CN111239222A - Ionic liquid electrolyte and electrochemical gas sensor - Google Patents
Ionic liquid electrolyte and electrochemical gas sensor Download PDFInfo
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Abstract
The invention provides an ionic liquid electrolyte and an electrochemical gas sensor. The electrochemical gas sensor includes an electrolyte. The electrolyte comprises A-type ionic liquid, and the A-type ionic liquid comprises one or more of 1-ethyl, 3-methylimidazole thiocyanate, 1-ethyl, 3-methylimidazole acetate and 1-ethyl, 3-methylimidazole nitrate. The electrochemical gas sensor according to the present invention has improved durability and extended service life.
Description
Technical Field
The present invention relates to a sensor, and more particularly, to an ionic liquid electrolyte and an electrochemical gas sensor including the same.
Background
In recent years, the problem of environmental pollution is increasingly highlighted, and a series of air pollution problems such as haze, acid rain and the like greatly influence the life of people. Therefore, there is an urgent need for accurate monitoring of harmful gases and effective control of pollutant emissions of the harmful gases.
An electrochemical gas sensor is a test element capable of converting chemical signals into electric signals, and is a core component for monitoring gas concentration. The basic measurement element of an electrochemical gas sensor is an electrochemical cell comprising at least two electrodes, e.g., a working electrode (or sensing electrode) and a counter electrode, a working electrode (or sensing electrode), a counter electrode and a reference electrode, etc., in contact with each other via an electrolyte (i.e., an ionic conductor, which may also be referred to as an electrolyte). The working electrode of the electrochemical gas sensor is in communication with the external environment (e.g., the atmosphere), and the counter electrode is sealed inside the sensor and in communication with the gas chamber sealed inside. The target gas in the external environment (i.e., the gas to be analyzed) can flow to the working electrode and undergo (redox) chemical reaction with the electrode material, and the generated redox current is in direct proportion to the concentration of the target gas in the external environment. The real-time online monitoring of the concentration change of the target gas can be realized by monitoring the current change.
At present, most of electrolytes in commercially available electrochemical sensors are inorganic salt aqueous solutions or sulfuric acid aqueous solutions, and because water has an unavoidable evaporation phenomenon, the amount of electrolytes in such sensors gradually decreases with the evaporation of water, so that phenomena such as drying and circuit breaking occur in the electrochemical sensors, the sensitivity of the electrochemical sensors is continuously reduced (for example, the sensitivity reduction value is less than or equal to 1%/month), and the service life of the electrochemical sensors is shortened (generally less than two years). Here, the sensitivity refers to the ratio of the output current to the target gas concentration, and is expressed in nA/ppm.
Ammonia gas is a harmful gas with pungent odor, and belongs to alkaline gas. Fig. 1 shows a schematic diagram of a decay change process of an output current in an ammonia gas atmosphere, as shown in fig. 1, ammonia gas starts to be introduced at a point a, air starts to be introduced at a point B, and a time period P between the point a and the point B represents a time period in the ammonia gas atmosphere, as can be seen from fig. 1, under a certain ammonia gas concentration, an output current (also called a response current) of an electrochemical gas sensor in the prior art cannot be kept stable after reaching a platform current (i.e., an output current proportional to a target gas concentration), but gradually decreases with time, that is, a current decay phenomenon occurs, so that the electrochemical sensor cannot effectively and accurately respond to a concentration change of an external target gas.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, it is an object of the present invention to provide an ionic liquid electrolyte that is less volatile and has good durability in ammonia sensing.
Another object of the present invention is to provide a rechargeable lithium battery having appropriate (e.g., excellent) cycle life and safety characteristics.
One aspect of the invention provides an electrochemical gas sensor that includes an electrolyte. The electrolyte comprises A-type ionic liquid, wherein the A-type ionic liquid comprises one or more of 1-ethyl, 3-methylimidazole thiocyanate, 1-ethyl, 3-methylimidazole acetate and 1-ethyl, 3-methylimidazole nitrate.
Alternatively, the electrolyte may further include one or more of a B-type ionic liquid, a lithium salt, and graphene oxide.
Alternatively, the class B ionic liquid may comprise one or more of 1-ethyl, 3-methylimidazole bisfluorosulfonyl imide salt, 1-ethyl, 3-methylimidazole bistrifluoromethanesulfonyl imide salt, 1-ethyl, 3-methylimidazole trifluoromethanesulfonate, 1-ethyl, 3-methylimidazole tetrafluoroborate, 1-hydroxyethyl, 3-methylimidazole tetrafluoroborate.
