CN116482185A - CO sensor gas-sensitive layer and application thereof in lithium battery energy storage system - Google Patents
CO sensor gas-sensitive layer and application thereof in lithium battery energy storage system Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
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- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention relates to the technical field of gas monitoring, and discloses a CO sensor gas-sensitive layer and application thereof in a lithium battery energy storage system. The invention utilizes electrostatic adsorption to lead the modified Ti to be 3 C 2 The nano sheets and the graphene oxide are alternately stacked and self-assembled into a multi-layer structure, and the multi-layer structure can reduce the self-stacking of the graphene oxide and prevent the aggregation of the graphene oxide. Based on the skillfully utilizing urea in Ti 3 C 2 In situ thermal decomposition between/rGO multilayer material layersTo increase the interlayer spacing and thereby construct an ideal nanoscale transmission channel. Ti with the special nanoscale transmission channel 3 C 2 When being used as a gas sensitive layer of a gas sensor, the rGO multilayer material not only has extremely high sensitivity and selectivity to CO, but also has excellent reversibility and cycle stability, and is particularly suitable for monitoring characteristic gas CO generated when a lithium battery energy storage device is out of control, thereby realizing early warning of fire disaster of the lithium battery energy storage system.
Description
Technical Field
The invention relates to the technical field of gas monitoring, in particular to a CO sensor gas-sensitive layer and application thereof in a lithium battery energy storage system.
Background
In recent years, electrochemical energy storage represented by lithium batteries has been increased in an explosive manner in China, and currently, the number of electrochemical energy storage projects under construction in China exceeds 600, and the estimated 2025 year is up to more than 30 GW. The lithium iron phosphate battery has the advantages of high output voltage, high energy density, long cycle life and the like, and is widely applied to the field of large-scale energy storage. However, the existing lithium iron phosphate battery is not intrinsically safe due to the adoption of flammable and explosive electrolyte, and the battery is easy to generate thermal runaway under the abuse condition, so that the system-scale fire explosion accident is developed. The fire accident of the lithium ion battery energy storage system occurs.
In the initial stage of thermal runaway of the lithium iron phosphate battery, some combustible gases such as H can be generated by side reaction of electrolyte 2 CO, etc. The combustible gas generated after the battery faults in the atmosphere are monitored, so that the occurrence of the battery fire can be perceived in advance, further early warning is carried out in advance, and a reliable means is provided for taking effective measures to inhibit the battery fire. The gas sensor-based realization of rapid and efficient combustible gas monitoring has important significance for the health state assessment of the lithium ion battery and the development of high-precision early warning technology.
Graphene, as a two-dimensional carbon material, has excellent mechanical, electrical, thermal and optical properties. However, the graphene film is easy to agglomerate in the assembly process, so that an internal nanoscale transport channel is influenced, the electrochemical activity of the graphene film is poor, and the application of the graphene film in gas sensing is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a CO sensor gas-sensitive layer and application thereof in a lithium battery energy storage system. The invention utilizes electrostatic adsorption to lead the modified Ti to be 3 C 2 The nano sheets and the graphene oxide are alternately stacked and self-assembled into a multi-layer structure, and the multi-layer structure can reduce the self-stacking of the graphene oxide and prevent the aggregation of the graphene oxide. Based on the skillfully utilizing urea in Ti 3 C 2 In situ thermal decomposition between/rGO multi-layer material layers to increase interlayer spacing, thereby constructing an ideal nanoscale transmission channel. Ti with the special nanoscale transmission channel 3 C 2 When being used as a gas sensitive layer of a gas sensor, the rGO multilayer material not only has extremely high sensitivity and selectivity to CO, but also has excellent reversibility and cycle stability, and is particularly suitable for monitoring characteristic gas CO generated when a lithium battery energy storage system is out of control, thereby realizing early warning of fire disaster of the lithium battery energy storage system.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a CO sensor gas-sensitive layer, which is Ti 3 C 2 The preparation method of the rGO film comprises the following steps:
s1: adding Ti to the stirred HCl/LiF mixture 3 AlC 2 Continuously stirring the powder for reaction, centrifuging the obtained mixed solution, repeatedly washing and centrifuging the centrifugal precipitate, collecting the precipitate, redispersing the precipitate in a dodecyl dimethyl benzyl ammonium chloride aqueous solution, carrying out water bath oscillation heating treatment, adding urea into the obtained suspension, carrying out ultrasonic treatment, centrifuging, and collecting the supernatant to obtain the modified Ti 3 C 2 A nanosheet dispersion.
