CN111982748A - Performance detection method of proton exchange membrane fuel cell catalyst slurry - Google Patents
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Abstract
The invention relates to a method for detecting the performance of catalyst slurry of a proton exchange membrane fuel cell, which comprises the following steps: adding the catalyst slurry prepared according to the original formula into a rotary rheometer, and setting a test temperature; performing a steady state viscosity measurement in a first rotation mode; performing a rheological profile measurement in a second rotation mode; performing viscoelasticity measurement in oscillation mode; performing thixotropy measurement in a third rotation mode; and determining the microstructure and the coating performance of the catalyst slurry according to the measured apparent viscosity, rheological curve, amplitude scanning and thixotropic ring, judging that the performance detection is passed if the microstructure and the coating performance of the catalyst slurry are consistent with the design target, and otherwise, changing the formula of the catalyst slurry, and performing the performance detection after re-preparation until the performance detection is passed. Compared with the prior art, the method is based on rheological property test, and the microstructure and the coating performance of the slurry can be rapidly and accurately determined through rheological property measurement results, so that the formula optimization efficiency is improved, and the catalyst slurry is ensured to be consistent with the design target.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cell detection, in particular to a method for detecting the performance of catalyst slurry of a proton exchange membrane fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of clean emission, high energy conversion efficiency and the like, and have wide application prospects in the fields of automobiles, portable power sources, distributed power stations and the like. PEM fuel cell pass H2And O2An important component of a proton exchange membrane fuel cell is the Catalytic Layer (CL), which serves as the site for the electrochemical reaction, whose microstructure controls the transport properties of electrons, protons, reactants and products, which are critical to the performance of the fuel cell. One of the challenges of current fuel cells is the lack of a reasonable method to effectively design catalytic layers with optimal microstructures.
The microstructure of the catalytic layer is mainly controlled by the catalyst slurry preparation process. The microstructure of the catalyst slurry plays a crucial role in forming an optimal catalytic layer, which is mainly influenced by the interaction between the catalyst and the ionic polymer and the catalytic layer coating and drying processes. However, the current catalyst slurry formulations are optimized experimentally: chinese patent CN201110048293 provides a preparation method of catalyst slurry, one of thickener ethylene glycol, glycerol and polyethylene glycol is added into the slurry, and the stabilizer is triton x-100, thereby improving the stability of the catalyst slurry; patent CN2012101938301 adopts a method of adding a high molecular polymer dispersant into proton exchange membrane fuel cell catalyst slurry, wherein the dispersant is one or a mixture of any two or more of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), polyethylene oxide (PEO) and Polyacrylamide (PAM); patent CN2010101765623 discloses a method for preparing catalyst slurry, which changes the composition and addition sequence of organic solvent in the slurry, firstly, using isopropanol, ethanol, ethylene glycol and the like to prepare catalyst slurry in a solution state, and then dripping the formed slurry into acetic acid butyl acetate under the condition of ultrasonic oscillation to further form the catalyst slurry in a colloid state.
In the methods, the formula of the catalyst slurry is optimized through experiments, so that a satisfactory result can be obtained through repeated experiments, the efficiency is low, and the produced catalyst slurry cannot meet the subsequent coating processing requirements due to lack of detection on the relevant performance of the catalyst slurry, so that the fuel cell cannot reach an ideal working state.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for detecting the performance of catalyst slurry of a proton exchange membrane fuel cell, which accurately and reliably evaluates the relevant performance of the catalyst slurry by performing rheological property test on the catalyst slurry, so as to accurately judge whether the produced catalyst slurry can meet the coating processing requirement, and further perform targeted improvement on the catalyst slurry formula.