Alternatively, the lithium salt may be lithium chloride, lithium bromide, lithium iodide or lithium carbonate.
Alternatively, the graphene oxide may be a powder or a suspended aqueous solution.
Alternatively, the mass ratio of the class a ionic liquid to the class B ionic liquid may be 60: 5-60: 50. preferably, the mass ratio of the class a ionic liquid to the class B ionic liquid may be 60: 20-60: 30
Alternatively, the mass ratio of the class a ionic liquid to the lithium salt may be 60: 3-60: 40. preferably, the mass ratio of the group a ionic liquid to the lithium salt may be 60: 8-60: 20;
alternatively, the mass ratio of the class a ionic liquid to the graphene oxide may be 60: 0.01-60: 0.3. preferably, the mass ratio of the class a ionic liquid to the graphene oxide may be 60: 0.05-60: 0.1.
alternatively, electrochemical gas sensors may be used to detect ammonia, hydrogen sulfide, sulfur dioxide or nitrogen dioxide.
In another aspect of the invention, an ionic liquid electrolyte is provided, the ionic liquid electrolyte comprising a class a ionic liquid comprising one or more of 1-ethyl, 3-methylimidazole thiocyanate, 1-ethyl, 3-methylimidazole acetate, and 1-ethyl, 3-methylimidazole nitrate.
Alternatively, the electrolyte may further include one or more of a B-type ionic liquid, a lithium salt, and graphene oxide.
Alternatively, the class B ionic liquid may comprise one or more of 1-ethyl, 3-methylimidazole bisfluorosulfonyl imide salt, 1-ethyl, 3-methylimidazole bistrifluoromethanesulfonyl imide salt, 1-ethyl, 3-methylimidazole trifluoromethanesulfonate, 1-ethyl, 3-methylimidazole tetrafluoroborate, 1-hydroxyethyl, 3-methylimidazole tetrafluoroborate.
Alternatively, the lithium salt may be lithium chloride, lithium bromide, lithium iodide or lithium carbonate.
Alternatively, the graphene oxide may be a powder or a suspended aqueous solution.
Alternatively, the mass ratio of the class a ionic liquid to the class B ionic liquid may be 60: 5-60: 50. preferably, the mass ratio of the class a ionic liquid to the class B ionic liquid may be 60: 20-60: 30
Alternatively, the mass ratio of the class a ionic liquid to the lithium salt may be 60: 3-60: 40. preferably, the mass ratio of the group a ionic liquid to the lithium salt may be 60: 8-60: 20;
alternatively, the mass ratio of the class a ionic liquid to the graphene oxide may be 60: 0.01-60: 0.3. preferably, the mass ratio of the class a ionic liquid to the graphene oxide may be 60: 0.05-60: 0.1.
alternatively, the ionic liquid electrolyte may be used as an electrolyte in an electrochemical sensor that can be used to detect ammonia, hydrogen sulfide, sulfur dioxide, or nitrogen dioxide.
Compared with the prior art, the invention has the beneficial effects that: the durability of the electrochemical gas sensor is improved, and the service life of the electrochemical gas sensor is prolonged.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a graphical representation of the output current versus time of a prior art electrochemical gas sensor.
Fig. 2 is a schematic diagram of the output current of the electrochemical gas sensor S1 with respect to time.
Fig. 3 is a graph of the results of a service life test of the electrochemical gas sensor S1.
Fig. 4 is a schematic diagram of output current versus time when the electrochemical gas sensor is used for testing ammonia gas, hydrogen sulfide, sulfur dioxide and nitrogen dioxide respectively.
Fig. 5 is a graph showing the change in output current with respect to time of the electrochemical gas sensor S2.
Fig. 6 is a schematic diagram of the output current of the electrochemical gas sensor S3 with respect to time.
Fig. 7 is a graph showing the change in output current with respect to time of the electrochemical gas sensor S4.
Fig. 8 is a graph showing the change in output current with respect to time of the electrochemical gas sensor S5.
Fig. 9 is a schematic diagram of the output current of the electrochemical gas sensor S6 with respect to time.