In S1, the invention uses HCl/LiF to make the layered material Ti 3 AlC 2 Etching and removing the Al layer in the alloy, repeatedly washing and centrifuging to obtain stripped Ti 3 C 2 A nano-sheet. Dispersing it in aqueous solution of dodecyl dimethyl benzyl ammonium chloride for modification, and introducing dodecyl dimethyl benzyl ammonium chloride into Ti 3 C 2 The nano-sheet layer obtains positively charged modified Ti 3 C 2 The nano-sheet is continuously added with urea on the basis to obtain the modified Ti containing urea 3 C 2 A nanosheet dispersion.
S2: and (3) preparing graphene oxide dispersion liquid.
S3: dropwise adding the graphene oxide dispersion liquid to the modified Ti under stirring 3 C 2 Obtaining Ti from the nano-sheet dispersion liquid 3 C 2 GO dispersion, ti 3 C 2 Graphene oxide and modified Ti in GO dispersion 3 C 2 The mass ratio of the nano-sheets is 7:3-9:1; ultrasonic treatment of Ti 3 C 2 Spreading the GO dispersion liquid in a mould, drying, carrying out heat treatment at 300-350 ℃ to decompose urea, and then reducing graphene oxide under the condition of heat preservation and hydrogen introduction to obtain Ti 3 C 2 The rGO film is the gas-sensitive layer of the CO sensor.
In S3, the graphene oxide dispersion is added dropwise to the modified Ti 3 C 2 Obtaining Ti from the nano-sheet dispersion 3 C 2 Spreading the GO dispersion liquid in a mould to prepare a film, and modifying Ti due to negative charge of graphene oxide in the drying process 3 C 2 The nano-sheet has positive charge, so that the nano-sheet and the nano-sheet can spontaneously react under the action of electrostatic adsorptionAnd the graphene oxide is alternately stacked and assembled to form a multilayer structure, and the self-stacking of the graphene oxide can be reduced and the aggregation of the graphene oxide can be prevented by the multilayer structure. At the same time, as the solvent gradually decreases during the drying process, urea also deposits between layers of the multilayer structure, forming a layer of Ti loaded with urea 3 C 2 The graphene oxide is reduced and converted into Ti in the subsequent hydrogen-introducing high-temperature environment of the/GO multilayer material 3 C 2 The electrical conductivity of the rGO multilayer material is enhanced; at the same time urea is at high temperature at Ti 3 C 2 The interlayer in-situ decomposition of the/rGO multilayer material generates gases, and the generation of the gases causes the volume to be increased, so that the interlayer spacing can be remarkably increased, and an ideal nanoscale transmission channel is constructed. The team of the invention found that Ti with the special nanoscale transmission channel 3 C 2 The rGO multilayer material has extremely high sensitivity and selectivity to CO when being used as a gas sensitive layer of a gas sensor, has excellent reversibility and cycle stability, and is particularly suitable for monitoring characteristic gas CO generated when a lithium battery energy storage device is out of control.
The invention further discovers that in order to obtain an ideal nanoscale transmission channel, graphene oxide and modified Ti in S3 3 C 2 The mass ratio of the nano-sheets is critical, if modified Ti 3 C 2 The relative content of the nano sheets is excessive, the effective contact probability between rGO nano sheets in the film is easy to reduce excessively, the interaction between layers is reduced, the interlayer conductivity of the film is affected, and the mechanical property is reduced; on the contrary, if the relative content is too small, the problem of self-stacking in the rGO film forming process cannot be fully solved, and the self-aggregation phenomenon cannot be effectively prevented.
