identical with the constituent of anode electrode (3), and ingredient is one kind or its group of following substance
It closes:
La1-x Sr x MnO3,x=0.2~0.4,
La1-x Sr x CoO3,x=0.2~0.4,
La1-x Sr x FeO3,x=0.2~0.4,
La1-x Sr x NiO3,x=0.2~0.4,
Nd2NiO4、
Sr2Fe1.5Mo0.5O6；
The electrolyte layer (1) with a thickness of 5~100 μm；The thickness of the cathode electrode (2) and anode electrode (3) is respectively
80~180 μm；
The dielectric film its per hour oxygen making amount be 83~125ml h-1cm-2。
2. using the method for producing oxygen through of dielectric film described in claim 1, it is characterised in that: by the cathode electrode of the dielectric film
(2) it is placed in air side on one side, applies cathode potential to it, the oxygen in air obtains electronics and becomes oxonium ion；The oxygen from
After son reaches anode electrode (3) through dielectric film, loses electronics and be oxidized to oxygen；The operating temperature of the dielectric film
It is 500~1000 DEG C, operating voltage is 50~300mV.
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| CN108682884B (en) * | 2018-04-27 | 2021-05-25 | 山东理工大学 | Oxygen ion type composite electrolyte of intermediate-temperature solid oxide fuel cell and preparation method thereof |
| CN108905628B (en) * | 2018-06-29 | 2021-07-13 | 东南大学 | Control device based on direct oxygen enrichment of cellulose acetate membrane electrodialysis air |
| CN109626333B (en) * | 2019-01-25 | 2019-12-31 | 北京汉华元生科技有限公司 | Electrochemistry ceramic membrane oxygen generator and oxygen generating equipment thereof |
| CN113511633A (en) * | 2021-07-15 | 2021-10-19 | 云南安锋气体有限公司 | Integrated preparation process of high-purity oxygen |
| CN116003130A (en) * | 2022-04-20 | 2023-04-25 | 临沂临虹无机材料有限公司 | Method for manufacturing multilayer ceramic wafer by cast film and powder dry pressing |
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