Fig. 10 is a graph showing the change in output current with respect to time of the electrochemical gas sensor S7.
Detailed Description
Hereinafter, an ionic liquid electrolyte and an electrochemical gas sensor according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
Aiming at the problem of attenuation of output current in an ammonia atmosphere, the inventor finds that the main generation reasons are as follows: in gas sensing processes, only the working and counter electrodes emitThe equilibrium of the raw (redox) reaction (i.e., the electron gain and electron loss between the two electrodes are identical) is reached, and the sensor can maintain a stable output current. However, the electrochemical oxidation of ammonia is a step-by-step dehydrogenation process. When the ammonia gas diffuses to the gas-solid-liquid three-phase interface of the working electrode, the ammonia gas undergoes an oxidation reaction under the catalysis, and H is continuously released into the electrolyte+The ammonia gas is easily dissolved in the electrolyte excessively and reacts with the generated H+Combined to form NH4 +. NH generated at the working electrode4 +And H+Should then diffuse to the counter electrode for a reduction reaction to occur. However, NH4 +Ratio H+The diffusion rate is much slower, so that the reduction reaction at the counter electrode is slower and slower as the ammonia gas is continuously dissolved, and the response current to be detected is gradually reduced. Since the sensor cannot maintain a stable output current in an ammonia atmosphere, the concentration of the target gas in the environment cannot be accurately detected.
Ionic liquids are defined as liquid salts with melting points below 100 ℃, which may be referred to as room temperature (e.g., about 25 ℃) molten salts, which generally consist of large organic cationic groups and inorganic anionic groups, with many excellent physicochemical properties, such as: negligible saturated vapor pressure values (non-volatile), a wide electrochemical window, good electrical conductivity, and good thermal stability, which make ionic liquids an excellent electrolyte in electrochemical gas sensors.
An ionic liquid electrolyte according to an exemplary embodiment of an aspect of the present invention may include a class a ionic liquid. Among them, the class a ionic liquid may include one or more of 1-ethyl, 3-methylimidazole thiocyanate represented by the following chemical formula 1, 1-ethyl, 3-methylimidazole acetate represented by the following chemical formula 2, and 1-ethyl, 3-methylimidazole nitrate represented by the following chemical formula 3.
Chemical formula 3
The A-type ionic liquid has the characteristic of non-volatility, has good durability in the ammonia sensing process, can ensure long-term physical and chemical stability, and can serve as a solvent in an ionic liquid electrolyte.
The ionic liquid electrolyte may further include one or more of a B-type ionic liquid, a lithium salt, graphene oxide.
Among them, the class B ionic liquid may include one or more of 1-ethyl, 3-methylimidazole bis-fluorosulfonyl imide salt represented by the following chemical formula 4, 1-ethyl, 3-methylimidazole bis-trifluoromethanesulfonyl imide salt represented by the following chemical formula 5, 1-ethyl, 3-methylimidazole trifluoromethanesulfonate salt represented by the following chemical formula 6, 1-ethyl, 3-methylimidazole tetrafluoroborate salt represented by the following chemical formula 7, 1-hydroxyethyl, 3-methylimidazole tetrafluoroborate salt represented by the following chemical formula 8.
Chemical formula 6
Chemical formula 7
Chemical formula 8
The B-type ionic liquid has strong hydrogen bond effect and can be dissolved in the electrolyte to form ammonia NH3Interaction, weakening of dissolved NH3To obtain H+The ability of the cell to perform. And anion pair H of class B ionic liquids+Has strong solvating power and can react with NH4 +Competition H+. These factors together affect NH4 +Is balanced to reduce NH4 +The cumulative amount of (c). But because of H in the reaction process+Generated while fluorine-containing anions encounter H+Then, HF is generated by decomposition, so that the electrolyte is gradually deteriorated, and a three-phase interface of gas-solid-liquid is damaged, which is not favorable for the long-term stability of the sensor. The A-type ionic liquid has better ion conductivity and stronger dissolving capacity, and can maintain the stability of a phase interface. Dissolving B type ionic liquid in A type ionic liquid can reduce fluorine-containing anions and H+The contact time of (3) can avoid the decomposition of fluorine-containing anions and maintain the stability of a phase interface. Therefore, the B-type ionic liquid is matched with the A-type ionic liquid to adjust NH4 +The ionization balance of ions in the electrolyte and the protection of H+The stability in the electrolyte is ensured, so that the attenuation of the output current of the electrochemical gas sensor under the condition of ammonia atmosphere is obviously inhibited.
