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CN110697693B - Graphene nanosheet material, and rapid manufacturing method and application thereof - Google Patents

Graphene nanosheet material, and rapid manufacturing method and application thereof Download PDF

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CN110697693B
CN110697693B CN201910844594.7A CN201910844594A CN110697693B CN 110697693 B CN110697693 B CN 110697693B CN 201910844594 A CN201910844594 A CN 201910844594A CN 110697693 B CN110697693 B CN 110697693B
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郝奕舟
吴永生
陈剑豪
王天戌
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Guangzhou Moxi Technology Co ltd
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Abstract

Graphene nanoplatelets, a rapid manufacturing method and applications thereof, the method comprising: and rapidly preparing the graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using a mixed gas of a carbon-containing gas and an auxiliary gas as a carbon source. The composite conductive slurry is prepared based on the graphene nanosheet material and comprises the graphene nanosheet material, a conductive polymer, a dispersing agent, a stabilizing agent and a solvent.

Description

Graphene nanosheet material, and rapid manufacturing method and application thereof
Technical Field
The present disclosure relates to graphene nanoplatelets, rapid manufacturing methods and applications thereof.
Background
Graphene (Graphene) is a two-dimensional crystal composed of 1 to 10 layers of carbon atoms. In 2004, physicists andrelim and consanguin norworth schloff, manchester university, uk, succeeded in isolating graphene from graphite, confirming that it can exist alone, and thus both people together won the 2010 nobel prize for physics.
At present, graphene has very promising applications in many aspects, but has many technical problems to be solved in the practical process.
Disclosure of Invention
The embodiment of the invention provides a graphene nanosheet material and a rapid manufacturing method thereof, and the method comprises the following steps: a Plasma Enhanced Chemical Vapor Deposition (PECVD) method is adopted, and a mixed gas of carbon-containing gas and auxiliary gas is used as a reaction gas source to rapidly prepare the graphene nanosheet material.
According to an embodiment of the invention, in the growth process of the graphene nano sheet material, a magnetic field perpendicular to the air flow is applied to the plasma, and the magnetic field strength is 1-10 μ T; preferably 3. Mu.T to 6. Mu.T.
According to one embodiment of the invention, during the growth of the graphene nano sheet material, a voltage of-5V to-20V relative to plasma is applied to the substrate; preferably, a voltage of-10V to-15V with respect to plasma is applied to the substrate.
According to an embodiment of the invention, the growth temperature range of the graphene nanosheet material grown on the functional substrate is 750-1100 ℃, preferably 850-950 ℃;
preferably, the volume ratio of the carbon-containing gas to the auxiliary gas is 1.
Preferably, the volume ratio of the argon gas, the nitrogen gas and the hydrogen gas in the auxiliary gas is 10.
Preferably, the carbon-containing gas comprises CH 4 、C 2 H 4 ，C 2 H 2 、C 2 F 6 。
Embodiments of the present invention provide a graphene nanosheet material manufactured according to the aforementioned method, the graphene nanosheet material having a specific surface area of 300m 2 /g～900m 2 (ii) in terms of/g. In accordance with one embodiment of the present invention,
the shape of the single graphene nanosheet is close to that of a petal, or is straight, or has a certain radian and is partially curled, and the shape comprises a flat shape, a wrinkled shape, an arc shape and a wave shape.
According to an embodiment of the present invention, the graphene nanoplatelets of the graphene nanoplatelet material have a size of 10nm to 50nm, preferably 15nm to 30nm;
preferably, the thickness of the nanosheet in the graphene nanosheet material is 0.33nm to 3.5nm, preferably 0.9nm to 2.6nm;
preferably, the graphene nanosheet material is porous, and the pore size is 5nm to 100nm, preferably 10nm to 30nm;
preferably, the graphene nanosheet material is porous in the inside and has a porosity of 3cm 3 /g～5cm 3 G, preferably 3.5cm 3 /g～4.5cm 3 /g；
Preferably, the density of the graphene nanosheet material is 0.2g/cm 3 ～0.6g/cm 3 Preferably 0.3g/cm 3 ～0.5g/cm 3 ；
Preferably, the graphene nanosheet material comprises particles composed of the graphene nanosheets, the particle size is 500 nm-1500 nm, preferably 800 nm-1100 nm, and the particles are irregular in shape.
Preferably, a bifurcation structure is formed among the multiple graphene nanosheets; a small part of the overlapping is not more than 30 percent;
