CN111323417A - Rapid detection method and rapid determination method for storage stability of graphene material dispersion liquid - Google Patents
Rapid detection method and rapid determination method for storage stability of graphene material dispersion liquid Download PDFInfo
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Abstract
The invention provides a method for detecting the storage stability of a graphene material dispersion liquid, which comprises the following steps of firstly carrying out metallographic phase detection on the graphene material dispersion liquid to obtain the dispersion state and/or morphology condition of a graphene material in a dispersion liquid system; then centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid; detecting whether the bottom of the centrifugate is caked and/or whether the centrifugate is layered; stirring the centrifugate obtained in the step, and performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology of the graphene materials on the lower layer of the centrifugate in a dispersion system; and finally comparing the metallographic detection results in the two steps to judge the storage stability of the graphene material dispersion liquid. The rapid detection method can rapidly detect the dispersity of the graphene material dispersion liquid, particularly the dispersity and stability after long-time storage, by a simple centrifugal separation and stirring method.
Description
Technical Field
The invention belongs to the technical field of graphene, relates to a detection method and a determination method for storage stability of a graphene material dispersion liquid, and particularly relates to a rapid detection method and a rapid determination method for storage stability of a graphene material dispersion liquid.
Background
The graphene is a single-layer carbon atom tightly stacked into a two-dimensional hexagonal honeycomb lattice structure, all carbon atoms are connected in an sp2 hybridization mode, microscopically, a single-layer graphene film is not a two-dimensional flat structure but has a stable micro-wavy single-layer structure on a nanometer scale, and is a unique two-dimensional free-state atomic crystal found at present, macroscopically, the graphene can be warped into zero-dimensional fullerene, rolled into a one-dimensional carbon nanotube or stacked into three-dimensional graphite, and the unique two-dimensional periodic honeycomb lattice structure of the graphene has excellent performance due to the existence of a stable carbon six-membered ring, wherein the thickness of the single-layer graphene is only 0.35nm, the graphene is the lightest and thinnest material known at present, and the electron mobility at room temperature is 2 × 105cm2·V-1·s-11/300 for light speed, the theoretical specific surface area can reach 2630m2·g-1The light absorption of the whole wave band is only 2.3 percent, and the heat conductivity is as high as 5000 W.m-1·K-1Young's modulus exceeds 1100GPa, tensile strength exceeds 130GPa, toughness is very good, and when external mechanical force is applied, carbon atoms can adapt to external force through bending deformation without rearranging the carbon atoms, so that the structure is kept stable. These characteristics make it very suitable for being used in multiple disciplines and fields, it is used widely in the energy storage material, environmental engineering, sensitive sensing aspect, is called "black gold" or "the king of new material", and the latent application prospect is extensive, have become focus and research hot all over the world at present.
Although graphene has excellent performance, in practical application, graphene has a plurality of problems and restriction factors, and the most important problem is that graphene is easy to agglomerate, thereby causing difficulty in dispersibility. Due to the fact that strong van der waals acting force exists among the graphene, the graphene cannot be stably dispersed in a solvent, and is easy to agglomerate together again after being dispersed and difficult to open, so that research, application and industrialization of the graphene are greatly restricted, and particularly the problem of storage of manufacturers and users in subsequent actual industrialization is caused.
And with the further development and application of graphene, the requirements of people on the quality of graphene products are more and more strict, the requirements on the quality of graphene dispersion liquid are naturally higher and higher, and due to the defects that the graphene dispersion liquid is easy to settle and delaminate in the storage process, a settling layer is not easy to disperse again and the like, the production of products downstream of the graphene dispersion liquid is greatly influenced. Therefore, the storage stability of the graphene dispersion has become one of its important indicators.
However, how to detect the dispersibility of the graphene product and ensure the storage stability becomes a current technical difficulty, and how to rapidly judge the long-term storage performance of the graphene product dispersion is a blank in the field.
Therefore, how to find a method for detecting the dispersibility and storage stability of the graphene material and perform rapid and effective detection and analysis has become one of the problems to be solved by many graphene manufacturers and downstream customers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for detecting and determining storage stability of a dispersion liquid of a graphene material, and in particular, a method for rapidly detecting and determining storage stability of a dispersion liquid of a graphene material, which can rapidly detect dispersibility and stability of a dispersion liquid of a graphene material, and can rapidly determine storage stability of a dispersion liquid of a graphene material within 6 months.
The invention provides a method for detecting storage stability of a graphene material dispersion liquid, which comprises the following steps:
1) performing metallographic detection on the graphene material dispersion liquid to obtain the dispersion state and/or morphology condition of the graphene material in a dispersion liquid system;
2) centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid;
detecting whether the bottom of the centrifugate is caked and/or whether the centrifugate is layered;
4) stirring the centrifugate obtained in the step, and performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology condition of the graphene materials on the lower layer of the centrifugate in a dispersion system;
5) comparing the metallographic detection results obtained in the step 1) and the step 4) to judge the storage stability of the graphene material dispersion liquid.
Preferably, the graphene-based material comprises one or more of graphene, graphene oxide, reduced graphene oxide and modified graphene;
the solvent of the graphene-based material dispersion liquid comprises water and/or an organic solvent;
the mass concentration of the graphene material dispersion liquid is 0.1-3%.
Preferably, the organic solvent comprises one or more of ethanol, xylene, n-butanol, isopropanol, propylene glycol methyl ether, epoxy resin, acrylic resin, polyurethane and alkyd resin;
the rotating speed of the centrifugal treatment is 200-1000 r/min;
the time of the centrifugal treatment is 30-240 min.
