CN113504282A - Preparation method of oxygen reference electrode material and oxygen determination probe - Google Patents
Preparation method of oxygen reference electrode material and oxygen determination probe Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 93
- 239000001301 oxygen Substances 0.000 title claims abstract description 93
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000007772 electrode material Substances 0.000 title claims abstract description 38
- 239000000523 sample Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000000694 effects Effects 0.000 abstract description 9
- 230000010287 polarization Effects 0.000 abstract description 7
- 239000011651 chromium Substances 0.000 abstract description 6
- 239000011258 core-shell material Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000003411 electrode reaction Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000009628 steelmaking Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229940117975 chromium trioxide Drugs 0.000 description 4
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 206010021143 Hypoxia Diseases 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007954 hypoxia Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
- C01G37/033—Chromium trioxide; Chromic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
Abstract
The invention discloses a preparation method of an oxygen reference electrode material and an oxygen determination probe, comprising the following steps: adding polyvinyl alcohol into deionized water to prepare a mixed solution with a target concentration; adding a chelating dispersant into the mixed solution, and heating to a first preset temperature to obtain a modified solution; adding metal oxide powder into the modified solution, and mixing to obtain a dispersion solution; adding chromium powder into the dispersion solution, and dispersing to obtain a dispersion solution; preparing the oxygen reference electrode from the granulated powder obtained after the dispersion is irritated. According to the embodiment of the invention, intermolecular combination of metal chromium and metal oxide is realized through the synergistic effect of polyvinyl alcohol and chelating dispersant, so that a perfect core-shell structure is formed, the reaction activity of the electrode material is improved, and the polarization effect of electrode reaction is effectively overcome.
Description
Technical Field
The invention relates to the technical field of oxygen sensors, in particular to a preparation method of an oxygen reference electrode material and an oxygen determination probe.
Background
The online detection and monitoring of the oxygen content in the steelmaking process play an important role in improving the steelmaking quality, increasing the steelmaking efficiency and reducing the steelmaking cost. However, the existing hypoxia oxygen determination probe suitable for the refining links such as CAS, LF, RH and the like is basically monopolized by foreign technologies, the domestic oxygen determination probe cannot meet the requirements of hypoxia oxygen determination and aluminum determination, and the difference mainly focuses on the accuracy, stability and sensitivity of the oxygen determination battery and has a great difference compared with the imported battery. The key for restricting the level of the domestic oxygen determination probe is two, one is a high-quality zirconia solid electrolyte tube, and the other is a high-reactivity oxygen reference electrode material.
Most of the existing oxygen determination reference electrode improvement methods adopt means of adjusting the formula and mixing mode of oxygen electrode materials, chemical treatment and the like, can only basically meet the requirement of oxygen measurement in a medium-high oxygen section, but cannot meet the requirement of low-oxygen aluminum determination, especially cannot simultaneously take the measurements of medium-high oxygen and low-oxygen aluminum determination into consideration, cannot meet the requirement of a steelmaking site, and cannot realize import substitution in the true sense.
Disclosure of Invention
The embodiment of the invention provides a preparation method of an oxygen reference electrode material and an oxygen determination probe, which are used for solving the problem that the polarization effect of the oxygen electrode material obviously causes the reduction of the measurement accuracy and stability in a low-oxygen aluminum determination measurement section, meeting the measurement requirement of low-oxygen aluminum determination and simultaneously considering the measurement of the oxygen content in a medium-high oxygen section.
The embodiment of the invention provides a preparation method of an oxygen reference electrode material, which comprises the following steps:
adding polyvinyl alcohol into deionized water to prepare a mixed solution with a target concentration;
adding a chelating dispersant into the mixed solution, and heating to a first preset temperature to obtain a modified solution;
adding metal oxide powder into the modified solution, and mixing to obtain a dispersion solution;
adding chromium powder into the dispersion solution, and dispersing to obtain a dispersion solution;
preparing the oxygen reference electrode from the granulated powder obtained after the dispersion is irritated.
In one embodiment, the first predetermined temperature range is [40 ℃ to 60 ℃ ].
In one embodiment, the metal oxide is chromium oxide, and/or iron trioxide;
adding metal oxide powder to the modification solution, and mixing comprises:
adding metal oxide powder into the modified solution, and continuously stirring for a first preset time.
In one embodiment, the metal oxide has a particle size in the range of [30nm-100nm ].
In one embodiment, the adding of chromium powder to the dispersion solution comprises:
and adding the chromium powder into the dispersion solution at a preset speed, and continuously stirring for a second preset time after the chromium powder is added.