The lithium salt may be lithium chloride, lithium bromide, lithium iodide or lithium carbonate. Alkaline substances (e.g., potassium, sodium, etc.) can affect H in the electrolyte+Stability of (2) to H+More, faster, and dissolved ammonia gas combination to NH4 +This causes the response current to decay faster. The addition of lithium salt can not only improve the ionic conductivity of the electrolyte, but also prevent H+The stability of (c) has an influence. Among them, increasing the ionic conductivity is advantageous for increasing the response speed and response current。
The graphene oxide may be a powder or a suspended aqueous solution. The active site of the electrochemical gas sensor is a three-phase interface of 'gas-solid-liquid', and the 'gas' refers to a gas film when ammonia gas contacts; "solid" refers to the surface of the catalyst on the gas diffusion electrode; the liquid refers to the liquid film of the electrolyte, and the joint positions of the three interfaces are active sites for catalytic reaction. Because the surface of the graphene oxide contains a large number of hydroxyl groups, when a proper amount of graphene oxide exists in the liquid film, the hydroxyl groups can improve the acting force of the liquid film and ammonia molecules, improve the gas-liquid film mass transfer speed at a three-phase interface, and further improve the response value and the response speed. Meanwhile, hydroxyl groups existing in the electrolyte can also interact with ammonia dissolved in the electrolyte to weaken the combined H+Thereby increasing H+Stability of (2).
The mass ratio of the class A ionic liquid to the class B ionic liquid can be 60: 5-60: 50. the mass ratio of the A-type ionic liquid to the lithium salt may be 60: 3-60: 40. the mass ratio of the class a ionic liquid to the graphene oxide may be 60: 0.01-60: 0.3. the proportion can ensure that the electrolyte can effectively adjust ionization balance, slow down the decomposition of fluorine-containing anions and cannot generate great influence on the conductivity. However, if the amount of the B ionic liquid added is too large (for example, exceeds the upper limit value of the above ratio), the phase interface becomes unstable, and if the amount added is too small (for example, below the lower limit value of the above ratio), the ionization balance in the electrolyte cannot be effectively controlled. An excessively small amount of the lithium salt (for example, less than the lower limit value of the above ratio) does not significantly improve the conductivity, whereas an excessively large amount (for example, more than the upper limit value of the above ratio) destroys the electrostatic balance of the ionic liquid itself and decomposes the ionic liquid since the solubility of the ionic liquid to the lithium salt is limited. Since graphene oxide itself has poor conductivity, the influence of its addition amount on the response speed exhibits a volcanic curve, and too much (e.g., exceeding the upper limit value of the above ratio) causes a decrease in conductivity, while too little (e.g., falling below the lower limit value of the above ratio) does not significantly increase the response speed.
Preferably, the mass ratio of the class a ionic liquid to the class B ionic liquid may be 60: 15-60: 30. the mass ratio of the A-type ionic liquid to the lithium salt may be 60: 5-60: 20. the mass ratio of the class a ionic liquid to the graphene oxide may be 60: 0.02-60: 0.1.
preferably, the mass ratio of the class a ionic liquid to the class B ionic liquid may be 60: 20-60: 30. the mass ratio of the A-type ionic liquid to the lithium salt may be 60: 8-60: 20. the mass ratio of the class a ionic liquid to the graphene oxide may be 60: 0.05-60: 0.1.
the ionic liquid electrolyte according to an exemplary embodiment of the present invention may be obtained by mixing one or more of a group B ionic liquid, a lithium salt, and graphene oxide with a group a ionic liquid. For example, in one embodiment, the ionic liquid electrolyte may be obtained by directly mixing a class a ionic liquid and a class B ionic liquid. In another embodiment, the ionic liquid electrolyte may be obtained by first dissolving the lithium salt with water and then mixing with the a ionic liquid. In yet another embodiment, the ionic liquid electrolyte may be obtained by first dissolving powdered graphene oxide in water and then mixing with the a ionic liquid.
An exemplary embodiment of another aspect of the invention provides an electrochemical gas sensor comprising a housing and an electrode and an ionic liquid electrolyte as described above contained in the housing.