Preferably, in S1, the concentration of HCl in the HCl/LiF mixed solution is 8-10mol/L, and the concentration of LiF is 0.06-0.07g/mL; the Ti is 3 AlC 2 The solid-to-liquid ratio of the powder to the HCl/LiF mixed solution is 0.6-0.7g:15mL; the temperature of the continuous stirring reaction is 30-40 ℃ and the time is 45-50h.
Preferably, in S1, the centrifugal speed of the mixed solution is 8000-12000rpm, and the time is 25-35min; the washing and centrifugation are repeated until the pH of the centrifuged supernatant is > 6.
Preferably, in S1, the concentration of the dodecyl dimethyl benzyl ammonium chloride aqueous solution is 1-2mmol/L; the temperature of the water bath oscillation heating treatment is 50-60 ℃ and the time is 4-6h.
Preferably, in S1, the suspension is sonicated for a period of time ranging from 0.5 to 1.5 hours, at a centrifugation speed ranging from 3000 to 4000rpm, for a period of time ranging from 0.5 to 1.5 hours.
Preferably, in S1, the modified Ti 3 C 2 Modified Ti in nano-sheet dispersion 3 C 2 The content of the nano-sheet is 6-10mg/mL, and the content of urea is 0.1-1.0mol/L.
Preferably, S2 specifically includes: adding the ground graphite oxide into water to obtain 80-120mg/mL graphite oxide dispersion liquid; ultrasonic stripping is carried out for 25-35min at 45-55 ℃ and 80-120W, and ultrasonic stripping is repeated for a plurality of times, thus obtaining uniform and stable graphene oxide dispersion liquid.
Preferably, in S3, the time of the ultrasonic treatment is 5-15min; the drying temperature is room temperature and the drying time is 40-50h; the heat treatment time is 1-2h, and the reduction time of graphene oxide by introducing hydrogen is 2-4h.
Preferably, in S3: the thickness of the gas-sensitive layer of the CO sensor is 5-15 micrometers.
In a second aspect, the invention provides an application of the gas-sensitive layer of the CO sensor in a lithium battery energy storage device.
Compared with the prior art, the invention has the beneficial effects that: the invention utilizes electrostatic adsorption to lead the modified Ti to be 3 C 2 The nano sheets and the graphene oxide are alternately stacked and self-assembled into a multi-layer structure, and the multi-layer structure can reduce the self-stacking of the graphene oxide and prevent the aggregation of the graphene oxide. Based on the skillfully utilizing urea in Ti 3 C 2 In situ thermal decomposition between/rGO multi-layer material layers to increase interlayer spacing, thereby constructing an ideal nanoscale transmission channel. Ti with the special nanoscale transmission channel 3 C 2 The rGO multilayer material has extremely high sensitivity and selectivity to CO when being used as a gas sensitive layer of a gas sensor, and has excellent reversibilityThe performance and the cycle stability are particularly suitable for monitoring characteristic gas CO generated when the lithium battery energy storage device is out of control, so that the early warning of fire disaster of the lithium battery energy storage system is realized.
Drawings
FIG. 1 is a diagram of Ti in example 1 3 C 2 Cross-sectional scanning electron microscope image of/rGO film;
FIG. 2 is a diagram of Ti in example 1 3 C 2 And Ti is 3 C 2 XRD pattern of rGO film;
FIG. 3 is a diagram of Ti in example 1 3 C 2 Cycling stability test pattern of/rGO film.
Detailed Description
The invention is further described below with reference to examples.
The preparation method of the gas-sensitive layer of the CO sensor comprises the following steps:
s1: adding Ti into the stirred HCl/LiF mixed solution (the concentration of HCl is 8-10mol/L, the concentration of LiF is 0.06-0.07 g/mL) 3 AlC 2 Powder (Ti) 3 AlC 2 15mL of mixed solution of powder and HCl/LiF at a solid-liquid ratio of 0.6-0.7 g), continuously stirring at 30-40 ℃ for reacting for 45-50h, centrifuging (8000-12000 rpm,25-35 min), repeatedly washing and centrifuging the centrifugal precipitate with deionized water until the pH value of the centrifugal supernatant is more than 6, collecting the precipitate and redispersing the precipitate in 1-2mmol/L of dodecyl dimethyl benzyl ammonium chloride aqueous solution, performing water bath oscillation heating treatment at 50-60 ℃ for 4-6h, adding urea to the obtained suspension until the content is 0.1-1.0mol/L, performing ultrasonic treatment for 0.5-1.5h, centrifuging (3000-4000 rpm,0.5-1.5 h), and collecting the supernatant to obtain the modified Ti of 6-10mg/mL 3 C 2 A nanosheet dispersion.