The purpose of the invention can be realized by the following technical scheme: a performance detection method of proton exchange membrane fuel cell catalyst slurry comprises the following steps:
s1, preparing catalyst slurry of the proton exchange membrane fuel cell according to the original formula for later use;
s2, adding the prepared catalyst slurry into a rotary rheometer, and setting a test temperature;
s3, carrying out steady-state viscosity measurement on the catalyst slurry in a first rotation mode to obtain the apparent viscosity of the catalyst slurry;
s4, performing rheological curve measurement on the catalyst slurry in a second rotation mode to obtain a rheological curve of the catalyst slurry;
s5, performing viscoelasticity measurement on the catalyst slurry in an oscillation mode to obtain amplitude scanning of the catalyst slurry;
s6, carrying out thixotropy measurement on the catalyst slurry in a third rotation mode to obtain a thixotropic ring of the catalyst slurry;
s7, determining the microstructure and the coating performance of the catalyst slurry according to the apparent viscosity, the rheological curve, the amplitude scanning and the thixotropic ring of the catalyst slurry;
s8, comparing the microstructure and the coating performance of the catalyst slurry with a design target, if the microstructure and the coating performance of the catalyst slurry are consistent with the design target, judging that the performance detection of the catalyst slurry is passed, otherwise, changing the formula of the catalyst slurry, preparing the catalyst slurry again, and returning to the step S2 until the performance detection of the catalyst slurry is passed.
Further, in the step S1, the original recipe specifically includes: and sequentially adding a catalyst, water, Nafion and isopropanol, wherein the solid content of the catalyst is 0.01-20% by mass.
Further, the catalyst is specifically a platinum-containing catalyst.
Further, the specific process of preparing the proton exchange membrane fuel cell catalyst slurry in step S1 is as follows:
s11, sequentially adding the production raw materials into a container according to the original formula, and mixing to obtain a mixture;
s12, ultrasonically dispersing the mixture at 20-30 ℃ for 10-30 minutes, and then dispersing for 20-50 minutes by using a homogenizer to finally obtain the catalyst slurry for the proton exchange membrane fuel cell.
Further, the rotational rheometer in step S2 is embodied as a double slit coaxial cylindrical rotor structure.
Further, the testing temperature in the step S2 is specifically 20-30 ℃.
Further, the first rotation mode includes two constant shear rates: 1 to 5S-1And 80 to 120S-1。
Further, the shear rate of the second rotation mode is 0.001-1500S-1。
Furthermore, the frequency scanning angular frequency omega of the oscillation mode ranges from 0.1 to 100 rad/s.
Further, the third rotation mode specifically is: the shear rate is gradually increased from 0 to 1000-1500S-1And is constant at 1000-1500S-10.5-2 minutes, then the shear rate is 1000-1500S-1Gradually decrease to 0S-1。
Compared with the prior art, the invention has the following advantages:
the invention can quickly and accurately determine the microstructure and the coating performance of the catalyst slurry by performing rheological property test on the catalyst slurry and utilizing the apparent viscosity, rheological curve, viscoelasticity and thixotropy obtained by the test, thereby quickly and accurately judging whether the catalyst slurry meets the design target, being beneficial to performing targeted formula improvement on the catalyst slurry and solving the problem of low efficiency of the traditional repeated experiment method.
Secondly, the microstructure and the coating performance of the catalyst slurry can be visually and accurately determined through the rheological property test result of the catalyst slurry based on the rheological property test method, so that reliable data support is provided for the subsequent optimization of the catalyst slurry formula, the accuracy of the formula optimization can be ensured, and the catalyst slurry produced after optimization can be consistent with the design target.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is a graphical representation of the rheology curves of catalyst slurries at different solids contents in the examples;
FIG. 3 is a schematic diagram showing thixotropy of catalyst pastes of different solid contents in examples;
FIG. 4 is a graph showing the amplitude sweep of the catalyst slurry at 12% solids in the examples.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Examples
Rheology is a promising approach to the study of catalyst slurries, from the point of view of the internal interactions of the slurry to study the microstructure of complex slurry systems, and furthermore during slurry coating the rheological properties play a crucial role in the processing behaviour. Rheological properties, including viscosity, thixotropy and viscoelasticity, directly affect the slurry coating quality and catalytic layer performance. Viscosity and thixotropy are the static properties of a slurry, the viscoelastic properties of a slurry are defined by its elastic/storage modulus (G') and viscosity/loss modulus (G ″), and the dynamic properties of a slurry, the elastic modulus providing information about the solid phase properties of the slurry, while the viscous modulus reveals its liquid properties.