The electrode may be a gas diffusion electrode and may be made by printing an electrode material on a hydrophobic gas permeable membrane. The number of electrodes may be at least two. In one embodiment, an electrochemical gas sensor can include a working electrode, a counter electrode, and a reference electrode. The electrode material may be any known material in the art suitable for ammonia electrochemical sensors, such as a mono-or binary metal of Pt, Ir, Au, Pb, Ag, Ru, Rh, Cu, Ni, Ti, etc., an oxide of these metals, a mixture of these metals and metal oxides, or carbon black. The electrodes may have any suitable planar shape.
The housing may be a generally cylindrical structure with a gas chamber. The housing may include at least one opening through which the target gas may enter the electrochemical gas sensor. The housing may be formed of ABS plastic (acrylonitrile, butadiene, styrene copolymer) PPO plastic (polyphenylene oxide) or any other corrosion resistant, electrically non-conductive material.
The ionic liquid electrolyte may be adsorbed or impregnated on other supports (e.g., cotton sheets).
Structures and fabrication methods for electrochemical gas sensors pertaining to the present disclosure are known in the art. The housing, electrodes, etc. required for electrochemical gas sensors are commercially available.
Examples of the invention
Hereinafter, examples of the present invention are described. However, these examples are not to be construed in any way as limiting the scope of the invention.
Preparation of ionic liquid electrolyte
The mixed ionic liquid electrolyte provided in the following examples is based on the total mass of the class a ionic liquid as a reference standard.
Example 1
1-ethyl, 3-methylimidazolium thiocyanate: graphene oxide 60 g: an ionic liquid electrolyte was prepared at a ratio of 0.06 g.
Example 2
1-ethyl, 3-methylimidazolium thiocyanate: 1-ethyl, 3-methylimidazolium bistrifluoromethanesulfonimide salt: lithium chloride 60 g: 20 g: 10g of the ionic liquid electrolyte was prepared.
Example 3
1-ethyl, 3-methylimidazole acetate: 1-ethyl, 3-methylimidazolium bistrifluoromethanesulfonimide salt: lithium bromide 60 g: 25g of: an ionic liquid electrolyte was prepared at a ratio of 13 g.
Example 4
1-ethyl, 3-methylimidazolium thiocyanate: 1-ethyl, 3-methylimidazolium bistrifluoromethanesulfonimide salt: lithium chloride 60 g: 28 g: an ionic liquid electrolyte was prepared at a ratio of 16 g.
Example 5
1-ethyl, 3-methylimidazolium thiocyanate: 1-ethyl, 3-methylimidazolium bis fluorosulfonyl imide salt: lithium iodide 60 g: 25g of: 15g of the ionic liquid electrolyte was prepared.
Example 6
1-ethyl, 3-methylimidazolium thiocyanate: 1-hydroxyethyl, 3-methylimidazolium tetrafluoroborate 60 g: an ionic liquid electrolyte was prepared at a ratio of 25 g.
Example 7
1-ethyl, 3-methylimidazole nitrate: lithium iodide 60 g: 15g of the ionic liquid electrolyte was prepared.
Manufacture of electrochemical gas sensors
Electrochemical gas sensors S1 to S7 were assembled using the working electrode and the counter electrode and the ionic liquid electrolytes according to examples 1 to 7, respectively.
Evaluation example: sensing performance test of electrochemical gas sensor
The electrochemical gas sensors S1 to S7 were subjected to a sensing performance test under a dynamic atmosphere of 50ppm ammonia gas (150mL/min), the response recovery of the electrochemical sensors S1 to S7 was tested, the test results of which are shown in fig. 2 to fig. 10, and the service life of the electrochemical sensor S1 was tested, the test results of which are shown in fig. 3, and the response recovery of the electrochemical sensor S4 to ammonia gas, hydrogen sulfide, sulfur dioxide, and nitrogen dioxide were tested, the test results of which are shown in fig. 4.
As shown in fig. 2 to 10, the electrochemical gas sensors S1 to S7 assembled from the electrochemical gas sensors according to examples 1 to 7 can maintain a stable output current in an ammonia gas atmosphere without a phenomenon of current decay, unlike the electrochemical gas sensors according to the related art shown in fig. 1. As shown in FIG. 3, the output current of the electrochemical gas sensor S1 assembled according to example 1 was stably maintained in the range of 2500 to 3000nA (sensitivity, 50 to 60nA/ppm) in the continuous 500-day test, and there was no tendency of a decrease in sensitivity. The durability (the sensitivity drop value is about 1%/month) of the electrochemical gas sensor is superior to that of the electrochemical gas sensor in the prior art, and the service life of the electrochemical gas sensor is greatly prolonged.