S2: adding the ground graphite oxide into water to obtain 80-120mg/mL graphite oxide dispersion liquid; ultrasonic stripping is carried out for 25-35min at 45-55 ℃ and 80-120W, and ultrasonic stripping is repeated for a plurality of times, thus obtaining uniform and stable graphene oxide dispersion liquid.
S3: dropwise adding the graphene oxide dispersion liquid to the modified Ti under stirring 3 C 2 Obtaining Ti from the nano-sheet dispersion liquid 3 C 2 GO dispersion, ti 3 C 2 Graphene oxide and modified Ti in GO dispersion 3 C 2 The mass ratio of the nano-sheets is 7:3-9:1; treating with ultrasonic for 5-15min, and collecting Ti 3 C 2 Spreading the GO dispersion liquid in a mould, drying at room temperature for 40-50h, heat treating at 300-350deg.C for 1-2h to decompose urea, and reacting at heat preservation under hydrogen gas condition for 2-4h to reduce graphene oxide to obtain Ti with thickness of 5-15 μm 3 C 2 The rGO film is the gas-sensitive layer of the CO sensor.
Example 1
S1: to a stirred 15mL HCl/LiF mixture (HCl concentration 9mol/L, liF content 1 g) was added 0.7g Ti 3 AlC 2 Continuously stirring and reacting powder for 48h at 35 ℃, centrifuging (10000 rpm,30 min), repeatedly washing and centrifuging the centrifugal precipitate with deionized water until the pH value of the centrifugal supernatant is more than 6, collecting precipitate and redispersing the precipitate in 1.5mmol/L dodecyl dimethyl benzyl ammonium chloride aqueous solution, carrying out water bath oscillation and heating treatment at 55 ℃ for 5h, then adding urea to the obtained suspension until the content is 0.6mol/L, carrying out ultrasonic treatment for 1h, centrifuging (3500 rpm,1 h), and collecting supernatant to obtain 8mg/mL modified Ti 3 C 2 A nanosheet dispersion.
S2: adding the ground graphite oxide into distilled water to obtain a graphite oxide dispersion liquid with the concentration of 100 mg/mL; ultrasonic stripping is carried out for 30min at 50 ℃ and 100W, and ultrasonic stripping is repeated for 3 times, so that uniform and stable graphene oxide dispersion liquid is obtained.
S3: dropwise adding the graphene oxide dispersion liquid to the modified Ti under stirring 3 C 2 Obtaining Ti from the nano-sheet dispersion liquid 3 C 2 GO dispersion, ti 3 C 2 Graphene oxide and modified Ti in GO dispersion 3 C 2 The mass ratio of the nano-sheets is 8:2; ultrasonic treating for 10min, and collecting Ti 3 C 2 Spreading the/GO dispersion in a glass culture dish with diameter of 80 mm, drying at room temperature for 48 hr, reacting at 325deg.C for 1.5 hr to decompose urea, and reacting at a temperature maintaining condition with hydrogen for 3 hr to reduce graphene oxide to obtain Ti with thickness of about 10 μm 3 C 2 rGO films, i.eIs a gas-sensitive layer of the CO sensor.
As shown in FIG. 1, the Ti prepared in example 1 3 C 2 Cross-sectional scanning electron microscope of the rGO film, from which Ti can be seen 3 C 2 The sheets firmly attach or intercalate into the rGO layer, exhibiting a distinct porous intercalation structure. This structure makes Ti 3 C 2 And rGO reduces self-stacking, can effectively prevent re-stacking of rGO layers, enlarges the interlayer spacing, forms ideal nanoscale transport channels, improves electrochemical performance, and has high sensitivity and high selectivity for CO gas.
