CN109142405B - Quantitative analysis method for graphene/carbon nanotube composite conductive slurry - Google Patents
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Abstract
The invention relates to a quantitative analysis method of graphene/carbon nano tube composite conductive slurry, which comprises the steps of firstly carrying out XRD spectrum acquisition on graphene/carbon nano tube conductive slurry with different proportions for several times, respectively calculating the average values of 2 theta values and half-height width values beta of diffraction peaks of different composite conductive slurry (002) by using the XRD spectrum, and obtaining the La values of the graphene/carbon nano tube conductive slurry with different proportions by a formula La = [ (1.78tan theta)/beta ] + 1. And (3) making a first-order curve of a series of La values and the graphene/carbon nanotube ratios of the corresponding slurry, and taking the curve as a standard curve. And then obtaining the La value of the graphene/carbon nanotube composite conductive slurry to be detected by the same method, wherein the value corresponding to the ratio on the standard curve is the ratio of graphene to carbon nanotubes in the graphene/carbon nanotube composite conductive slurry to be detected. The method is simple and rapid to operate, has high accuracy, and has application prospects in quantitative analysis and rapid evaluation of the graphene/carbon nanotube composite conductive slurry for the lithium ion battery.
Description
Technical Field
The invention relates to the field of quantitative analysis of graphene composite conductive paste, in particular to a quantitative analysis method of graphene/carbon nanotube composite conductive paste.
Background
With the rapid development of the power lithium ion battery industry, higher requirements are put forward on the performance of the lithium ion battery anode material and the performance of the finished battery. The gram capacity exertion, rate capability, cycle performance and the like of the material can be improved by adding the conductive agent with excellent conductivity and stable structure in the preparation process of the positive electrode material, and the energy density, rate capability, cycle performance and the like of the battery can be improved by adding the conductive agent with excellent conductivity and stable structure in the preparation process of the battery. Graphene and carbon nanotubes both have high conductivity, and graphene and carbon nanotubes are compounded to form a conductive agent with an excellent conductivity and a stable three-dimensional network structure, so that the conductive agent is widely applied to the fields of power lithium batteries and the like.
At present, a plurality of manufacturers capable of providing graphene/carbon nanotube composite conductive paste finished products in the market are available, and the product price is relatively high. The price of the graphene/carbon nanotube composite conductive paste mainly depends on the content of graphene in the paste, and the content of graphene in the composite conductive paste is provided by conductive paste manufacturers, so that the positive right to the price of the graphene/carbon nanotube composite conductive paste is mastered in the hands of the conductive paste manufacturers. The manufacturers of lithium ion power batteries use the graphene/carbon nanotube composite conductive paste in a large scale, and a method with high speed, high efficiency and high accuracy is needed to quantitatively analyze the content of graphene in the graphene/carbon nanotube composite conductive paste, so as to take the initiative in business negotiation.
Disclosure of Invention
The invention aims to provide a quantitative analysis method of graphene/carbon nanotube composite conductive slurry.
In order to solve the above problems, the present invention provides the following technical solutions:
a quantitative analysis method of graphene/carbon nanotube composite conductive slurry comprises the following steps:
(1) preparing graphene/carbon nano tube composite conductive slurry with different proportions, respectively baking and drying the graphene/carbon nano tube composite conductive slurry, and grinding the mixture to obtain powder;
(2) respectively carrying out multiple XRD tests on the ground different graphene/carbon nano tube composite conductive slurry powder to respectively obtain multiple groups of XRD patterns and original data;
(3) calculating and fitting the average value of a plurality of groups of XRD original data of different graphene/carbon nanotube composite conductive slurry powders, respectively calculating the 2 theta value and the full width at half maximum beta value of the (002) diffraction peak, and obtaining the corresponding La value through a formula La = [ (1.78tan theta)/beta ] + 1;
(4) drawing a curve chart of the obtained La value and the graphene ratio in the corresponding composite slurry to obtain primary curves of different graphene ratios and the La value, namely standard curves;
(5) taking the graphene/carbon nano tube composite conductive slurry dry powder to be tested to perform XRD test, obtaining an XRD spectrum and original data, and calculating the La value according to the method in the step (3);
(6) and (4) determining the graphene proportion of the La value obtained in the step (5) on the standard curve obtained in the step (4) as the proportion of graphene in the composite conductive paste to be tested.
Preferably, the drying manner in the step (1) is one of conventional air atmosphere drying, inert gas atmosphere drying and vacuum drying.
Preferably, the baking and drying temperature in step (1) does not exceed 120 ℃.
Preferably, the method for fitting the average value of the XRD raw data of different graphene/carbon nanotube composite conductive paste powders in the step (3) is Guss fitting.
