CN109180951B - Preparation method of poly-amino organic-inorganic hybrid compound and application of poly-amino organic-inorganic hybrid compound as hydrogen fluoride gas sensor - Google Patents
Preparation method of poly-amino organic-inorganic hybrid compound and application of poly-amino organic-inorganic hybrid compound as hydrogen fluoride gas sensor Download PDFInfo
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Abstract
The invention discloses a polyamino organic-inorganic hybrid compound, a preparation method thereof and application of the compound as a hydrogen fluoride gas sensor. The organic-inorganic hybrid compound of the polyamine group has a metal-organic framework structure, is stable in structure, is sensitive to hydrogen fluoride gas, and has good selectivity to gas. The method can be used for preparing a high-quality novel hydrogen fluoride gas sensor and embedding the high-quality novel hydrogen fluoride gas sensor into a power battery management system, so that trace leakage of electrolyte of the power battery is monitored, the leakage condition of the power battery is found in the early stage, the service life of the battery is prolonged, and the safety of people and vehicles is improved. The gas sensor disclosed by the invention is applied to the industries of medical treatment, environmental protection, war industry, aerospace, industrial production, wearable equipment and the like.
Description
Technical Field
The invention relates to a preparation method and application of a hydrogen fluoride gas sensitive material, in particular to a metal organic framework compound material, application and a preparation method thereof, which are applied to the technical fields of electrochemical functional materials and power batteries.
Background
China is a large country with petroleum import, eighty percent of the petroleum import of China is used for consumption of automobiles, and the fuel vehicles bring a headache pollution problem, the world countries basically set the fuel vehicles to be released before 2030 years at present, and new energy automobiles, especially pure electric automobiles, are developed and meet the opportunity. In addition, people have a demand for vehicle intellectualization, electric vehicles are rapidly developed, and by 2018 'data of China automobile industry Association', the sales volume of new energy vehicles in China has been continuously released for the first world in three years, and 2016 (2016 global electric vehicle prospect) published by 2016 (International energy agency) in 2016 requires that the number of electric vehicles in 2020 world ranges reaches 2000 thousands. In 2017, the new energy automobiles in China are sold in 77.7 thousands. At present, through market cultivation of new energy vehicles, the acceptance of the new energy vehicles in market mountains reaches over 90 percent, and the development of pure electric new energy vehicles in the future has great potential.
However, the power battery always has certain risks in terms of safety, and in particular, the improper operation of the power battery during production, packaging and use can cause electrolyte leakage of the power battery. The current solution for BMS (battery management systems) is thermal management monitoring for leakage of power battery electrolyte, i.e. when there is a leakage in the battery, abnormal operation can cause the battery to overheat, causing BMS alarms. But the monitoring of the thermal management system cannot ensure the instantaneity and the safety. Because the time from heating to burning (explosion) of the power battery is from a few seconds to a few tens of seconds, and most abnormal heating is usually irreversible, which is why spontaneous combustion often occurs in pure electric vehicles. It is important to early detect the leakage problem of the power battery.
The electrolyte of the power battery can be various, but considering the performance, safety and recyclability of the battery, most of the electrolyte of the power battery on the market is lithium hexafluorophosphate (LiPF)6). Once leaked into the air, lithium hexafluorophosphate reacts with water vapor in the air to generate hydrogen fluoride gas, and the related chemical reaction equation is as follows: 2LiPF6+2H2O→ 2PF5+2HF ≈ 2 LiOH. If the specific induction of the generated hydrogen fluoride gas can be realized, the monitoring of the electrolyte leakage can be realized earlier. The leakage of the battery can be known in advance, so that the early discovery and the early maintenance can be realized, and the loss caused by the damage of the battery is reduced. In addition, the hydrogen fluoride is a strong toxic gas, and the safety of operators is guaranteed by realizing early monitoring. At present, the method for detecting the hydrogen fluoride gas aiming at the leakage of the electrolyte of the power battery is not visible for a long time, and the method for detecting the hydrogen fluoride gas aiming at the hydrogen fluoride gasThe monitoring and the ascertaining of whether the power battery leaks belongs to a new subject, and no relevant report that the hydrogen fluoride gas detection sensitive material is applied to the technical field of the power battery is found so far.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a preparation method of a polyamine-based organic-inorganic hybrid compound and application of the polyamine-based organic-inorganic hybrid compound as a hydrogen fluoride gas sensor. The polyamine organic-inorganic hybrid compound can be used for preparing a high-quality novel hydrogen fluoride gas sensor and is embedded into a power Battery Management System (BMS), so that trace leakage of electrolyte of a power battery is monitored, the leakage condition of the power battery is discovered in the early stage, the service life of the battery is prolonged, and the safety of people and vehicles is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a multi-amino organic-inorganic hybrid compound uses chromium ions as connecting points and 2, 5-diamino-terephthalic acid as a ligand to form a skeleton, so as to form a porous and multi-amino polymer material and form a metal-organic skeleton molecular structure.