Understanding the rheological property of the catalyst slurry has important significance for establishing the relationship between the structure, the performance and the processing of the catalyst slurry, and is beneficial to optimizing the slurry formula, improving the coating efficiency and reasonably designing the catalyst layer. The viscosity curve represents the flow characteristics of the slurry at different shear rates, not only can reflect the interaction among the catalyst, the ionomer and the solvent in the slurry, but also can evaluate the performance of the slurry, the storage and transportation stability and the dispersion performance of a sample can be evaluated by testing the zero-shear viscosity, and the construction performance and the stirring production performance of the sample can be evaluated by testing the viscosity at a high shear rate. The dispersibility of the slurry can be determined by measuring the degree of thixotropy of the slurry, which is determined by determining the area of the hysteresis curve between the sweep up and sweep down of the viscosity-shear rate curve. Viscoelasticity reflects the detailed information of the strength of the particle network within the catalyst slurry, with a large elastic modulus generally indicating a good slurry structure and a large viscous modulus indicating a non-elastic sample. Because different coating modes require different slurry rheological properties, such as a screen printing technology, the slurry is required to have high viscosity under low shear and low viscosity under high shear, and the structure recovery speed can be fast; for vacuum spraying, the slurry needs to have a very low viscosity to facilitate rapid atomization and uniform spraying of the slurry. Therefore, aiming at different slurry coating technologies, the rheological property of the slurry can be reasonably designed by regulating and controlling the slurry formula.
Therefore, the invention is based on the rheological property test method, carries out performance detection on the catalyst slurry of the proton exchange membrane fuel cell, and can quickly and accurately determine the microstructure and the coating performance of the catalyst slurry according to the detection result, thereby being beneficial to carrying out targeted improvement and optimization on the catalyst slurry formula in the follow-up process and ensuring that the optimized catalyst slurry can be consistent with the design target.
As shown in fig. 1, a method for detecting the performance of catalyst slurry of a proton exchange membrane fuel cell includes the following steps:
s1, preparing the catalyst slurry of the proton exchange membrane fuel cell according to an original formula for later use, wherein the original formula specifically comprises: sequentially adding a catalyst, water, Nafion and isopropanol, wherein the mass ratio of the solid content of the catalyst is 0.01-20%, and the catalyst is specifically a platinum-containing catalyst;
the preparation process specifically comprises the following steps:
according to the original formula, sequentially adding the production raw materials into a container to be mixed to obtain a mixture;
ultrasonically dispersing the mixture at 20-30 ℃ for 10-30 minutes, and then dispersing for 20-50 minutes by using a homogenizer to finally obtain proton exchange membrane fuel cell catalyst slurry;
s2, adding the prepared catalyst slurry into a rotary rheometer, and setting a test temperature, wherein the rotary rheometer is specifically of a double-slit coaxial cylindrical rotor structure, and the test temperature is specifically 20-30 ℃;
s3, carrying out steady-state viscosity measurement on the catalyst slurry in a first rotation mode to obtain the apparent viscosity of the catalyst slurry, wherein the apparent viscosity is measured at a constant shear rate of 1-5S-1And 80 to 120S-1Measuring the apparent viscosity of the catalyst slurry;
s4, performing rheological curve measurement on the catalyst slurry in a second rotation mode to obtain the rheological curve of the catalyst slurry, wherein the rheological curve is specifically the rheological curve of the catalyst slurry within the shear rate range of 0.001-1500S-1Measuring under the condition to obtain a rheological curve of the catalyst slurry;
s5, performing viscoelasticity measurement on the catalyst slurry in an oscillation mode to obtain amplitude scanning of the catalyst slurry, wherein the frequency scanning angular frequency omega of the oscillation mode is 0.1-100 rad/S;
s6, carrying out thixotropy measurement on the catalyst slurry in a third rotation mode to obtain a thixotropic ring of the catalyst slurry, and the specific process is as follows:
the shear rate is gradually increased from 0 to 1000-1500S-1Constant at 1000-1500S-10.5-2 minutes;
then the shear rate is 1000-1500S-1Gradually decrease to 0S-1Measuring to obtain a thixotropic ring of the catalyst slurry;
s7, determining the microstructure and the coating performance of the catalyst slurry according to the apparent viscosity, the rheological curve, the amplitude scanning and the thixotropic ring of the catalyst slurry;
s8, comparing the microstructure and the coating performance of the catalyst slurry with a design target, if the microstructure and the coating performance of the catalyst slurry are consistent with the design target, judging that the performance detection of the catalyst slurry is passed, otherwise, changing the formula of the catalyst slurry, preparing the catalyst slurry again, and returning to the step S2 until the performance detection of the catalyst slurry is passed.