The invention has the beneficial effects that: characterization means such as AFM, HRTEM and Raman can be used for independently performing characterization analysis on carbon group materials such as graphene and carbon nanotubes, but the graphene/carbon nanotube composite conductive slurry is a complex composite system, and the characterization means cannot accurately and effectively perform qualitative and quantitative analysis. However, the diffraction peak position, the 2 theta value and the full width at half maximum of the XRD diffraction characteristic peak of the graphene and the carbon nano tube with different layer numbers can generate corresponding obvious changes along with the change of the layer numbers and the proportion, so that the XRD becomes an effective means for qualitatively and quantitatively characterizing the graphene and carbon nano tube composite system; the method provided by the invention is simple and rapid to operate, has high accuracy, and has application prospects in quantitative analysis and rapid evaluation of the graphene/carbon nanotube composite conductive slurry for the lithium ion battery.
Drawings
FIG. 1 is an XRD fitting spectrogram of dry graphene/carbon nanotube conductive paste powders with four different proportions, which are prepared in embodiments 1-3 of the present invention;
FIG. 2 is a standard curve diagram obtained by calculation according to examples 1 to 3 of the present invention;
fig. 3 is an XRD fitting graph and a corresponding graphene ratio graph of the graphene/carbon nanotube composite conductive paste to be measured in embodiment 1 of the present invention, wherein points circled in the right graph are analyzed points to be measured;
fig. 4 is an XRD fitting graph and a corresponding graphene ratio graph of the graphene/carbon nanotube composite conductive paste to be measured in embodiment 2 of the present invention, wherein points circled in the right graph are analyzed points to be measured;
fig. 5 is an XRD fitting graph and a corresponding graphene ratio graph of the graphene/carbon nanotube composite conductive paste to be measured in embodiment 3 of the present invention, wherein points circled in the right graph are analyzed points to be measured.
Detailed Description
The embodiments of the invention will be described in detail below with reference to the drawings, but the invention can be implemented in many different ways as defined and covered by the claims.
Example 1:
(1) preparing graphene/carbon nano tube composite conductive slurry with different graphene ratios of 0%, 40%, 60% and 100%, respectively, baking, drying and grinding to obtain powder;
(2) respectively carrying out multiple XRD tests on the ground different graphene/carbon nanotube composite conductive slurry powders to respectively obtain multiple groups of XRD patterns and original data, as shown in figure 1;
(3) calculating the average value of a plurality of groups of XRD original data of different graphene/carbon nanotube composite conductive paste powders, performing Guss fitting, calculating that the 2 theta values of (002) diffraction peaks of 0%, 40%, 60% and 100% graphene/carbon nanotube composite conductive paste dry powders with the graphene proportions are 25.60896, 25.68946, 25.82917 and 26.14061 respectively and the full width at half maximum beta value is 0.051572407, 0.037052523, 0.034677811 and 0.025815336 respectively, and obtaining corresponding La values of 8.8402, 11.9482, 13.7635 and 16.9994 respectively through a formula La = [ (1.78tan theta)/beta ] + 1;
(4) making a curve chart of the obtained La value and the graphene ratio in the corresponding composite slurry to obtain a primary curve, namely a standard curve, of different graphene ratios and the La value, as shown in figure 2;
(5) taking dry powder of graphene/carbon nanotube composite conductive slurry to be tested (wherein the graphene proportion is within the range of 90 +/-0.05%) to perform XRD test, obtaining an XRD map and original data, fitting to obtain 2 theta values of (002) diffraction peaks which are 26.09262 respectively and half-height-width values which are 0.026965 respectively, and calculating the La value to be 16.288 according to the method in the step (3);
(6) and (3) the proportion of the graphene corresponding to the La value obtained in the step (5) on the standard curve obtained in the step (4) is 90.01%, and as shown in fig. 3, the test result is very close to the proportion of the graphene in the composite conductive paste to be tested.
Example 2:
(1) preparing graphene/carbon nano tube composite conductive slurry with different graphene ratios of 0%, 40%, 60% and 100%, respectively, baking, drying and grinding to obtain powder;
(2) respectively carrying out multiple XRD tests on the ground different graphene/carbon nanotube composite conductive slurry powders to respectively obtain multiple groups of XRD patterns and original data, as shown in figure 1;
(3) calculating the average value of a plurality of groups of XRD original data of different graphene/carbon nanotube composite conductive paste powders, performing Guss fitting, calculating that the 2 theta values of (002) diffraction peaks of 0%, 40%, 60% and 100% graphene/carbon nanotube composite conductive paste dry powders with the graphene proportions are 25.60896, 25.68946, 25.82917 and 26.14061 respectively and the full width at half maximum beta value is 0.051572407, 0.037052523, 0.034677811 and 0.025815336 respectively, and obtaining corresponding La values of 8.8402, 11.9482, 13.7635 and 16.9994 respectively through a formula La = [ (1.78tan theta)/beta ] + 1;
(4) drawing a curve chart of the obtained La value and the proportion of the graphene in the corresponding composite slurry to obtain the La value; a primary curve, i.e. a standard curve, of different graphene ratios and La values, as shown in fig. 2;
(5) taking dry powder of graphene/carbon nanotube composite conductive slurry to be tested (wherein the graphene proportion is within the range of 50 +/-0.05%) to perform XRD test, obtaining an XRD map and original data, fitting to obtain (002) diffraction peaks, wherein the 2 theta value is 26.03235 and the full width at half maximum value beta is 0.034881 respectively, and calculating the La value to be 12.792 according to the method in the step (3);
(6) and (3) the proportion of the graphene corresponding to the La value obtained in the step (5) on the standard curve obtained in the step (4) is 49.9%, and the test result is very close to the proportion of the graphene in the composite conductive paste to be tested.