Preferably, the bottom of the detection centrifugate is specifically as follows:
vertically placing the centrifugate, and detecting the bottom of the centrifugate through a device;
the device comprises one or more of a paint mixing knife, a medicine spoon and a glass rod.
Preferably, the step 2) is specifically:
centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid;
detecting whether the bottom of the centrifugate is caked or not and/or observing whether the layering phenomenon exists or not;
when the bottom of the centrifugate has caking and/or layering, the storage stability of the graphene material dispersion liquid is unqualified;
step 4) is carried out when there is no caking at the bottom of the centrate and/or stratification is present.
Preferably, the stirring comprises low speed stirring;
the stirring speed is 40-70 r/min;
the stirring time is 1-5 min.
Preferably, the alignment is specifically:
in the metallographic detection results of the step 1) and the step 4), the consistency of the dispersion state and/or the morphology condition of the graphene material is more than or equal to 80%;
the storage stability is in particular a storage stability within 12 months.
Preferably, the storage stability is in particular a storage stability within 6 months;
the similarity between the metallographic detection result obtained in the step 4) and the metallographic detection result obtained after the graphene material dispersion liquid is conventionally stored for 6 months is more than or equal to 90%.
Preferably, in the step 1) and the step 4), the metallographic detection specifically comprises: selecting different sampling points to perform multiple metallographic detection and/or selecting different microscopic metallographic fields of the same sample to perform multiple metallographic detection;
the number of times is 2-10.
The invention provides a method for judging storage stability of a graphene material dispersion liquid, which comprises the following steps:
1) centrifuging and stirring the graphene material dispersion liquid to obtain a centrifugal liquid;
the rotating speed of the centrifugal treatment is 200-1000 r/min;
the time of the centrifugal treatment is 30-240 min;
2) performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology condition of the graphene material on the lower layer of the centrifugate in a dispersion system;
the similarity between the dispersion state and/or morphology of the graphene material at the lower layer of the centrifugate in a dispersion system and the dispersion state and/or morphology of the graphene material at the lower layer of the dispersion after 6 months of storage of the graphene material dispersion under metallographic detection is more than or equal to 90%.
The invention provides a method for detecting the storage stability of a graphene material dispersion liquid, which comprises the following steps of firstly carrying out metallographic phase detection on the graphene material dispersion liquid to obtain the dispersion state and/or morphology condition of a graphene material in a dispersion liquid system; then centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid; detecting whether the bottom of the centrifugate is caked and/or whether the centrifugate is layered; stirring the centrifugate obtained in the step, and performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology of the graphene materials on the lower layer of the centrifugate in a dispersion system; and finally comparing the metallographic detection results obtained in the step 1) and the step 4) to judge the storage stability of the graphene material dispersion liquid. Compared with the prior art, the invention aims at the current situation that the existing detection method rarely relates to an effective method specially used for detecting the dispersity and long-term stability of the graphene material dispersion liquid, and the storage stability of the graphene dispersion liquid becomes an important index of the graphene dispersion liquid along with the further development and application of the graphene. Meanwhile, although there is a method for detecting ash content and solid content in the graphene dispersion liquid, the dispersion performance is difficult to judge through the detection result of the ash content, and the solid content value also has the problems of large error, poor parallelism and the like due to relatively low solid content in the graphene dispersion liquid.
The invention provides a method for rapidly detecting the dispersity and stability of a graphene material dispersion liquid, which can rapidly detect the dispersity of the graphene material dispersion liquid, particularly the dispersity and stability after long-time storage, effectively solves the problems of poor dispersity, long-time storage agglomeration and difficult determination of the dispersity stability of the graphene dispersion liquid in practical application, and can detect the stability of the graphene dispersion liquid after long-time storage compared with the current situation that the stability of the graphene dispersion liquid can be detected after the graphene dispersion liquid is stored under actual natural conditions.
Experimental results show that the method adopts a centrifugal mode, and can quickly judge the difference of dispersibility and stability of the graphene dispersion liquid after long-term storage for 6 months. The dispersion state and/or morphology condition of the graphene material dispersion liquid obtained by the method of the invention is more than or equal to 90% of the dispersion state and/or morphology condition of the lower layer of the dispersion liquid after the graphene material dispersion liquid is stored for 6 months under metallographic detection.
Drawings
FIG. 1 is a photograph showing the appearance of graphene dispersion OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention after standing for 6 months;
FIG. 2 is a photograph of a bottom layer sampled with a knife after the graphene dispersions OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention are left for 6 months;
FIG. 3 is a metallographic microscope photograph of graphene dispersions OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention before being placed;
FIG. 4 is a metallographic microscope photograph of the graphene dispersions OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention after being left for 6 months;
fig. 5 is a photograph of a sample bottom layer sampled by a knife after the graphene dispersion provided in example 2 of the present invention is naturally placed for 6 months and centrifuged;
fig. 6 is a photograph of the graphene dispersion provided in example 2 of the present invention after being naturally left for 6 months and treated by the present invention;
fig. 7 is a metallographic microscope photograph of the graphene dispersion provided in example 2 of the present invention after being naturally stored for 6 months and subjected to an initial treatment;
fig. 8 is a photograph of two graphene dispersions provided in example 3 of the present invention, which are subjected to centrifugation and other steps, and then the bottom layer is sampled by a knife;
fig. 9 is a metallographic microscope photograph of two graphene dispersions according to embodiment 3 of the present invention after treatment;
fig. 10 is a photograph of two graphene dispersions provided in example 4 of the present invention, which are subjected to centrifugation and other steps, and then the bottom layer is sampled by a knife;
fig. 11 is a metallographic microscope photograph of two graphene dispersions provided in example 4 of the present invention after treatment.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts the purity requirements of analytical purity or the purity requirements of the conventional graphene preparation field.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a method for detecting storage stability of a graphene material dispersion liquid, which comprises the following steps:
1) performing metallographic detection on the graphene material dispersion liquid to obtain the dispersion state and/or morphology condition of the graphene material in a dispersion liquid system;
2) centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid;
detecting whether the bottom of the centrifugate is caked and/or whether the centrifugate is layered;
4) stirring the centrifugate obtained in the step, and performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology condition of the graphene materials on the lower layer of the centrifugate in a dispersion system;
5) comparing the metallographic detection results obtained in the step 1) and the step 4) to judge the storage stability of the graphene material dispersion liquid.