Although it is described above that the electrochemical gas sensor according to the exemplary embodiment of the present invention is used to detect ammonia gas, the present invention is not limited thereto, and may also be used to detect other gases such as hydrogen sulfide, sulfur dioxide, nitrogen dioxide, and the like, as shown in fig. 4.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. An electrochemical gas sensor comprising an electrolyte, wherein the electrolyte comprises a class a ionic liquid comprising one or more of 1-ethyl, 3-methylimidazole thiocyanate, 1-ethyl, 3-methylimidazole acetate, 1-ethyl, 3-methylimidazole nitrate.
2. The electrochemical gas sensor according to claim 1, wherein the electrolyte further comprises one or more of a B-type ionic liquid, a lithium salt, graphene oxide, wherein,
the class B ionic liquid comprises one or more of 1-ethyl, 3-methylimidazole bisfluorosulfonyl imide salt, 1-ethyl, 3-methylimidazole bistrifluoromethanesulfonyl imide salt, 1-ethyl, 3-methylimidazole trifluoromethanesulfonate, 1-ethyl, 3-methylimidazole tetrafluoroborate, 1-hydroxyethyl, 3-methylimidazole tetrafluoroborate;
the lithium salt is lithium chloride, lithium bromide, lithium iodide or lithium carbonate;
the graphene oxide is powder or a suspension water solution.
3. Electrochemical gas sensor according to claim 2,
the mass ratio of the A-type ionic liquid to the B-type ionic liquid is 60: 5-60: 50; the mass ratio of the A-type ionic liquid to the lithium salt is 60: 3-60: 40; the mass ratio of the A-type ionic liquid to the graphene oxide is 60: 0.01-60: 0.3.
4. the electrochemical gas sensor according to claim 3, wherein the mass ratio of the class A ionic liquid to the class B ionic liquid is 60: 20-60: 30, of a nitrogen-containing gas; the mass ratio of the A-type ionic liquid to the lithium salt is 60: 8-60: 20; the mass ratio of the A-type ionic liquid to the graphene oxide is 60: 0.05-60: 0.1.
5. the electrochemical gas sensor according to claim 1, wherein the electrochemical gas sensor is for detecting ammonia, hydrogen sulfide, sulfur dioxide or nitrogen dioxide.
6. An ionic liquid electrolyte comprising a class a ionic liquid comprising one or more of 1-ethyl, 3-methylimidazole thiocyanate, 1-ethyl, 3-methylimidazole acetate, and 1-ethyl, 3-methylimidazole nitrate.
7. The ionic liquid electrolyte of claim 6 further comprising one or more of a class B ionic liquid, a lithium salt, graphene oxide, wherein,
the class B ionic liquid comprises one or more of 1-ethyl, 3-methylimidazole bisfluorosulfonyl imide salt, 1-ethyl, 3-methylimidazole bistrifluoromethanesulfonyl imide salt, 1-ethyl, 3-methylimidazole trifluoromethanesulfonate, 1-ethyl, 3-methylimidazole tetrafluoroborate, 1-hydroxyethyl, 3-methylimidazole tetrafluoroborate;
the lithium salt is lithium chloride, lithium bromide, lithium iodide or lithium carbonate;
the graphene oxide is powder or a suspension water solution.
8. The ionic liquid electrolyte of claim 7, wherein the mass ratio of the class A ionic liquid to the class B ionic liquid is 60: 5-60: 50, the mass ratio of the A-type ionic liquid to the lithium salt is 60: 3-60: 40, the mass ratio of the A-type ionic liquid to the graphene oxide is 60: 0.01-60: 0.3.
9. the ionic liquid electrolyte of claim 8, wherein the mass ratio of the class a ionic liquid to the class B ionic liquid is 60: 20-60: 30, the mass ratio of the A-type ionic liquid to the lithium salt is 60: 8-60: 20, the mass ratio of the A-type ionic liquid to the graphene oxide is 60: 0.05-60: 0.1.