FIG. 2 is Ti 3 C 2 And Ti prepared in example 1 3 C 2 XRD pattern of rGO. As can be seen from the figure, 6 o The nearby peak is typically Ti 3 C 3 Characteristic peaks indicating Ti 3 C 3 The crystal structure is very small. And Ti is 3 C 3 After being compounded with rGO, ti is reserved 3 C 3 Characteristic peaks, and characteristic peaks belonging to rGO appear, which indicates Ti 3 C and rGO are compounded and have no effect on Ti 3 C 3 The structure of the material itself is affected.
FIG. 3 shows the Ti of example 1 under CO test at a concentration of 1ppm 3 C 2 The rGO film is assembled into the cyclic stability performance of the CO sensor. As shown in fig. 3, 9 repeated performance tests were performed, the CO sensor was responded to in a CO airtight box for 3min, and was returned to the air for 3min. It is evident from fig. 3 that the CO sensor response to CO was substantially unchanged during the 9 replicates, which not only demonstrates the extremely high sensitivity of the CO sensor comprising the gas sensitive layer of the CO sensor of the present invention to CO monitoring, but also demonstrates its excellent sensing cycle reversibility and repeatability stability to CO.
Examples 2 to 7 and comparative examples 1 to 5 are different from example 1 as shown in the following table:
performance comparison
Note that: the detection method of the lowest detection limit of CO in the table above is to test response values at 0.1ppm, 0.5ppm, 1ppm, 5ppm and 10ppm respectively, and the lowest concentration at which the response values can appear is the lowest detection limit of CO.
The comparison of the data in the table above shows that:
the minimum detection limit of CO is generally significantly higher than that of example 1 in comparative examples 1 to 5, and the decrease of the response value of CO gas after 9 cycles is more obvious. The reason for analysis is mainly that:
comparative example 1 Using a single rGO as the CO sensor gas sensitive layer raw material, rGO readily self-stacks during film formation, resulting in reduced interlayer spacing, resulting in a minimum detection limit for CO of greater than 1ppm, resulting in no cycling data at 1ppm
Comparative example 2 differs from example 1 in that dodecyldimethylbenzyl ammonium chloride was not used for Ti 3 C 2 Modified to form Ti during film formation 3 C 2 Failure to self-assemble with GO by electrostatic interaction, resulting in Ti 3 C 2 Failure to form a highly ordered alternating multi-layer intercalation structure with GO results in poor sensitivity to CO and cycling stability as in example 1.
Comparative example 3 differs from example 1 in that urea was not loaded and thermal decomposition was performed during the film-forming process, although Ti 3 C 2 The alternating multi-layer intercalation structure can still be formed with GO, but the nanoscale transmission channels between layers are not stable enough, the interlayer spacing is easy to be reduced again after the circulation for a plurality of times, and the circulation stability is inferior to that of the embodiment 1.
Comparative examples 4 and 5 differ from example 1 in that GO: ti 3 C 2 The proportions are different. Wherein, in comparative example 4, ti 3 C 2 Higher ratio of (c) and lower ratio of (c) comparative example 5. Ti (Ti) 3 C 2 The ratio to GO directly affects Ti 3 C 2 Microstructure of rGO multilayer material, ti 3 C 2 Too high or too low a ratio results in a film that is less sensitive to CO and less stable to cycling than example 1.
Example 1, example 2 and example 5 differ in GO: ti 3 C 2 The proportions are different. The data rule shows that the film has the most ideal performance at the ratio of 80:20 in example 1, wherein the cycle stability of the film to CO is increased and then reduced in the ratio range of 70:30 to 90:10.