Example 3:
(1) preparing graphene/carbon nano tube composite conductive slurry with different graphene ratios of 0%, 40%, 60% and 100%, respectively, baking, drying and grinding to obtain powder;
(2) respectively carrying out multiple XRD tests on the ground different graphene/carbon nanotube composite conductive slurry powders to respectively obtain multiple groups of XRD patterns and original data, as shown in figure 1;
(3) calculating and fitting the average values of multiple groups of XRD original data of different graphene/carbon nanotube composite conductive paste powders, calculating that the 2 theta values of (002) diffraction peaks of graphene, which are 0%, 40%, 60% and 100% of graphene/carbon nanotube composite conductive paste dry powder respectively, are 25.60896, 25.68946, 25.82917 and 26.14061 and the full width at half maximum beta is 0.051572407, 0.037052523, 0.034677811 and 0.025815336 respectively, and obtaining corresponding La values 8.8402, 11.9482, 13.7635 and 16.9994 respectively through a formula La = [ (1.78tan theta)/beta ] + 1;
(4) drawing a curve chart of the obtained La value and the proportion of the graphene in the corresponding composite slurry to obtain the La value; a primary curve, i.e. a standard curve, of different graphene ratios and La values, as shown in fig. 2;
(5) taking dry powder of graphene/carbon nanotube composite conductive slurry to be tested (wherein the graphene proportion is within the range of 20 +/-0.05%) to perform XRD test, obtaining an XRD map and original data, fitting to obtain (002) diffraction peaks, wherein the 2 theta value is 26.02422 and the full width at half maximum value beta is 0.04654 respectively, and calculating the La value to be 10.465 according to the method in the step (3);
(6) and (3) the proportion of the graphene corresponding to the La value obtained in the step (5) on the standard curve obtained in the step (4) is 20%, and the test result is very close to the proportion of the graphene in the composite conductive paste to be tested.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (4)
1. A quantitative analysis method for graphene/carbon nanotube composite conductive slurry is characterized by comprising the following steps:
(1) preparing graphene/carbon nano tube composite conductive slurry with different proportions, respectively baking and drying the graphene/carbon nano tube composite conductive slurry, and grinding the mixture to obtain powder;
(2) respectively carrying out multiple XRD tests on the ground different graphene/carbon nano tube composite conductive slurry powder to respectively obtain multiple groups of XRD patterns and original data;
(3) calculating and fitting the average value of a plurality of groups of XRD original data of different graphene/carbon nanotube composite conductive slurry powders, respectively calculating the 2 theta value and the full width at half maximum beta value of the (002) diffraction peak, and obtaining the corresponding La value through a formula La = [ (1.78tan theta)/beta ] + 1;
(4) drawing a curve chart of the obtained La value and the graphene ratio in the corresponding composite slurry to obtain primary curves of different graphene ratios and the La value, namely standard curves;
(5) taking the graphene/carbon nano tube composite conductive slurry dry powder to be tested to perform XRD test, obtaining an XRD spectrum and original data, and calculating the La value according to the method in the step (3);
(6) and (4) determining the graphene proportion of the La value obtained in the step (5) on the standard curve obtained in the step (4) as the proportion of graphene in the composite conductive paste to be tested.
2. The quantitative analysis method of graphene/carbon nanotube composite conductive paste according to claim 1, wherein the drying manner in step (1) is one of conventional air atmosphere drying, inert gas atmosphere drying, and vacuum drying.
3. The quantitative analysis method for graphene/carbon nanotube composite conductive paste according to claim 1, wherein the baking and drying temperature in step (1) is not more than 120 ℃.
4. The method for quantitatively analyzing graphene/carbon nanotube composite conductive paste according to claim 1, wherein the method for fitting the average value of XRD raw data of different graphene/carbon nanotube composite conductive paste powders in the step (3) is Guss fitting.
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