In one embodiment, the particle size range of the chromium powder satisfies [10 μm-100 μm ].
In one embodiment, the preparation of the oxygen reference electrode from the granulated powder obtained after agitation of the dispersion comprises:
introducing oxygen into the granulation powder in a tubular atmosphere furnace, and heating to a second preset temperature;
and calcining the granulated powder for a third preset time to obtain the oxygen reference electrode.
The embodiment of the invention also provides an oxygen determination probe, which comprises a shell, a zirconium oxide tube and an oxygen reference electrode material prepared by the preparation method of the oxygen reference electrode material; the oxygen reference electrode material is disposed within the zirconia tube; the zirconia tube comprises a first end and a second end which are opposite, the first end of the zirconia tube is embedded into the shell, the second end of the zirconia tube extends out of the shell, and the second end is used as a detection part of the oxygen determination probe.
According to the embodiment of the invention, intermolecular combination of metal chromium and metal oxide is realized through the synergistic effect of polyvinyl alcohol and chelating dispersant, so that a perfect core-shell structure is formed, the reaction activity of the electrode material is improved, and the polarization effect of electrode reaction is effectively overcome, so that the prepared oxygen reference electrode material meets the measurement requirement of low-oxygen aluminum determination, and meanwhile, the oxygen content determination of medium and high-oxygen sections can be considered.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a basic flow chart of a method for preparing a reference electrode material according to an embodiment of the disclosure.
Fig. 2 is an SEM picture of a reference material prepared in an example of the present disclosure.
Fig. 3 is a schematic diagram of a basic structure of an oxygen determination probe according to an embodiment of the present disclosure.
FIG. 4 is a schematic enlarged view of a portion of an oxygen determination probe according to an embodiment of the present disclosure.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
In the low-oxygen aluminum determination link, because the oxygen content in the molten steel is extremely low, the oxygen reference electrode not only needs to overcome volume shrinkage at high temperature, but also needs to overcome the polarization effect of the reference electrode.
An embodiment of the present invention provides a method for preparing an oxygen reference electrode material, and as shown in fig. 1, the preparation method disclosed in this disclosure starts with step S101, adding polyvinyl alcohol to deionized water to prepare a mixed solution with a target concentration. For example, the ultra-low molecular weight polyvinyl alcohol may be added to a device with heating and stirring functions, and then deionized water may be added, thereby mixing to form a mixed solution having a concentration of less than 1%. And then, step S102 is executed, after the chelating dispersant is added into the mixed solution, the mixed solution is heated to a first preset temperature, and a modified solution is obtained. ST-40 can be selected as the chelating dispersant, the chelating dispersant is continuously heated to a first preset temperature through the device, and the modified solution is obtained after uniform stirring. Next, step S103 is performed, and metal oxide powder is added to the modified solution and mixed to obtain a dispersion solution. And then step S104 is executed, chromium powder is added into the dispersion solution, and dispersion is carried out to obtain dispersion liquid. And finally, step S105 is carried out, and the oxygen reference electrode is prepared from the granulated powder obtained after the dispersion liquid is irritated.
According to the embodiment of the invention, intermolecular combination of metal chromium and metal oxide is realized through the synergistic effect of polyvinyl alcohol and chelating dispersant, so that a perfect core-shell structure is formed, the reaction activity of the electrode material is improved, and the polarization effect of electrode reaction is effectively overcome, so that the prepared oxygen reference electrode material meets the measurement requirement of low-oxygen aluminum determination, and meanwhile, the oxygen content determination of medium and high-oxygen sections can be considered.
In one embodiment, the first predetermined temperature range is [40 ℃ to 60 ℃ ]. Specifically, heating to [40 ℃ to 60 ℃) can be carried out by the apparatus, with thorough stirring during the heating.
In one embodiment, the metal oxide is chromium oxide, and/or iron trioxide; adding metal oxide powder to the modification solution, and mixing comprises: adding metal oxide powder into the modified solution, and continuously stirring for a first preset time. In one embodiment, the metal oxide has a particle size in the range of [30nm-100nm ]. Specifically, the metal oxide in this example may be chromium trioxide or iron trioxide, or may be a combination of chromium trioxide and iron trioxide in a certain mass ratio. For example, in the case where both chromium trioxide and iron trioxide are used, the mass ratio range of iron trioxide to chromium trioxide satisfies [ 1%, 200% ]. The grain diameter range of the chromium sesquioxide and/or the ferric oxide satisfies [30nm-100nm ].