10. the ionic liquid electrolyte of claim 6, wherein the ionic liquid electrolyte is used as an electrolyte in an electrochemical sensor for detecting ammonia, hydrogen sulfide, sulfur dioxide, or nitrogen dioxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113295749A (en) * | 2021-05-21 | 2021-08-24 | 宁夏医科大学 | Nitrogen-doped graphene/ionic liquid composite material modified glassy carbon electrode, preparation method thereof and epinephrine quantitative detection method |
| CN114624312A (en) * | 2022-01-06 | 2022-06-14 | 郑州大学 | Preparation method of solid electrolyte flexible material and electrochemical gas sensor |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417407A (en) * | 2002-12-12 | 2003-05-14 | 中国科学院化学研究所 | Room temperature ionic liquid containing unsaturated double bond and its prepn and application |
| JP2004333163A (en) * | 2003-04-30 | 2004-11-25 | Riken Keiki Co Ltd | Electrochemical gas sensor |
| CN102227629A (en) * | 2008-12-01 | 2011-10-26 | Msa奥尔有限责任公司 | Electrochemical gas sensors with ionic liquid electrolyte systems |
| CN102468515A (en) * | 2010-11-05 | 2012-05-23 | 海洋王照明科技股份有限公司 | Lithium ion battery and preparation method thereof |
| CN102768901A (en) * | 2012-08-06 | 2012-11-07 | 张宝生 | Long-life capacitance battery |
| CN103682287A (en) * | 2013-12-19 | 2014-03-26 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-based composite anode material, preparation method thereof and battery |
| CN103787981A (en) * | 2012-10-31 | 2014-05-14 | 海洋王照明科技股份有限公司 | Imidazoles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof |
| CN104078686A (en) * | 2013-03-26 | 2014-10-01 | Sk新技术株式会社 | Current collector for secondary battery and secondary battery comprising the same |
| CN104193685A (en) * | 2014-09-29 | 2014-12-10 | 陕西科技大学 | Preparing method of thiocyanate functionalized ionic liquid electrolyte |
| WO2015032480A1 (en) * | 2013-09-09 | 2015-03-12 | Dräger Safety AG & Co. KGaA | Liquid electrolyte for an electrochemical gas sensor |
| CN105925246A (en) * | 2016-04-16 | 2016-09-07 | 吉林大学 | Electricity generated acid produced by blending substances with changeable oxidation state and electrolyte and applications thereof |
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN108795407A (en) * | 2018-07-06 | 2018-11-13 | 常州铱视光电科技有限公司 | Based on the electroluminescent sour electrochromic material acted on and prepare electrochromic device |
| CN109004192A (en) * | 2018-07-16 | 2018-12-14 | 郑州大学 | Combination electrode, the battery and preparation method thereof of graphene/graphene oxide cladding |
| CN109745833A (en) * | 2019-03-07 | 2019-05-14 | 中国科学院过程工程研究所 | A kind of hydroxyl proton type ionic liquid absorbent efficiently separating recycling ammonia |
| CN109810295A (en) * | 2018-12-29 | 2019-05-28 | 青岛科技大学 | A kind of preparation method of moisture-sensitive sensing membrane |
| CN110090566A (en) * | 2019-05-10 | 2019-08-06 | 郑州大学 | A kind of sulfonated polyether-ether-ketone-ionic liquid composite membrane, preparation method and its in CO2Application in separation |
-
2020
- 2020-01-16 CN CN202010046794.0A patent/CN111239222B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417407A (en) * | 2002-12-12 | 2003-05-14 | 中国科学院化学研究所 | Room temperature ionic liquid containing unsaturated double bond and its prepn and application |
| JP2004333163A (en) * | 2003-04-30 | 2004-11-25 | Riken Keiki Co Ltd | Electrochemical gas sensor |
| CN102227629A (en) * | 2008-12-01 | 2011-10-26 | Msa奥尔有限责任公司 | Electrochemical gas sensors with ionic liquid electrolyte systems |
| CN102468515A (en) * | 2010-11-05 | 2012-05-23 | 海洋王照明科技股份有限公司 | Lithium ion battery and preparation method thereof |