According to the invention, firstly, metallographic detection is carried out on the graphene material dispersion liquid to obtain the dispersion state and/or morphology condition of the graphene material in the dispersion liquid system.
The definition of the metallographic detection is not particularly limited, and the definition of the metallographic detection known to those skilled in the art can be used, and those skilled in the art can select and adjust the metallographic detection according to the actual detection condition, the product requirement and the quality requirement, and the metallographic detection in the invention is preferably performed by a metallographic microscope.
The metallographic detection parameters are not particularly limited in principle, and conventional parameters of the graphene material solution for metallographic detection known by those skilled in the art can be selected and adjusted by those skilled in the art according to actual detection conditions, product requirements and quality requirements, and the times of the metallographic detection in the invention are preferably the times that the dispersion state and morphology of the graphene material in the graphene material solution can be seen clearly, more preferably 5-100 times, more preferably 20-80 times, more preferably 40-60 times, and particularly may be 5 times, 10 times, 20 times, 50 times, 100 times, more preferably 10 times, 20 times, 50 times.
The invention can better and accurately and rapidly detect the dispersion performance and the long-term storage stability of the graphene material dispersion liquid, and the detailed detection method improves the usability and the parallelism degree, and the metallographic detection in the steps is specifically as follows: and selecting different sampling points for carrying out multiple metallographic detection and/or selecting different microscopic metallographic view fields of the same sample for carrying out multiple metallographic detection. More preferably, different sampling points are selected for multiple metallographic detection or different microscopic metallographic fields of the same sample are selected for multiple metallographic detection. Therefore, the dispersion state of the graphene materials in the detected dispersion liquid can be more accurately reflected by metallographic detection. The multiple times of the invention are preferably 2 to 10 times, more preferably 3 to 9 times, and even more preferably 5 to 7 times.
The definition of the graphene-based material is not particularly limited, and may be defined by the definition of the graphene-based material known to those skilled in the art, and those skilled in the art can select and adjust the material according to the actual application, product requirements, and quality requirements, and the graphene-based material of the present invention is preferably graphene in a broad sense, and may also be referred to as graphene and its derivatives or graphene, and preferably includes one or more of narrow sense graphene, graphene oxide, reduced graphene oxide, and modified graphene, more preferably is single-layer graphene, few-layer graphene, multi-layer graphene, graphene oxide, reduced graphene oxide, or modified graphene, and more preferably is graphene, graphene oxide, or reduced graphene oxide.
The parameters of the graphene are not particularly limited, and the parameters of the graphene material known to those skilled in the art can be used, and those skilled in the art can select and adjust the parameters according to the actual application situation, the composite situation and the product performance, the number of the sheets of the graphene material is preferably 1 to 5, also can be 2 to 4, or 1 to 3, and the like, and specifically, the proportion of the graphene with the sheets being 5 or less is preferably greater than or equal to 80%, more preferably greater than or equal to 85%, and more preferably greater than or equal to 90%. The thickness of the graphene-like material sheet layer is preferably 0.7-2 nm, more preferably 1.0-1.8 nm, and more preferably 1.2-1.5 nm. The sheet diameter of the graphene-based material sheet is preferably 7-20 μm, more preferably 10-18 μm, and still more preferably 12-15 μm. The specific surface area of the graphene material is preferably 400-600 m2(ii)/g, more preferably 420 to 580m2(iv)/g, more preferably 450 to 550m2/g。
The solvent in the dispersion liquid of graphene materials is not particularly limited, and may be selected and adjusted by the skilled in the art according to the actual application, the product requirement and the quality requirement. The solvent of the graphene-based material dispersion liquid preferably includes water and/or an organic solvent, and more preferably water or an organic solvent. Wherein the organic solvent preferably comprises one or more of ethanol, xylene, n-butanol, isopropanol, propylene glycol methyl ether, epoxy resin, acrylic resin, polyurethane and alkyd resin, more preferably ethanol, xylene, n-butanol, isopropanol, propylene glycol methyl ether, epoxy resin, acrylic resin, polyurethane or alkyd resin.
The concentration of the dispersion liquid of graphene-based materials is not particularly limited in principle, and may be a conventional concentration of the dispersion liquid of graphene-based materials known to those skilled in the art, and those skilled in the art can select and adjust the concentration according to actual application conditions, product requirements and quality requirements, and the concentration of the dispersion liquid of graphene-based materials is preferably 0.1-3%, more preferably 0.5-2.5%, and more preferably 1.0-2.0%, in order to better and rapidly detect the dispersion performance and long-term storage stability of the dispersion liquid of graphene-based materials.
In principle, the definition of the dispersion state and/or morphology of the graphene-based material in the dispersion system is not particularly limited, and the detection condition of the conventional metallographic detection of the graphene-based material dispersion liquid, which is well known to those skilled in the art, may be used. Wherein, metallographic examination can clearly see whether the graphene material has agglomeration phenomenon, and the degree of agglomeration of the graphene material can be seen through the depth of color and the distribution of the material, namely the dispersion performance of the graphene material is reflected. Meanwhile, the morphology of the graphene material in the dispersion liquid system can be obtained by the morphology of the material in the metallographic photograph.