As a preferred technical scheme of the invention, the organic-inorganic hybrid material three-dimensional framework stereo structure of the polyamine-based organic-inorganic hybrid compound comprises the following structural formula components:
as a preferred technical scheme of the invention, the organic-inorganic hybrid compound of the polyamine group has the following planar molecular structural formula of the organic-inorganic hybrid material:
the application of the polyamine organic-inorganic hybrid compound can be used for responding to gas with the concentration of hydrogen fluoride gas not higher than 1000ppm and detecting the hydrogen fluoride gas.
As a preferred embodiment of the present invention, the use of the polyamine-based organic-inorganic hybrid compound is useful for detecting hydrogen fluoride gas in response to a gas having a hydrogen fluoride gas concentration of 0.05ppm to 100 ppm.
The invention relates to a hydrogen fluoride gas sensor prepared from a polyamine organic-inorganic hybrid compound, which is characterized in that the organic-inorganic hybrid compound of polyamine is coated on a QCM quartz crystal microbalance to obtain a QCM element, and the prepared QCM element is arranged on a hydrogen fluoride gas sensor module to obtain the QCM hydrogen fluoride gas sensor.
The invention relates to application of a hydrogen fluoride gas sensor, which is characterized in that the hydrogen fluoride gas sensor is arranged in a power battery management system to monitor the electrolyte leakage of a power battery.
The invention relates to a preparation method of a hydrogen fluoride gas sensor, which comprises the following steps:
(1) dissolving the polyamine organic-inorganic hybrid compound in deionized water, and preparing hydrogen fluoride sensitive material slurry with the concentration of not less than 1mg/ml after ultrasonic dispersion treatment for at least 10 minutes;
(2) coating the hydrogen fluoride sensitive material slurry prepared in the step (1) on a QCM quartz crystal microbalance by using a micropipettor to prepare a hydrogen fluoride sensitive material film, and quickly drying and curing the hydrogen fluoride sensitive material film at the temperature of not higher than 40 ℃ by using nitrogen as a protective gas; then manufacturing a silver layer electrode on the surface of the hydrogen fluoride sensitive material film, and loading the hydrogen fluoride sensitive material film on the silver electrode to form a sandwich structure to obtain the QCM hydrogen fluoride sensitive element;
(3) and (3) then, loading the QCM hydrogen fluoride sensitive element prepared in the step (2) on a QCM hydrogen fluoride module to prepare the QCM hydrogen fluoride gas sensor.