In this embodiment, for three catalyst slurries with different solid contents, the method provided by the present invention is respectively adopted to perform performance detection, where the solid content of the first catalyst slurry is 12%, the solid content of the second catalyst slurry is 8%, and the solid content of the third catalyst slurry is 0.1%, because the viscosities of the second and third catalyst slurries are very low (the solid contents are low) and exhibit newtonian fluid characteristics, according to the rheological characteristics of the slurries, only apparent viscosity, rheological curve and thixotropy test are performed on the second catalyst slurry, and only apparent viscosity and rheological curve test are performed on the third catalyst slurry, and the performance detection processes of the three catalyst slurries with different solid contents specifically include:
firstly, detecting the performance of catalyst slurry with the solid content of 12 percent:
(1) weighing 11.613 g of 60% Pt/C catalyst, adding 20 g of deionized water, then adding 3.8710 g of 5% Nafion, and finally adding 20 g of isopropanol to prepare the proton exchange membrane fuel cell catalyst slurry to be tested, wherein the solid content of the catalyst slurry is 12%, and then respectively subjecting the catalyst slurry to ultrasonic dispersion for 10 minutes at 25 ℃ and dispersion for 30 minutes by a homogenizer;
(2) the rotational rheometer adopts the company of Antopa corporation, the model of the rotational rheometer is MCR302, the measuring rotor is a double-slit coaxial cylinder, the temperature control system is a semiconductor coaxial cylinder temperature control system, then, the prepared catalyst slurry is added into the rheometer, and the measurement temperature is controlled to be 25 ℃;
(3) the catalyst slurry was subjected to steady state viscosity measurement in a rotating mode, each at a constant shear rate of 5S-1And 100S-1Measuring the apparent viscosity of the catalyst slurry;
(4) performing rheological curve measurement on the catalyst slurry in a rotating mode, wherein the shear rate range is 0.001-1500S-1；
(5) Performing viscoelasticity measurement on the catalyst slurry in an oscillation mode, wherein the frequency scanning angular frequency omega ranges from 0.1 to 100 rad/s;
(6) carrying out thixotropy measurement on the catalyst slurry in a rotating mode, and gradually increasing the shear rate from 0 to 1000-1500S-1Constant at 1000-1500S-10.5-2 minutes, then 1000-1500S-1Gradually decrease to 0S-1And obtaining the thixotropic ring of the catalyst slurry.
Secondly, detecting the performance of the catalyst slurry with the solid content of 8 percent:
(1) weighing 3.3645 g of 60% Pt/C catalyst, adding 20 g of deionized water, then adding 1.1215 g of 5% Nafion, and finally adding 20 g of isopropanol to prepare the catalyst slurry of the proton exchange membrane fuel cell to be tested, wherein the solid content of the catalyst slurry is 8%, and then respectively carrying out ultrasonic dispersion on the catalyst slurry for 10 minutes at 25 ℃ and dispersion on the catalyst slurry for 30 minutes by a homogenizer;
(2) the rotational rheometer adopts the company of Antopa corporation, the model of the rotational rheometer is MCR302, the measuring rotor is a double-slit coaxial cylinder, the temperature control system is a semiconductor coaxial cylinder temperature control system, then, the prepared catalyst slurry is added into the rheometer, and the measurement temperature is controlled to be 25 ℃;
(3) the catalyst slurry was subjected to steady state viscosity measurement in a rotating mode, each at a constant shear rate of 5S-1And 100S-1Measuring the apparent viscosity of the catalyst slurry;
(4) to catalyze in a rotating modeThe slurry is subjected to rheological curve measurement, and the shear rate is in the range of 0.001-1500S-1；
(5) Carrying out thixotropy measurement on the catalyst slurry in a rotating mode, and gradually increasing the shear rate from 0 to 1000-1500S-1Constant at 1000-1500S-10.5-2 minutes, then 1000-1500S-1Gradually decrease to 0S-1And obtaining the thixotropic ring of the catalyst slurry.