Centrifuging the graphene material dispersion liquid to obtain a centrifugate;
and detecting whether the bottom of the centrifugate is agglomerated and/or whether the centrifugate is layered.
The centrifugal treatment parameters are not particularly limited in principle, and a person skilled in the art can select and adjust the centrifugal treatment parameters according to actual application conditions, product requirements and quality requirements, the centrifugal treatment speed is preferably changed in direct proportion to the concentration of the graphene dispersion liquid and in inverse proportion to time, and the centrifugal treatment speed is preferably changed in 200-1000 r/min, more preferably 300-900 r/min, more preferably 400-800 r/min, and more preferably 500-700 r/min. The time of the centrifugal treatment is preferably changed in direct proportion to the concentration of the graphene dispersion liquid and in inverse proportion to the rotating speed, and the specific time is preferably 30-240 min, more preferably 60-210 min, more preferably 90-180 min, and more preferably 120-150 min.
The invention is not particularly limited in principle to the detection mode for detecting the bottom of the centrifugate, and a person skilled in the art can select and adjust the detection mode according to the actual application condition, the product requirement and the quality requirement, and the invention standardizes the detection method for better and rapidly detecting the dispersion performance and the long-term storage stability of the graphene material dispersion liquid, wherein the detection mode for detecting the bottom of the centrifugate specifically comprises the following steps: the centrifugate was placed vertically and the bottom of the centrifugate was detected by the device. The device of the present invention preferably comprises one or more of a paint mixing knife, a spatula and a glass rod, more preferably a paint mixing knife, a spatula or a glass rod.
The invention relates to a complete and detailed detection method capable of better and rapidly detecting the dispersion performance and long-term storage stability of graphene material dispersion liquid, wherein the step 2) is preferably as follows:
centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid;
detecting whether the bottom of the centrifugate is caked or not and/or observing whether the layering phenomenon exists or not;
when the bottom of the centrifugate has caking and/or layering, the storage stability of the graphene material dispersion liquid is unqualified;
step 4) is carried out when there is no caking at the bottom of the centrate and/or stratification is present.
The detection of whether the bottom of the centrifugate is caked or not and/or the observation of whether the demixing phenomenon exists or not are more preferably the detection of whether the bottom of the centrifugate is caked or not and the observation of whether the demixing phenomenon exists or not.
When the bottom of the centrifugate is agglomerated and/or a delamination phenomenon is observed, more preferably, when the bottom of the centrifugate is agglomerated or a delamination phenomenon is observed, it is judged that the storage stability of the dispersion liquid of the graphene-based material is poor and the requirement of the long-term storage stability cannot be satisfied. And when no caking exists at the bottom of the centrifugate and/or no layering phenomenon exists in observation, more preferably, no caking exists at the bottom of the centrifugate and no layering phenomenon exists in observation, judging that the storage stability of the graphene material dispersion liquid is good, meeting the requirement of long-term storage stability, and carrying out detection in the subsequent steps.
According to the invention, after the centrifugate obtained in the above steps is stirred, the lower layer of the centrifugate is taken for metallographic detection, and the dispersion state and/or morphology condition of the graphene material at the lower layer of the centrifugate in a dispersion system is obtained.
The stirring parameters are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application situation, the product requirements and the quality requirements. The rotation speed of the stirring is preferably 40-70 r/min, more preferably 45-65 r/min, and more preferably 50-60 r/min. The time of the centrifugal treatment is preferably 30-240 min, more preferably 60-210 min, more preferably 90-180 min, and more preferably 120-150 min.
In principle, the present invention is not particularly limited in definition of the dispersion state and/or morphology of the graphene-based material in the lower layer of the centrifugate in the dispersion system, and the detection condition of the conventional metallographic detection of the graphene-based material dispersion well known to those skilled in the art can be used, and those skilled in the art can select and adjust the dispersion state and/or morphology of the graphene-based material in the lower layer of the centrifugate in the dispersion system, preferably including the dispersion state and morphology of the graphene-based material in the lower layer of the centrifugate in the dispersion system according to the actual application condition, the product requirement and the quality requirement.
The invention can better and accurately and rapidly detect the dispersion performance and the long-term storage stability of the graphene material dispersion liquid, and the detailed detection method improves the usability and the parallelism degree, and the metallographic detection in the steps is specifically as follows: and selecting different sampling points for carrying out multiple metallographic detection and/or selecting different microscopic metallographic view fields of the same sample for carrying out multiple metallographic detection. More preferably, different sampling points are selected for multiple metallographic detection or different microscopic metallographic fields of the same sample are selected for multiple metallographic detection. Therefore, the dispersion state of the graphene materials in the detected dispersion liquid can be more accurately reflected by metallographic detection. The multiple times of the invention are preferably 2 to 10 times, more preferably 3 to 9 times, and even more preferably 5 to 7 times.
Finally, comparing the metallographic detection results obtained in the step 1) and the step 4) to judge the storage stability of the graphene material dispersion liquid. Namely, the storage stability of the dispersion liquid of the graphene-based material is judged by comparing the dispersion state and/or morphology of the graphene-based material in the dispersion liquid system in the step 1) and the step 4).
The specific way of the comparison is not particularly limited, and a person skilled in the art can select and adjust the comparison according to the actual application situation, the product requirements and the quality requirements, and the comparison is specifically preferably as follows:
in the metallographic detection results of the step 1) and the step 4), the consistency of the dispersion state and/or the morphology condition of the graphene material is more than or equal to 80%. The uniformity is more preferably 83% or more, more preferably 85% or more, and still more preferably 90% or more.