A method for preparing the polyamine-based organic-inorganic hybrid compound of the invention comprises the following steps:
a. according to Cr3+:2, 5-diamino-terephthalic acid: the molar ratio of NaOH is 1:1:2, soluble trivalent chromium salt, 2, 5-diamino-terephthalic acid and NaOH are taken as solutes and mixed into deionized water together, and the mixture is stirred until the solutes are dissolved to obtain Cr3+Polyamine organic-inorganic mixed solution with the concentration not higher than 0.133 mol/L; preferably, the soluble trivalent chromium salt is Cr (NO)3)3、CrCl3、Cr2(SO4)3Any one salt or a mixed salt of any plurality thereof;
b. then transferring the polyamine organic-inorganic mixed solution prepared in the step b into a reaction kettle for hydrothermal treatment, and carrying out hydrothermal reaction at the temperature of not less than 150 ℃ for at least 10 hours to obtain a reaction product system solution;
c. naturally cooling the reaction product system solution obtained in the step b to room temperature, centrifuging, washing with DMF and ethanol for at least 1 time respectively, adding ethanol into the washed product, keeping the ethanol mixture of the product at the temperature of not higher than 100 ℃ for at least 24 hours, and removing the solvent in the product mixture by a supercritical vacuum drying method to obtain the polyamine organic-inorganic hybrid compound product.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the organic-inorganic hybrid compound of the polyamine group has a metal-organic framework structure, is stable in structure, sensitive to hydrogen fluoride gas and good in gas selectivity;
2. the polyamine organic-inorganic hybrid compound is applied to a hydrogen fluoride gas sensor and is embedded into the conventional Battery Management System (BMS), so that the leakage condition of the electrolyte of the power battery is monitored, the safety of people and vehicles is ensured, and the service life of the battery is prolonged; the gas sensor has reliable detection result and low cost, can realize long-term continuous detection, and is suitable for being applied to power batteries to realize continuous safety monitoring of hydrogen fluoride gas;
3. the method can be applied to the preparation of the hydrogen fluoride gas sensor, the gas sensor is a high-tech and high-technology barrier industry, the application scene of the gas sensor is wide, and the gas sensor is applied to the industries such as medical treatment, environmental protection, military industry, aerospace, industrial production, wearable equipment and the like.
Drawings
FIG. 1 is a three-dimensional skeleton structure of an organic-inorganic hybrid compound of polyamine group according to an embodiment of the present invention.
FIG. 2 is a continuous step injection test chart of the hydrogen difluoride gas sensor according to the embodiment of the present invention.
FIG. 3 is a diagram showing the gas selectivity test of a hydrogen difluoride gas sensor according to an embodiment of the present invention.
FIG. 4 is a diagram illustrating repeatability tests of a hydrogen difluoride gas sensor according to an embodiment of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example one
In this example, a polyamino organic-inorganic hybrid compound is formed by using chromium ions as the connecting points and 2, 5-diamino-terephthalic acid as the ligand to form a skeleton, and a porous, polyamino polymer material is formed to form a metal-organic skeleton molecular structure. In this example, the polyamine-based organic-inorganic hybrid compound has an organic-inorganic hybrid material three-dimensional framework three-dimensional structure comprising the following structural formula:
in this example, the organic-inorganic hybrid compound of the polyamine group has the planar molecular structural formula of the organic-inorganic hybrid material:
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this example, the application of the polyamine-based organic-inorganic hybrid compound can be used for detecting hydrogen fluoride gas in response to a gas having a hydrogen fluoride gas concentration of 0.05ppm to 1000 ppm.
In this example, a QCM element was obtained by coating a QCM quartz crystal microbalance with the hydrogen fluoride gas sensor prepared from the polyamine-based organic-inorganic hybrid compound of example one, and the QCM element was placed on a hydrogen fluoride gas sensor module to obtain a QCM hydrogen fluoride gas sensor. The embodiment is a USB interface type hydrogen fluoride gas sensor based on a QCM element, and the hydrogen fluoride gas sensor module is also provided with a display device which can display the hydrogen fluoride gas concentration data of a sample to be detected. And arranging a hydrogen fluoride gas sensor in a power battery management system to monitor the electrolyte leakage of the power battery.
The preparation method of the hydrogen fluoride gas sensor comprises the following steps:
(1) dissolving the polyamine-based organic-inorganic hybrid compound of claim 1 in deionized water, and performing ultrasonic dispersion treatment for 10 minutes to prepare hydrogen fluoride sensitive material slurry with a concentration of 1 mg/ml;
(2) coating the hydrogen fluoride sensitive material slurry prepared in the step (1) on a QCM quartz crystal microbalance by using a micropipette to prepare a hydrogen fluoride sensitive material film, and quickly drying and curing the hydrogen fluoride sensitive material film at the temperature of 40 ℃ by using nitrogen as a protective gas; then manufacturing a silver layer electrode on the surface of the hydrogen fluoride sensitive material film, and loading the hydrogen fluoride sensitive material film on the silver electrode to form a sandwich structure to obtain the QCM hydrogen fluoride sensitive element;
(3) and (3) then, loading the QCM hydrogen fluoride sensitive element prepared in the step (2) on a QCM hydrogen fluoride module to prepare the QCM hydrogen fluoride gas sensor. The embodiment can prepare the USB interface hydrogen fluoride gas sensor based on the QCM hydrogen fluoride sensitive element.