Thirdly, detecting the performance of the catalyst slurry with the solid content of 0.1 percent:
(1) weighing 0.0496 g of 60% Pt/C catalyst, adding 20 g of deionized water, then adding 0.331 g of 5% Nafion, and finally adding 20 g of isopropanol to prepare the catalyst slurry of the proton exchange membrane fuel cell to be tested, wherein the solid content of the catalyst slurry is 0.1%, and then respectively carrying out ultrasonic dispersion for 10 minutes at 25 ℃ and dispersion for 30 minutes by a homogenizer;
(2) the rotational rheometer adopts the company of Antopa corporation, the model of the rotational rheometer is MCR302, the measuring rotor is a double-slit coaxial cylinder, the temperature control system is a semiconductor coaxial cylinder temperature control system, then, the prepared catalyst slurry is added into the rheometer, and the measurement temperature is controlled to be 25 ℃;
(3) the catalyst slurry was subjected to steady state viscosity measurement in a rotating mode, each at a constant shear rate of 5S-1And 100S-1Measuring the apparent viscosity of the catalyst slurry;
(4) performing rheological curve measurement on the catalyst slurry in a rotating mode, wherein the shear rate range is 0.001-1500S-1。
The steady state viscosity results for the catalyst slurries thus obtained are shown in table 1:
TABLE 1
| Shear rate (S)-1) | Solid content (%) | Apparent viscosity (mPa. S) |
| 100 | 12 | 16.52 |
| 1 | 12 | 56.31 |
| 100 | 8 | 6.26 |
| 1 | 8 | 6.57 |
| 100 | 0.1 | 3.25 |
| 1 | 0.1 | 3.55 |
As can be seen from Table 1, the shear rate is 1S-1The apparent viscosity of the slurry is more than 100S-1When the time is large, the apparent viscosity of the catalyst slurry is increased, and the larger the solid content is, the larger the change of the apparent viscosity is, which can indicate that the larger the solid content is, the more stable the slurry is.
The rheological curves of the obtained catalyst slurries with different solid contents are shown in fig. 2, and it can be seen from fig. 2 that when the solid content of the slurry is 0.1% and 8% along with the increase of the shear rate, the viscosity of the slurry is almost unchanged along with the change of the shear rate, and the Newtonian fluid characteristic is shown, and when the solid content of the slurry is 12%, the viscosity is reduced along with the increase of the shear rate, gradually becomes stable, and shows the shear thinning. Different shear rates have different applications in the slurry, for the slurry with the solid content of 12%, under a lower shear rate, Nafion in the slurry shows that molecular chains are mutually entangled on a microstructure, the viscosity value is larger at the moment, when the shear rate is increased, the slurry coating process can be simulated, at the moment, the hydrodynamic force is dominant, Nafion molecules become orderly arranged, and meanwhile, the aggregate is dispersed and the viscosity is reduced. For slurries with solids contents of 0.1% and 8%, the viscosity does not change with shear rate because of the lower Nafion content, the weaker Nafion ability to flocculate the particles, and the dominant brownian motion.
The thixotropic rings of the catalyst slurry with the solid content of 12% and the solid content of 8% are shown in fig. 3, and it can be seen from fig. 3 that the thixotropic ring area of the slurry with the solid content of 12% is larger than that of the slurry with the solid content of 8%, which shows that the thixotropy is higher when the solid content is higher, and the three-dimensional space network structure in the slurry can be reinforced by the increase of the solid content, so that the cross-linked structure becomes more difficult to break.
The amplitude sweep to obtain a catalyst slurry with 12% solids is shown in fig. 4, and it can be seen from fig. 4 that as the angular frequency increases, both the storage modulus G 'and the loss modulus G "increase, but both the storage modulus G' and the loss modulus G" are relatively small, indicating that the network structure within the slurry is relatively unstable.