Namely, when the dispersion state and/or morphology of the graphene-based material in the lower layer of the centrifugate in the step 4) in the dispersion system reaches 80% of the dispersion state and/or morphology of the graphene-based material in the dispersion system in the step 1), the storage stability of the graphene-based material dispersion liquid is considered to meet the requirement.
The specific time of the storage stability is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, the product requirements and the quality requirements, and the storage stability is particularly preferably within 12 months, more preferably within 6 months, in order to better quantify and improve the accuracy of the rapid detection of the dispersion property and the long-term storage stability of the dispersion liquid of the graphene-based material.
The storage conditions and manner of the present invention are not particularly limited, and may be those of ordinary storage of the dispersion of the graphene-based material, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the actual application, the product requirements and the quality requirements, and the storage of the present invention is preferably normal temperature storage and/or standing storage. Wherein the normal temperature is preferably 10-40 ℃.
The steps of the invention provide a method for rapidly detecting the storage stability of the graphene material dispersion liquid. By adopting the rapid detection method provided by the invention, the dispersion state and/or morphology of the finally obtained graphene material in the lower layer of the centrifugate in the dispersion liquid system has the similarity of more than or equal to 90%, more preferably more than or equal to 93%, and more preferably more than or equal to 95% with the dispersion state and/or morphology of the lower layer of the dispersion liquid after the graphene material dispersion liquid is stored for 6 months under the metallographic detection.
Therefore, the invention also provides a method for judging the storage stability of the graphene material dispersion liquid, which comprises the following steps:
1) centrifuging and stirring the graphene material dispersion liquid to obtain a centrifugal liquid;
the rotating speed of the centrifugal treatment is 200-1000 r/min;
the time of the centrifugal treatment is 30-240 min;
2) performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology condition of the graphene material on the lower layer of the centrifugate in a dispersion system;
the similarity between the dispersion state and/or morphology of the graphene material at the lower layer of the centrifugate in a dispersion system and the dispersion state and/or morphology of the graphene material at the lower layer of the dispersion after 6 months of storage of the graphene material dispersion under metallographic detection is more than or equal to 90%.
In the present invention, the selection and composition of the steps and parameters in the determination method, and the corresponding preference principle, and the selection and composition of the corresponding steps in the detection method, and the corresponding preference principle, may all be performed correspondingly, and are not described in detail herein.
The determination method provided by the present invention can be used for determining the storage stability of the graphene-based material dispersion liquid within 6 months. Namely, by observing the dispersion state and/or morphology of the graphene material in the lower layer of the centrifugate in the dispersion liquid system, the dispersion state and/or morphology of the graphene material in the dispersion liquid system after the graphene material dispersion liquid is stored for 6 months can be rapidly known. Therefore, whether the dispersion state meets the requirements of customers or not can be simply, conveniently and rapidly judged after the graphene is stored for 6 months, or a subsequent graphene application experiment is carried out, and whether the final application product meets the requirements or not is detected.
The invention provides a method for rapidly detecting and rapidly judging the storage stability of a graphene material dispersion liquid, which can rapidly detect the dispersibility of the graphene material dispersion liquid, particularly the dispersibility and the stability after long-time storage by combining the centrifugal separation of specific parameters with low-speed stirring, particularly a low-speed centrifugal technology, screening the storage stability of the graphene dispersion liquid under the condition of low rotating speed, effectively solving the problems of poor dispersibility, long-time storage agglomeration and difficult determination of dispersion stability of the graphene dispersion liquid in practical application, and providing technical support for clients to judge products by comparing with the current situation that the stability of the graphene dispersion liquid can be detected after the graphene dispersion liquid is stored under actual natural conditions, thereby greatly improving the stability of the subsequent product performance.
The detection method provided by the invention is convenient and rapid, simple to operate, low in equipment cost, mild, simple and efficient in condition, and more suitable for industrial popularization and application, and the time cost and the detection cost are greatly reduced.
Experimental results show that the method adopts a centrifugal mode, and can quickly judge the difference of dispersibility and stability of the graphene dispersion liquid after long-term storage for 6 months. The dispersion state and/or morphology condition of the graphene material dispersion liquid obtained by the method of the invention is more than or equal to 90% of the dispersion state and/or morphology condition of the lower layer of the dispersion liquid after the graphene material dispersion liquid is stored for 6 months under metallographic detection.
For further illustration of the present invention, the following will describe the method for detecting the storage stability of the graphene-based material dispersion and the method for determining the storage stability of the graphene-based material dispersion in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
The product with good dispersion and the product with poor dispersion are subjected to routine comparison experiments
(1) Preparing a dispersion liquid: two graphene dispersions with 3% graphene content were prepared.
Respectively, the conventional graphene dispersion liquid with poor dispersion performance is numbered as OBO-MG-1; and an European platinum graphene dispersion liquid with good dispersion performance, and the European platinum graphene dispersion liquid is numbered OBO-MG-2;
(2) comparative experiment under natural conditions: taking 50g of each of the two graphene dispersions obtained in the step 1), putting the two graphene dispersions into a glass bottle with the diameter of 30mm and the height of 100mm, and carrying out vacuum drying under natural conditions (temperature: 23 ± 2 ℃, humidity: 60 + -10 RH) for 6 months.
The samples of the graphene dispersions OBO-MG-1 and OBO-MG-2 of example 1 of the present invention were characterized after 6 months of storage.