The difference between examples 3-7 is that the urea content in the dispersion obtained in S1 increases, and the data show that the urea content also has an important effect on the cycle stability performance of the sensor, when the urea content is lower, ti 3 C 2 The amount of urea adhering between the layers of the GO multilayer material is small, so that the gas generated during the subsequent pyrolysis is also small, and therefore the effect of increasing the interlayer spacing is limited, and as the urea content increases, the effect is gradually evident as a whole. However, when the urea content is further increased, the mechanical properties of the film are lowered and the film is liable to break due to the excessively large interlayer spacing, and therefore the urea content is not more than 1.0mol/L at the highest, and the optimum range is 0.4 to 0.6mol/L.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A CO sensor gas sensitive layer characterized by: is Ti 3 C 2 The preparation method of the rGO film comprises the following steps:
s1: adding Ti to the stirred HCl/LiF mixture 3 AlC 2 Continuously stirring the powder for reaction, centrifuging the obtained mixed solution, repeatedly washing and centrifuging the obtained precipitate, collecting the precipitate, dispersing in dodecyl dimethyl benzyl ammonium chloride aqueous solution, performing water bath oscillation heating treatment, adding urea into the obtained suspension, performing ultrasonic treatment, centrifuging, and collecting supernatantTo modified Ti 3 C 2 A nanosheet dispersion;
s2: preparing graphene oxide dispersion liquid;
s3: dropwise adding the graphene oxide dispersion liquid to the modified Ti under stirring 3 C 2 Obtaining Ti from the nano-sheet dispersion liquid 3 C 2 GO dispersion, ti 3 C 2 Graphene oxide and modified Ti in GO dispersion 3 C 2 The mass ratio of the nano-sheets is 7:3-9:1; ultrasonic treatment of Ti 3 C 2 Spreading the GO dispersion in a mold, drying, decomposing urea by heat treatment at 300-350deg.C, and reducing graphene oxide by introducing hydrogen under heat preservation to obtain Ti 3 C 2 The rGO film is the gas-sensitive layer of the CO sensor.
2. The CO sensor gas sensitive layer of claim 1, wherein: in the step S1, the step of,
the concentration of HCl in the HCl/LiF mixed solution is 8-10mol/L, and the concentration of LiF is 0.06-0.07g/mL;
the Ti is 3 AlC 2 The solid-to-liquid ratio of the powder to the HCl/LiF mixed solution is 0.6-0.7g:15mL;
the temperature of the continuous stirring reaction is 30-40 ℃ and the time is 45-50h.
3. The CO sensor gas sensitive layer of claim 2, wherein: in the step S1, the step of,
centrifuging the mixed solution at 8000-12000rpm for 25-35min;
the washing and centrifugation are repeated until the pH of the centrifuged supernatant is > 6.
4. A CO sensor gas sensitive layer according to claim 2 or 3, characterized in that: in the step S1, the step of,
the concentration of the dodecyl dimethyl benzyl ammonium chloride aqueous solution is 1-2mmol/L;
the temperature of the water bath oscillation heating treatment is 50-60 ℃ and the time is 4-6h.
5. A CO sensor gas sensitive layer according to claim 2 or 3, characterized in that: in S1, the ultrasonic treatment time of the suspension is 0.5-1.5h, the centrifugal speed is 3000-4000rpm, and the time is 0.5-1.5h.
6. The CO sensor gas sensitive layer of claim 1, wherein: s1, the modified Ti 3 C 2 Modified Ti in nano-sheet dispersion 3 C 2 The content of the nano-sheet is 6-10mg/mL, and the content of urea is 0.1-1.0mol/L.
7. The CO sensor gas sensitive layer of claim 1, wherein: s2 specifically comprises: adding the ground graphite oxide into water to obtain 80-120mg/mL graphite oxide dispersion liquid; ultrasonic stripping is carried out for 25-35min at 45-55 ℃ and 80-120W, and ultrasonic stripping is repeated for a plurality of times, thus obtaining uniform and stable graphene oxide dispersion liquid.
8. The CO sensor gas sensitive layer of claim 1, wherein: in the step S3, the processing unit,
the ultrasonic treatment time is 5-15min;
the drying temperature is room temperature and the drying time is 40-50h;
the heat treatment time is 1-2h, and the reduction time of graphene oxide by introducing hydrogen is 2-4h.
9. The CO sensor gas sensitive layer of claim 1, wherein: s3: the thickness of the gas-sensitive layer of the CO sensor is 5-15 micrometers.
10. Use of a CO sensor gas sensitive layer according to any of claims 1-9 in a lithium-ion energy storage system after assembly as a CO sensor.
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