| CN102768901A (en) * | 2012-08-06 | 2012-11-07 | 张宝生 | Long-life capacitance battery |
| CN103787981A (en) * | 2012-10-31 | 2014-05-14 | 海洋王照明科技股份有限公司 | Imidazoles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof |
| CN104078686A (en) * | 2013-03-26 | 2014-10-01 | Sk新技术株式会社 | Current collector for secondary battery and secondary battery comprising the same |
| CN105492901A (en) * | 2013-09-09 | 2016-04-13 | 德尔格安全股份两合公司 | Liquid electrolyte for an electrochemical gas sensor |
| WO2015032480A1 (en) * | 2013-09-09 | 2015-03-12 | Dräger Safety AG & Co. KGaA | Liquid electrolyte for an electrochemical gas sensor |
| CN103682287A (en) * | 2013-12-19 | 2014-03-26 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-based composite anode material, preparation method thereof and battery |
| CN104193685A (en) * | 2014-09-29 | 2014-12-10 | 陕西科技大学 | Preparing method of thiocyanate functionalized ionic liquid electrolyte |
| CN105925246A (en) * | 2016-04-16 | 2016-09-07 | 吉林大学 | Electricity generated acid produced by blending substances with changeable oxidation state and electrolyte and applications thereof |
| CN107331853A (en) * | 2017-08-18 | 2017-11-07 | 郑州大学 | A kind of graphene composite multi-layer spherical manganic acid lithium electrode material with holes and its lithium ion battery of preparation |
| CN108795407A (en) * | 2018-07-06 | 2018-11-13 | 常州铱视光电科技有限公司 | Based on the electroluminescent sour electrochromic material acted on and prepare electrochromic device |
| CN109004192A (en) * | 2018-07-16 | 2018-12-14 | 郑州大学 | Combination electrode, the battery and preparation method thereof of graphene/graphene oxide cladding |
| CN109810295A (en) * | 2018-12-29 | 2019-05-28 | 青岛科技大学 | A kind of preparation method of moisture-sensitive sensing membrane |
| CN109745833A (en) * | 2019-03-07 | 2019-05-14 | 中国科学院过程工程研究所 | A kind of hydroxyl proton type ionic liquid absorbent efficiently separating recycling ammonia |
| CN110090566A (en) * | 2019-05-10 | 2019-08-06 | 郑州大学 | A kind of sulfonated polyether-ether-ketone-ionic liquid composite membrane, preparation method and its in CO2Application in separation |
Non-Patent Citations (8)
| Title |
|---|
| MIN YU 等: "Protic Ionic-Liquid-Supported Activated Carbon with Hierarchical Pores for Efficient NH3 Adsorption", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| MIN YU 等: "Protic Ionic-Liquid-Supported Activated Carbon with Hierarchical Pores for Efficient NH3 Adsorption", 《ACS SUSTAINABLE CHEM. ENG.》, vol. 7, 4 June 2019 (2019-06-04), pages 11769 - 11777 * |
| 孙国华 等: "1-乙基-3-甲基咪唑三氟乙酸盐作为电化学双电层电容器电解液的电化学性能", 《电化学》 * |
| 孙国华 等: "1-乙基-3-甲基咪唑三氟乙酸盐作为电化学双电层电容器电解液的电化学性能", 《电化学》, vol. 13, no. 1, 28 February 2007 (2007-02-28), pages 44 - 49 * |
| 李广伟 等: "离子液体在电流型电化学气体传感器中的应用", 《化工进展》 * |
| 李广伟 等: "离子液体在电流型电化学气体传感器中的应用", 《化工进展》, vol. 32, no. 10, 31 December 2013 (2013-12-31), pages 2409 - 2414 * |
| 李翠华 等: "新型离子液体用于碳糊电极的直接电化学研究", 《深圳大学学报(理工版)》 * |
| 李翠华 等: "新型离子液体用于碳糊电极的直接电化学研究", 《深圳大学学报(理工版)》, vol. 26, no. 4, 31 October 2009 (2009-10-31), pages 351 - 355 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113295749A (en) * | 2021-05-21 | 2021-08-24 | 宁夏医科大学 | Nitrogen-doped graphene/ionic liquid composite material modified glassy carbon electrode, preparation method thereof and epinephrine quantitative detection method |
| CN114624312A (en) * | 2022-01-06 | 2022-06-14 | 郑州大学 | Preparation method of solid electrolyte flexible material and electrochemical gas sensor |
| CN114624312B (en) * | 2022-01-06 | 2024-05-03 | 郑州大学 | Preparation method of solid electrolyte flexible material and electrochemical gas sensor |
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