Referring to fig. 1, fig. 1 is a photograph showing the appearance of graphene dispersions OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention after standing for 6 months. Wherein A is graphene dispersion liquid OBO-MG-1, and B is graphene dispersion liquid OBO-MG-2.
As can be seen from FIG. 1, after the graphene dispersion OBO-MG-1 with poor dispersibility is placed for 6 months, an obvious delamination phenomenon already occurs, and the graphene dispersion OBO-MG-2 with good dispersibility does not have a delamination phenomenon.
(3) And (3) observing whether the sample subjected to the experiment in the step 2) is layered or not by naked eyes, and observing whether the phenomenon of agglomeration or the like exists or not by penetrating a paint adjusting knife into the bottom, wherein if the phenomenon of layering and agglomeration exists, the storage stability of the dispersion liquid is proved to be poor.
The detection results of the samples of the graphene dispersion liquid OBO-MG-1 and OBO-MG-2 in example 1 of the invention after being placed for 6 months.
Referring to fig. 2, fig. 2 is a photograph of the graphene dispersion liquid OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention, which was sampled with a knife at the bottom layer after being left for 6 months. Wherein A is graphene dispersion liquid OBO-MG-1, and B is graphene dispersion liquid OBO-MG-2.
As can be seen from FIG. 2, after the graphene dispersion OBO-MG-1 with poor dispersibility is placed for 6 months, the knife adjustment sampling already has an obvious caking phenomenon, and the graphene dispersion OBO-MG-2 with good dispersibility can still naturally flow in a fluid state after the knife adjustment sampling.
(4) Respectively taking the two dispersions obtained in the step 2), placing the two dispersions for 6 months, and observing the morphological characteristics of the lower layer liquid under the metallographic phase.
The samples in example 1 of the present invention were characterized by metallographic microscopy before and after 6 months of storage.
Referring to fig. 3, fig. 3 is a metallographic microscope photograph of graphene dispersions OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention before being placed. Wherein A is graphene dispersion liquid OBO-MG-1, and B is graphene dispersion liquid OBO-MG-2.
Referring to fig. 4, fig. 4 is a metallographic microscope photograph of graphene dispersions OBO-MG-1 and OBO-MG-2 provided in example 1 of the present invention after being left for 6 months. Wherein A is graphene dispersion liquid OBO-MG-1, and B is graphene dispersion liquid OBO-MG-2.
As can be seen from fig. 3 and 4, after the graphene dispersion liquid with poor dispersibility is placed for 6 months, graphene sheets in the metallographic photograph are obviously agglomerated and have completely distorted in morphology, while after the graphene dispersion liquid with good dispersibility is placed for 6 months, graphene sheets in the metallographic photograph are not obviously agglomerated, and only part of graphene sheets are stacked in morphology and slightly increased.
Example 2
Experimental comparison of natural standing of dispersed graphene dispersion liquid for 6 months and direct centrifugal treatment of initial dispersion liquid
(1) Preparing a dispersion liquid: the olpt graphene dispersion OBO-MG-2 of example 1 was used.
Taking 50g of the graphene dispersion liquid obtained in the step 1), putting the graphene dispersion liquid into a glass bottle with the diameter of 30mm and the height of 100mm, and carrying out vacuum evaporation under a natural condition (temperature: 23 ± 2 ℃, humidity: 60 + -10 RH) for 6 months.
(2) Taking 45g of the graphene dispersion liquid obtained in the step 1), putting the graphene dispersion liquid into a 50ml centrifuge tube, and centrifuging for 4h at the rotation speed of 500 r/min.
(3) And (3) observing whether the sample subjected to the experiment in the step 2) is layered or not by naked eyes, and observing whether the phenomenon of caking or the like exists or not by penetrating a knife into the bottom, wherein if the phenomenon of layering and caking exists, the storage stability of the dispersion is proved to be poor.
The graphene dispersion liquid is naturally placed for 6 months, and the detection result of the graphene dispersion liquid sample after centrifugal treatment is obtained.
Referring to fig. 5, fig. 5 is a photograph of a sample bottom layer sampled by a knife after the graphene dispersion provided in example 2 of the present invention is naturally placed for 6 months and centrifuged. Wherein, a is the graphene dispersion after natural standing for 6 months, and B is the graphene dispersion after the treatment of the embodiment 2 of the invention.
As can be seen from fig. 5, after the two graphene dispersions are sampled by knife adjustment, the two graphene dispersions can naturally flow in a fluid state, and the states are substantially the same.
(4) And (3) stirring the centrifugate obtained in the step (2) for 1min under the low-speed condition that the rotating speed is 60r/min to obtain a sample.
And (3) naturally placing the graphene dispersion liquid for 6 months, and detecting the graphene dispersion liquid sample treated by the method.
Referring to fig. 6, fig. 6 is a photograph showing the appearance of the graphene dispersion provided in example 2 of the present invention after natural standing for 6 months and the treatment of the present invention. Wherein, a is the graphene dispersion after natural standing for 6 months, and B is the graphene dispersion after the treatment of the embodiment 2 of the invention.
As can be seen from fig. 6, after the graphene dispersion liquid OBO-MG-2 with good dispersibility was left for 6 months, the appearance of the dispersion liquid was substantially the same as that of the dispersion liquid after the initial direct centrifugation treatment, and there was no delamination.
(5) Stirring the samples obtained in the steps 1) and 2) for 1min at a low speed of 60r/min respectively, taking the lower layer liquid, and observing the morphological characteristics of the samples under a metallographic microscope respectively.
The graphene dispersion liquid OBO-MG-2 in the embodiment 2 of the invention is placed for 6 months and is respectively characterized by a metallographic microscope after being treated by the method.