In conclusion, the performance of the catalyst slurry is detected by the method provided by the invention, and the microstructure and the coating performance of the catalyst slurry can be intuitively, quickly and accurately determined according to the detection result, namely, the relationship among the structure and the performance of the catalyst slurry and the subsequent formula optimization can be established through the rheological property test of the catalyst slurry, so that the slurry formula can be efficiently optimized, the subsequent coating efficiency can be improved, and the catalyst layer can be reasonably designed.
Claims (10)
1. A performance detection method of proton exchange membrane fuel cell catalyst slurry is characterized by comprising the following steps:
s1, preparing catalyst slurry of the proton exchange membrane fuel cell according to the original formula for later use;
s2, adding the prepared catalyst slurry into a rotary rheometer, and setting a test temperature;
s3, carrying out steady-state viscosity measurement on the catalyst slurry in a first rotation mode to obtain the apparent viscosity of the catalyst slurry;
s4, performing rheological curve measurement on the catalyst slurry in a second rotation mode to obtain a rheological curve of the catalyst slurry;
s5, performing viscoelasticity measurement on the catalyst slurry in an oscillation mode to obtain amplitude scanning of the catalyst slurry;
s6, carrying out thixotropy measurement on the catalyst slurry in a third rotation mode to obtain a thixotropic ring of the catalyst slurry;
s7, determining the microstructure and the coating performance of the catalyst slurry according to the apparent viscosity, the rheological curve, the amplitude scanning and the thixotropic ring of the catalyst slurry;
s8, comparing the microstructure and the coating performance of the catalyst slurry with a design target, if the microstructure and the coating performance of the catalyst slurry are consistent with the design target, judging that the performance detection of the catalyst slurry is passed, otherwise, changing the formula of the catalyst slurry, preparing the catalyst slurry again, and returning to the step S2 until the performance detection of the catalyst slurry is passed.
2. The method for detecting the performance of the catalyst slurry for the proton exchange membrane fuel cell according to claim 1, wherein the original formula in the step S1 is specifically as follows: and sequentially adding a catalyst, water, Nafion and isopropanol, wherein the solid content of the catalyst is 0.01-20% by mass.
3. The method for detecting the performance of the proton exchange membrane fuel cell catalyst slurry as claimed in claim 2, wherein the catalyst is a platinum-containing catalyst.
4. The method for detecting the performance of the proton exchange membrane fuel cell catalyst slurry as claimed in claim 1, wherein the specific process of preparing the proton exchange membrane fuel cell catalyst slurry in the step S1 is as follows:
s11, sequentially adding the production raw materials into a container according to the original formula, and mixing to obtain a mixture;
s12, ultrasonically dispersing the mixture at 20-30 ℃ for 10-30 minutes, and then dispersing for 20-50 minutes by using a homogenizer to finally obtain the catalyst slurry for the proton exchange membrane fuel cell.
5. The method for detecting the performance of the catalyst slurry for the proton exchange membrane fuel cell according to claim 1, wherein the rotational rheometer in the step S2 is specifically a double-slit coaxial cylindrical rotor structure.
6. The method for detecting the performance of the catalyst slurry of the proton exchange membrane fuel cell according to claim 1, wherein the testing temperature in the step S2 is specifically 20-30 ℃.
7. The method of claim 1, wherein the first rotation mode comprises two constant shear rates: 1 to 5S-1And 80 to 120S-1。
8. The method for detecting the performance of the catalyst slurry for the proton exchange membrane fuel cell according to claim 1, wherein the shear rate of the second rotation mode is 0.001-1500S-1。
9. The method for detecting the performance of the proton exchange membrane fuel cell catalyst slurry as claimed in claim 1, wherein the frequency sweep angular frequency ω of the oscillation mode is in a range of 0.1 to 100 rad/s.
10. The method for detecting the performance of the catalyst slurry of the proton exchange membrane fuel cell according to claim 1, wherein the third rotation mode specifically comprises: the shear rate is gradually increased from 0 to 1000-1500S-1And is constant at 1000-1500S-10.5-2 minutes, then the shear rate is 1000-1500S-1Gradually decrease to 0S-1。
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