In one embodiment, the adding of chromium powder to the dispersion solution comprises: and adding the chromium powder into the dispersion solution at a preset speed, and continuously stirring for a second preset time after the chromium powder is added. In one embodiment, the particle size range of the chromium powder satisfies [10 μm-100 μm ]. Specifically, after the dispersion solution is obtained, the chromium powder can be added into the dispersion solution at a preset speed, the particle size range of the added chromium powder meets [ 10-100 μm ], and the adding speed is strictly controlled in the process of adding the chromium powder, so that the dispersion solution is ensured to be precipitated and uniformly dispersed. And after the chromium powder is added, continuously stirring for a second preset time period, for example, continuously stirring for 2 hours, or other preset time periods, wherein the condition that the chromium powder is uniformly dispersed is met.
In one embodiment, the preparation of the oxygen reference electrode from the granulated powder obtained after agitation of the dispersion comprises: introducing oxygen into the granulation powder in a tubular atmosphere furnace, and heating to a second preset temperature; and calcining the granulated powder for a third preset time to obtain the oxygen reference electrode. Specifically, a granulated powder can be obtained by a customized spray drying apparatus based on the aforementioned dispersion. And then placing the granulated powder in a tubular atmosphere furnace, introducing high-purity oxygen, calcining the granulated powder at a set temperature, and cooling to obtain a required finished product.
The following example also provides an embodiment of a method for preparing an oxygen reference electrode material:
case one
The first step is as follows: weighing 0.2 g of ultra-low molecular weight polyvinyl alcohol, adding the ultra-low molecular weight polyvinyl alcohol into a device with heating and stirring functions, adding deionized water to prepare 2L of solution with the concentration of about 0.1%, adding 2ml of chelating dispersant ST-40, heating to 40 ℃, and fully and uniformly stirring to form modified solution;
the second step is that: slowly adding 1 g of nano chromium oxide (the granularity is 30nm) and 0.1 g of nano iron oxide (the granularity is 30nm) into the modified solution, and fully stirring for 1 hour;
the third step: weighing 80 g of chromium powder (the granularity is 10 mu m), slowly adding the chromium powder into the dispersion liquid in the second step which is continuously stirred, strictly controlling the adding speed to ensure that the dispersion liquid is precipitated and uniformly dispersed, and continuously stirring for 2 hours after the addition is finished;
the fourth step: obtaining the granulated powder from the dispersion liquid treated in the third step through customized spray drying equipment;
the fifth step: and (3) placing the granulated powder in a tubular atmosphere furnace, introducing high-purity oxygen, heating to 600 ℃, fully calcining for 4 hours, cooling along with the furnace, and taking out to obtain the required oxygen reference electrode material finished product.
Case two
The first step is as follows: 0.5 g of ultra-low molecular weight polyvinyl alcohol is weighed and added into a device with heating and stirring functions, then deionized water is added to prepare 2L of solution with the concentration of about 0.1%, then 2ml of chelating dispersant ST-40 is added, the solution is heated to 50 ℃, and the modified solution is formed by fully and uniformly stirring.
The second step is that: slowly adding 8 g of nano chromium oxide (the granularity is 60nm) and 1 g of nano iron oxide (the granularity is 50nm) into the modified solution, and fully stirring for 1 hour;
the third step: weighing 90 g of chromium powder (the granularity is 40 mu m), slowly adding the chromium powder into the dispersion liquid in the second step which is continuously stirred, strictly controlling the adding speed to ensure that the dispersion liquid is precipitated and uniformly dispersed, and continuously stirring for 2 hours after the addition is finished;
the fourth step: obtaining the granulated powder from the dispersion liquid treated in the third step through customized spray drying equipment;
the fifth step: and (3) placing the granulated powder in a tubular atmosphere furnace, introducing high-purity oxygen, heating to 600 ℃, fully calcining for 4 hours, cooling along with the furnace, and taking out to obtain the required finished product.
Case three
The first step is as follows: weighing 1 g of ultra-low molecular weight polyvinyl alcohol, adding the ultra-low molecular weight polyvinyl alcohol into a device with heating and stirring functions, adding deionized water to prepare 2L of solution with the concentration of about 0.1%, adding 2ml of chelating dispersant ST-40, heating to 60 ℃, and fully and uniformly stirring to form modified solution.
The second step is that: 10 g of nanoscale chromium sesquioxide (85nm) and 2 g of nanoscale iron sesquioxide (90nm) are slowly added into the modified solution, and the mixture is fully stirred for 1 hour.