Referring to fig. 7, fig. 7 is a metallographic microscope photograph of the graphene dispersion provided in example 2 of the present invention after being naturally stored for 6 months and subjected to an initial treatment. Wherein, a is the graphene dispersion after natural standing for 6 months, and B is the graphene dispersion after the treatment of the embodiment 2 of the invention.
As can be seen from fig. 7, no significant agglomeration occurs in the metallographic photographs of the graphene dispersion after being placed for 6 months and after initial direct centrifugation, only a part of graphene sheets are stacked in the morphology and slightly increased, and the size, morphology and distribution state of the graphene sheets are substantially the same, and the consistency reaches 95%.
Meanwhile, aiming at the steps, the same sample is adopted to carry out comparison of three microscopic metallographic fields, and the results are basically consistent.
Example 3
The well dispersed product was compared to the poorly dispersed product in a centrifugation experiment.
(1) Preparing a dispersion liquid: the graphene dispersion liquid with poor dispersion performance in example 1 is also adopted, and is numbered as OBO-MG-1; and an European platinum graphene dispersion liquid with better dispersion performance, and the European platinum graphene dispersion liquid is numbered OBO-MG-2.
(2) Taking 45g of the graphene dispersion liquid obtained in the step 1), putting the graphene dispersion liquid into a 50ml centrifuge tube, and centrifuging for 4h at the rotation speed of 500 r/min.
(3) And (3) penetrating the sample after the experiment in the step 2) into the bottom by using a knife to observe whether the phenomena of caking and the like exist, and if the phenomena of caking exist, proving that the storage stability of the dispersion liquid is poor.
The two detection results of the graphene dispersion liquid samples centrifuged in the embodiment 3 of the present invention are shown.
Referring to fig. 8, fig. 8 is a photograph of two graphene dispersions provided in example 3 of the present invention, which are subjected to centrifugation and other steps, and then the bottom layer is sampled by a knife. Wherein A is graphene dispersion liquid OBO-MG-1, and B is graphene dispersion liquid OBO-MG-2.
As can be seen from fig. 8, after the graphene dispersion liquid OBO-MG-1 with poor dispersibility is subjected to centrifugal treatment, the knife adjustment sampling already has an obvious caking phenomenon, which is the same as the caking phenomenon after the same graphene dispersion liquid in example 1 is naturally placed for 6 months, while the graphene dispersion liquid OBO-MG-2 with better dispersibility can still naturally flow in a fluid state after the knife adjustment sampling, which is the same as the fluid state after the same graphene dispersion liquid in example 1 is naturally placed for 6 months.
(4) And (3) stirring the centrifugate obtained in the step (2) for 1min under the condition that the rotating speed is 60r/min to obtain a sample.
(5) Respectively taking the subnatant from the sample obtained in the step 4), and respectively observing the morphological characteristics of the subnatant under a metallographic microscope.
The two graphene dispersions provided in embodiment 3 of the present invention are characterized by a metallographic microscope.
Referring to fig. 9, fig. 9 is a metallographic microscope photograph of two graphene dispersions provided in example 3 of the present invention after being processed. Wherein A is graphene dispersion liquid OBO-MG-1, and B is graphene dispersion liquid OBO-MG-2.
As can be seen from fig. 9, after the graphene dispersion liquid OBO-MG-1 with poor dispersion performance is subjected to centrifugal treatment, graphene sheets in the metallographic photograph have obviously agglomerated and have completely distorted morphology, which is substantially the same as the morphology in the metallographic photograph after the same graphene dispersion liquid in example 1 is naturally placed for 6 months. The graphene dispersion liquid OBO-MG-2 with better dispersibility has no obvious agglomeration phenomenon, and only part of graphene sheets are stacked on the appearance and slightly increased, which is basically the same as the appearance in a metallographic picture of the same graphene dispersion liquid in the embodiment 1 after being naturally placed for 6 months.
As can be seen from comparison between fig. 9 and fig. 4, after the two graphene dispersions are naturally left for 6 months and treated by the present invention, the sizes, morphologies, colors, and distribution states of the sheets are substantially the same, and the consistency reaches 90%.
Meanwhile, according to the steps, the two processed graphene dispersion liquids are respectively sampled for three times and are observed by a metallographic microscope for comparison, and the results are basically consistent.
Example 4
Experimental comparison of well-dispersed products under different centrifugation rate conditions
(1) Preparing a dispersion liquid: the European platinum graphene dispersion with better dispersibility in example 1 was used and numbered OBO-MG-2.
(2) Taking 45g of the graphene dispersion liquid obtained in the step 1), putting the graphene dispersion liquid into a 50ml centrifugal tube, and centrifuging for 1h at the rotating speed of 1000r/min and 2h at the rotating speed of 1500r/min for observation.
(3) And (3) penetrating the sample after the experiment in the step 2) into the bottom by using a knife to observe whether the phenomena of caking and the like exist, and if the phenomena of caking exist, proving that the storage stability of the dispersion liquid is poor.
The two detection results of the graphene dispersion liquid samples centrifuged in the embodiment 4 of the present invention are shown.
Referring to fig. 10, fig. 10 is a photograph of two graphene dispersions provided in example 4 of the present invention, which are subjected to centrifugation and other steps, and then the bottom layer is sampled by a knife. Wherein A is the graphene dispersion liquid centrifuged for 1h at 1000r/min, and B is the graphene dispersion liquid centrifuged for 2h at 1500 r/min.