Testing and analyzing the performance of the sensor:
example NH2Application of MIL-002 organic-inorganic hybrid metal organic framework molecule hydrogen fluoride gas sensor sensitive material, coating the prepared sensitive material on a QCM quartz crystal microbalance, and finally using the prepared QCM element on a hydrogen fluoride gas sensor module. The method comprises the following steps: dissolving the prepared material in deionized water, performing ultrasonic dispersion, coating a sensitive material on the QCM element by using a micropipette, taking nitrogen as a protective gas, and quickly drying to prepare a sensitive film on a silver electrode, wherein the QCM hydrogen fluoride element is successfully prepared. And then, loading the QCM element on a self-developed QCM hydrogen fluoride module to obtain the QCM hydrogen fluoride gas sensor. The prepared device has good stability. The continuous step sample introduction test, the gas response selectivity test and the response repeatability test are respectively carried out on the sensor, and the continuous step sample introduction test, the gas response selectivity test and the response repeatability test are respectively shown in fig. 2, fig. 3 and fig. 4.
The hydrogen fluoride gas sensor of this example was used to perform continuous step injection tests on 500ppb, 1ppm, 2.5ppm, 5ppm, and 10ppm hydrogen fluoride gas, and fig. 2 is a continuous step injection test chart of the hydrogen fluoride gas sensor of this example. As can be seen from fig. 2, the hydrogen fluoride gas sensor prepared in this embodiment has a good response value to 500ppb hydrogen fluoride gas, and in the process of step sampling, as the concentration gradually deepens, the response curve has good incremental property and repeatability, and has extremely high sensitivity.
The hydrogen fluoride gas sensor of this example was used to selectively measure 1ppm of hydrogen fluoride, hydrogen sulfide, carbon dioxide, nitrogen dioxide, ammonia, nitrogen monoxide, hydrogen, and carbon monoxide gases. Fig. 3 is a gas selectivity test chart of the hydrogen fluoride gas sensor according to the present embodiment. Referring to fig. 3, it can be seen that the hydrogen fluoride gas sensor prepared in this embodiment has good selectivity for various interference gases, and has a response value for hydrogen fluoride 7 to 10 times that of the rest common interference gases, and the selectivity is excellent.
Using the hydrogen fluoride gas sensor of this example, a repeatability test was performed on a 500ppb hydrogen fluoride gas sensor, and fig. 4 is a repeatability test chart of the hydrogen fluoride gas sensor of this example. Referring to fig. 4, it can be seen that the response values of the hydrogen fluoride gas sensor prepared in this embodiment to 500ppb of hydrogen fluoride gas are substantially consistent, and the response effects are found to be substantially consistent after 2000 times of repeated cycle tests. NH of the above example2The synthesis of MIL-002 organic-inorganic hybrid metal organic framework molecule and the application thereof in QCM sensor for detecting hydrogen fluoride gas are the original invention. The sensor of the embodiment utilizes the high sensitivity and selectivity of the sensitive material to hydrogen fluoride and the stability of molecules, and also utilizes the advantages of low cost, simple device and easy integration of the QCM element. Meanwhile, a new idea is provided for the preparation of the sensitive material of the QCM sensing element, and a new energy application field is opened up for the application of metal organic framework molecules.