The third step: and weighing 99 g of chromium powder (the granularity is 95 microns), slowly adding the chromium powder into the dispersion liquid in the second step which is continuously stirred, strictly controlling the adding speed to ensure that the dispersion liquid is precipitated and uniformly dispersed, and continuously stirring for 2 hours after the addition is finished.
The fourth step: obtaining the granulated powder from the dispersion liquid treated in the third step through customized spray drying equipment;
the fifth step: and (3) placing the granulated powder in a tubular atmosphere furnace, introducing high-purity oxygen, heating to 600 ℃, fully calcining for 4 hours, cooling along with the furnace, and taking out to obtain the required finished product.
The preparation method of the oxygen reference electrode material disclosed by the invention can adopt a nano modification technology combined with a spray granulation method, and can realize that the micro structure of the oxygen electrode material forms a spherical core-shell structure by regulating and controlling the combination mode of the oxygen electrode material (metal chromium, chromium oxide and ferric oxide). As shown in fig. 2, the structure can be characterized in that the electrode oxidation-reduction reaction is very rapid, the electron transmission channel is smooth, the phenomenon that the electron transmission channel is blocked after a compact chromium oxide film is formed on the surface of a Cr particle in the traditional electrode material due to oxidation is avoided, and meanwhile, iron oxide existing as a catalyst is fully contacted with the chromium particle and the chromium oxide respectively, so that the polarization current appearing in the low-oxygen aluminum determination link can be rapidly released, the electrode potential is kept constant, the electrode polarization effect under the oxygen determination measurement condition is perfectly overcome, the measurement requirement of low-oxygen aluminum determination is met, and the measurement of medium and high oxygen content is considered.
The embodiment of the invention also provides an oxygen determination probe, as shown in fig. 3 and 4, which comprises a shell 1, a zirconia tube 2 and an oxygen reference electrode material 3 prepared by the preparation method of the oxygen reference electrode material. The oxygen reference electrode material 3 is disposed within the zirconia tube 2; the zirconia pipe 2 includes relative first end and second end, the first end embedding of zirconia pipe 2 casing 1, the second end of zirconia pipe 2 stretch out with outside the casing 1, the second end is as the detection portion of oxygen determination probe.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of an oxygen reference electrode material is characterized by comprising the following steps:
adding polyvinyl alcohol into deionized water to prepare a mixed solution with a target concentration;
adding a chelating dispersant into the mixed solution, and heating to a first preset temperature to obtain a modified solution;
adding metal oxide powder into the modified solution, and mixing to obtain a dispersion solution;
adding chromium powder into the dispersion solution, and dispersing to obtain a dispersion solution;
preparing the oxygen reference electrode from the granulated powder obtained after the dispersion is irritated.
2. The method of making an oxygen reference electrode material according to claim 1, wherein the first predetermined temperature range is [40 ℃ to 60 ℃ ].
3. The method of making an oxygen reference electrode material according to claim 1, wherein the metal oxide is chromium oxide, and/or iron oxide;
adding metal oxide powder to the modification solution, and mixing comprises:
adding metal oxide powder into the modified solution, and continuously stirring for a first preset time.
4. The method for producing an oxygen reference electrode material according to claim 1, wherein the metal oxide has a particle size in the range of [30nm-100nm ].
5. The method of making an oxygen reference electrode material of claim 1, wherein the adding chromium powder to the dispersion solution comprises:
and adding the chromium powder into the dispersion solution at a preset speed, and continuously stirring for a second preset time after the chromium powder is added.
6. The method for producing an oxygen reference electrode material according to claim 1, wherein the particle size range of the chromium powder satisfies [10 μm-100 μm ].
7. The method of preparing the oxygen reference electrode material according to claim 1, wherein the preparing the oxygen reference electrode from the granulated powder obtained after the dispersion is agitated comprises:
introducing oxygen into the granulation powder in a tubular atmosphere furnace, and heating to a second preset temperature;
and calcining the granulated powder for a third preset time to obtain the oxygen reference electrode.
8. An oxygen determination probe comprising a housing, a zirconia tube and an oxygen reference electrode material produced by the method of producing an oxygen reference electrode material according to any one of claims 1 to 7;
the oxygen reference electrode material is disposed within the zirconia tube;
the zirconia tube comprises a first end and a second end which are opposite, the first end of the zirconia tube is embedded into the shell, the second end of the zirconia tube extends out of the shell, and the second end is used as a detection part of the oxygen determination probe.
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2021
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