As can be seen from fig. 10, the graphene dispersion liquid after centrifugation for 1 hour at 1000r/min was still in a fluid state and naturally flowed after knife adjustment and sampling, which is the same as the fluid state of the same graphene dispersion liquid in example 1 after being naturally left for 6 months. However, the graphene dispersion knife adjustment sampling processed by centrifuging for 2 hours at 1500r/min has an obvious caking phenomenon, which is completely different from the caking phenomenon of the same graphene dispersion in example 1 after naturally standing for 6 months, and cannot reflect the real state of the graphene dispersion after naturally standing for 6 months.
(4) And (3) stirring the centrifugate obtained in the step (2) for 1min under the low-speed condition that the rotating speed is 60r/min to obtain a sample.
(5) Taking the subnatants of 1h and 2h in the step 4) respectively, and observing the morphological characteristics of the subnatants under a metallographic phase.
The two graphene dispersions provided in embodiment 4 of the present invention are characterized by a metallographic microscope.
Referring to fig. 11, fig. 11 is a metallographic microscope photograph of two graphene dispersions provided in example 4 of the present invention after being processed. Wherein A is the graphene dispersion liquid centrifuged for 1h at 1000r/min, and B is the graphene dispersion liquid centrifuged for 2h at 1500 r/min.
As can be seen from fig. 11, the graphene dispersion liquid treated by centrifugation for 1 hour at 1000r/min has no obvious agglomeration, and only a part of graphene sheets are stacked in the morphology and slightly increased, which is substantially the same as the morphology in the metallographic photograph of the same graphene dispersion liquid in example 1 after being naturally placed for 6 months. However, graphene sheets in the metallograph are obviously agglomerated and completely distorted in appearance after the graphene dispersion liquid is centrifuged for 2 hours at 1500r/min, which is obviously different from the appearance of the metallograph obtained after the same graphene dispersion liquid is naturally placed for 6 months in example 1, and cannot reflect the real state after the graphene dispersion liquid is naturally placed for 6 months.
The foregoing detailed description of the method for rapid detection and rapid determination of storage stability of a dispersion of graphene-based materials provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are provided to facilitate an understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination thereof. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for detecting storage stability of a graphene material dispersion liquid is characterized by comprising the following steps:
1) performing metallographic detection on the graphene material dispersion liquid to obtain the dispersion state and/or morphology condition of the graphene material in a dispersion liquid system;
2) centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid;
detecting whether the bottom of the centrifugate is caked and/or whether the centrifugate is layered;
4) stirring the centrifugate obtained in the step, and performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology condition of the graphene materials on the lower layer of the centrifugate in a dispersion system;
5) comparing the metallographic detection results obtained in the step 1) and the step 4) to judge the storage stability of the graphene material dispersion liquid.
2. The detection method according to claim 1, wherein the graphene-based material includes one or more of graphene, graphene oxide, reduced graphene oxide, and modified graphene;
the solvent of the graphene-based material dispersion liquid comprises water and/or an organic solvent;
the mass concentration of the graphene material dispersion liquid is 0.1-3%.
3. The detection method according to claim 2, wherein the organic solvent comprises one or more of ethanol, xylene, n-butanol, isopropanol, propylene glycol methyl ether, epoxy resin, acrylic resin, polyurethane, and alkyd resin;
the rotating speed of the centrifugal treatment is 200-1000 r/min;
the time of the centrifugal treatment is 30-240 min.
4. The detection method according to claim 1, wherein the detection of the bottom of the centrifugate specifically comprises:
vertically placing the centrifugate, and detecting the bottom of the centrifugate through a device;
the device comprises one or more of a paint mixing knife, a medicine spoon and a glass rod.
5. The detection method according to claim 2, wherein the step 2) is specifically:
centrifuging the graphene material dispersion liquid to obtain a centrifugal liquid;
detecting whether the bottom of the centrifugate is caked or not and/or observing whether the layering phenomenon exists or not;
when the bottom of the centrifugate has caking and/or layering, the storage stability of the graphene material dispersion liquid is unqualified;
step 4) is carried out when there is no caking at the bottom of the centrate and/or stratification is present.
6. The detection method according to claim 1, wherein the stirring includes low-speed stirring;
the stirring speed is 40-70 r/min;
the stirring time is 1-5 min.
7. The detection method according to any one of claims 1 to 6, wherein the comparison specifically is:
in the metallographic detection results of the step 1) and the step 4), the consistency of the dispersion state and/or the morphology condition of the graphene material is more than or equal to 80%;
the storage stability is in particular a storage stability within 12 months.
8. The assay according to any one of claims 1 to 6, wherein the storage stability is in particular a storage stability within 6 months;
the similarity between the metallographic detection result obtained in the step 4) and the metallographic detection result obtained after the graphene material dispersion liquid is conventionally stored for 6 months is more than or equal to 90%.
9. The detection method according to any one of claims 1 to 6, wherein in the step 1) and the step 4), the metallographic detection is specifically as follows: selecting different sampling points to perform multiple metallographic detection and/or selecting different microscopic metallographic fields of the same sample to perform multiple metallographic detection;
the number of times is 2-10.
10. A method for judging storage stability of a graphene material dispersion liquid is characterized by comprising the following steps:
1) centrifuging and stirring the graphene material dispersion liquid to obtain a centrifugal liquid;
the rotating speed of the centrifugal treatment is 200-1000 r/min;
the time of the centrifugal treatment is 30-240 min;
2) performing metallographic detection on the lower layer of the centrifugate to obtain the dispersion state and/or morphology condition of the graphene material on the lower layer of the centrifugate in a dispersion system;
the similarity between the dispersion state and/or morphology of the graphene material at the lower layer of the centrifugate in a dispersion system and the dispersion state and/or morphology of the graphene material at the lower layer of the dispersion after 6 months of storage of the graphene material dispersion under metallographic detection is more than or equal to 90%.
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