From the above test results, it can be known that the Quartz Crystal Microbalance (QCM) hydrogen fluoride gas sensor is prepared in the second embodiment based on the successful development of the sensitive material. The invention not only widens the application of the metal organic framework compound material in the sensitive material of the gas sensor, but also provides a stable, porous and high-sensitivity multi-amino sensitive material design method for the QCM sensor. The hydrogen fluoride gas sensor prepared in the second embodiment is subjected to selectivity, repeatability, sensitivity and stability detection, and the detection sensitivity is high. The performance is stable when the repeatability test is carried out for 2000 times of less than 500ppb, and the hydrogen fluoride gas response value is about 7 times of the hydrogen sulfide gas response value, the carbon dioxide gas response value, the nitrogen dioxide gas response value, the ammonia gas response value, the nitrogen monoxide gas response value, the hydrogen gas response value and the carbon monoxide gas response value, so that the selectivity is proved to be good. Example application of hydrogen difluoride gas sensor to a power cell management system: on the basis of successful development of sensor elements, in order to embed the hydrogen fluoride gas sensor in BNS, the hydrogen fluoride gas sensor is used for the first time on monitoring the electrolyte leakage of the power battery.
EXAMPLE III
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a method for preparing a polyamine-based organic-inorganic hybrid compound of the present invention comprises the following steps:
a. according to Cr3+:2, 5-diamino-terephthalic acid: the molar ratio of NaOH is 1:1:2, 2mmol of soluble trivalent chromium salt Cr (NO) is taken3)3·9H2O, 2mmol of 2, 5-diamino-terephthalic acid and 4mmol of NaOH are taken as solutes and mixed together into 15ml of deionized water, and the mixture is stirred until the solutes are dissolved to obtain the alloy containing Cr3+An organic-inorganic mixed solution of the polyamine group of (1);
b. then transferring the polyamine organic-inorganic mixed solution prepared in the step b into a reaction kettle with a solvent of 50ml for hydrothermal treatment, and carrying out hydrothermal reaction for 10 hours at 150 ℃ to obtain a reaction product system solution;
c. naturally cooling the reaction product system solution obtained in the step b to room temperature, centrifuging, washing with DMF and ethanol for 2 times respectively, adding ethanol into the cleaned product, keeping the ethanol mixture of the product at 100 ℃ for 24 hours, and removing the solvent in the product mixture by a supercritical vacuum drying method to obtain the polyamine organic-inorganic hybrid compound product. Referring to fig. 1, it can be seen that the prepared material has a structure of polyamine group and is structurally stable. This example enables the preparation of example NH2The MIL-002 organic-inorganic hybrid metal organic framework molecular hydrogen fluoride gas sensor sensitive material has the advantages of simple preparation route, high efficiency, easy control, high yield and low cost.
The planar molecular structural formula of the NH2-MIL-002MOF organic-inorganic hybrid sensitive material synthesized in the example is as follows:
the polyamine organic-inorganic hybrid compound prepared in this example uses chromium ions as a connection point, and 2, 5-diamino-terephthalic acid as a ligand to form a skeleton, and is a porous polyamino polymer material. The material is porous, provides a large specific surface area, so that gas is easily adsorbed, the selectivity and sensitivity to hydrogen fluoride gas are improved due to the existence of polyamino, and the whole framework has good stability, so that the material has good stability and repeatability in use. The sample prepared by the embodiment is stable for a long time and is suitable for long-term use on a power battery.
In summary, in order to achieve the purpose of monitoring the electrolyte leakage of the power battery by detecting the hydrogen fluoride gas, the invention mainly comprises three parts: firstly, preparing a sensitive material of a hydrogen fluoride gas sensor; secondly, preparing a hydrogen fluoride gas sensor element; and thirdly, applying the hydrogen fluoride gas sensor to a power Battery Management System (BMS). The hydrogen fluoride gas sensor is sensitive in response and is embedded in the conventional Battery Management System (BMS), so that the leakage condition of the electrolyte of the power battery is monitored, the safety of people and vehicles is ensured, and the service life of the battery is prolonged. The gas sensor has wide application scenes, and has application in the industries of medical treatment, environmental protection, military industry, aerospace, industrial production, wearable equipment and the like. The gas sensor has reliable detection result and low cost, can realize long-term continuous detection, and is suitable for being applied to power batteries to realize continuous safety monitoring of the hydrogen fluoride gas.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principles of the present invention should be made in an equivalent manner without departing from the spirit and principles of the present invention, and all of the technical principles and inventive concepts of the polyamine-based organic-inorganic hybrid compound, the method for preparing the same, and the application thereof as a hydrogen fluoride gas sensor fall within the scope of the present invention.
Claims (7)
1. Use of a polyamino organic-inorganic hybrid compound for detecting hydrogen fluoride gas in response to a gas having a hydrogen fluoride concentration of not more than 1000 ppm; the organic-inorganic hybrid compound of the polyamine takes chromium ions as connecting points and takes 2, 5-diamino-terephthalic acid as a ligand to form a skeleton, so as to form a porous polyamino polymer material and form a metal-organic skeleton molecular structure; the organic-inorganic hybrid compound of the polyamine group has a planar molecular structural formula as shown in the following:
2. use of organic-inorganic hybrid compounds of polyamines according to claim 1, wherein the concentration of hydrogen fluoride in the gas is between 0.05ppm and 100 ppm.
3. Use of a polyamine-based organic-inorganic hybrid compound according to claim 1, wherein said polyamine-based organic-inorganic hybrid compound is prepared by a process comprising the steps of:
a. according to Cr3+:2, 5-diamino-terephthalic acid: the molar ratio of NaOH is 1:1:2, soluble trivalent chromium salt, 2, 5-diamino-terephthalic acid and NaOH are taken as solutes and mixed into deionized water together, and the mixture is stirred until the solutes are dissolved to obtain Cr3+Polyamine organic-inorganic mixed solution with the concentration not higher than 0.133 mol/L;
b. then transferring the polyamine organic-inorganic mixed solution prepared in the step a into a reaction kettle for hydrothermal treatment, and carrying out hydrothermal reaction at the temperature of not less than 150 ℃ for at least 10 hours to obtain a reaction product system solution;
c. naturally cooling the reaction product system solution obtained in the step b to room temperature, centrifuging, washing with DMF and ethanol for at least 1 time respectively, adding ethanol into the washed product, keeping the ethanol mixture of the product at the temperature of not higher than 100 ℃ for at least 24 hours, and removing the solvent in the product mixture by a supercritical vacuum drying method to obtain the polyamine organic-inorganic hybrid compound product.
4. Use of a polyamine-based organic-inorganic hybrid compound according to claim 3 wherein in step a the soluble trivalent chromium salt is Cr (NO)3)3、CrCl3、Cr2(SO4)3Any one salt or a mixed salt of any plurality thereof.
5. A hydrogen fluoride gas sensor prepared by the use of the polyamine-based organic-inorganic hybrid compound according to claim 1, wherein: coating the polyamine organic-inorganic hybrid compound on a QCM quartz crystal microbalance to prepare a hydrogen fluoride sensitive material film, then loading the hydrogen fluoride sensitive material film on a silver electrode to obtain a QCM hydrogen fluoride sensitive element, and loading the QCM hydrogen fluoride sensitive element on a QCM hydrogen fluoride module to obtain the QCM hydrogen fluoride gas sensor.
6. Use of a hydrogen fluoride gas sensor according to claim 5, wherein: and arranging a hydrogen fluoride gas sensor in a power battery management system to monitor the electrolyte leakage of the power battery.
7. A method of manufacturing a hydrogen fluoride gas sensor according to claim 5, comprising the steps of:
(1) dissolving an organic-inorganic hybrid compound of polyamine in deionized water, and preparing hydrogen fluoride sensitive material slurry with the concentration of not less than 1mg/ml after ultrasonic dispersion treatment for at least 10 minutes;
(2) coating the hydrogen fluoride sensitive material slurry prepared in the step (1) on a QCM quartz crystal microbalance by using a micropipettor to prepare a hydrogen fluoride sensitive material film, and quickly drying and curing the hydrogen fluoride sensitive material film at the temperature of not higher than 40 ℃ by using nitrogen as a protective gas; then manufacturing a silver layer electrode on the surface of the hydrogen fluoride sensitive material film, and loading the hydrogen fluoride sensitive material film on the silver electrode to form a sandwich structure to obtain the QCM hydrogen fluoride sensitive element;
(3) and (3) then, loading the QCM hydrogen fluoride sensitive element prepared in the step (2) on a QCM hydrogen fluoride module to prepare the QCM hydrogen fluoride gas sensor.
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