preferably, the graphene nanoplatelets have the morphology shown in fig. 2.
According to an embodiment of the present invention, the graphene nanoplatelets particles have an SEM image as shown in fig. 1.
The embodiment of the invention provides a composite conductive paste, which comprises the graphene nanosheet material, a conductive polymer, a dispersant, a stabilizer and a solvent, wherein the viscosity of the graphene nanosheet material composite conductive paste is 8000-50000mPa.s, preferably 10000-25000mPa.s, and preferably 15000-20000mPa.s.
According to one embodiment of the invention, the fineness of the composite conductive paste is 5-50 microns, preferably 7-20 microns, and preferably 10-15 microns.
According to one embodiment of the invention, the conductivity of the composite conductive paste is 300-1000S/m, preferably 400-900S/m, and preferably 500-800S/m.
According to an embodiment of the present invention, the graphene nanoplatelets material includes graphene nanoplatelets particles and graphene nanoplatelets.
According to an embodiment of the present invention, the powder of graphene nanoplatelets has a conductivity of greater than 10 4 S.m -1 。
According to an embodiment of the present invention, the conductive polymer is at least one of polyaniline, polythiophene, and polypyrrole, and the mass of the conductive polymer accounts for 1 to 2% of the total mass of the slurry.
According to one embodiment of the invention, the dispersant is at least one of polyvinylpyrrolidone, polyacrylamide and sodium dodecyl benzene sulfonate; the mass of the dispersant accounts for 0.1-0.2 per mill of the total mass of the slurry.
According to one embodiment of the invention, the stabilizer is at least one of polyvinylidene fluoride, sodium carboxymethylcellulose, resin and polyacrylic acid, and the mass of the stabilizer accounts for 0.05-0.15 per mill of the total mass of the slurry.
According to an embodiment of the present invention, the solvent is one of water, N-methylpyrrolidone, and alcohol.
According to an embodiment of the invention, the graphene particles in the graphene nano sheet material composite conductive paste account for 1-10%, preferably 2-8%, and preferably 3-7% of the total mass of the paste.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below, and it is apparent that the drawings in the following description only relate to some embodiments of the present invention and are not limiting on the present invention.
Fig. 1 is a front-side (i.e., perpendicular to the substrate direction, or along the thickness direction of the graphene nanosheet material) SEM image of the graphene nanosheet material provided in example 4 of the present invention;
fig. 2 is a transmission electron microscope photograph of graphene nanoplatelets provided in embodiment 4 of the present invention;
fig. 3 is a charge and discharge curve of a battery prepared from the graphene composite conductive paste prepared in example 1 at different rates;
FIG. 4 is a charge-discharge curve of a battery prepared by using Super P as a conductive agent under different multiplying powers;
fig. 5 is a charge-discharge curve of a battery prepared by using common graphene as a conductive agent under different multiplying factors.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The rapid growth of high-quality graphene has always been a technical bottleneck restricting the large-scale commercial application of graphene. Although the preparation of graphene by using the PECVD method has been already 10 years old, the method has the disadvantages of slow speed of graphene growth, low yield and the like, and the production cost of the method is higher than that of other methods such as a chemical oxidation method and a physical method. However, the quality of the graphene prepared by the PECVD method is obviously superior to that of the graphene obtained by other methods, and the realization of large-scale preparation of the three-dimensional graphene by the PECVD method is always a hot spot in the field of graphene research. Other researchers in the field have tried various methods to increase the growth rate of graphene, such as increasing the amount of reactants, increasing the reaction temperature, changing the reaction formula, and the like. However, the growth rate is increased only in a limited way, and the quality of graphene is often seriously degraded, so that graphene cannot be obtained, and a large amount of amorphous carbon is obtained. In addition, for the three-dimensional graphene nanosheet with the nano-porous structure, the growth rate is greatly increased, the high quality is ensured, and meanwhile, the nano-porous structure of the three-dimensional graphene needs to be maintained unchanged, which is more difficult to add and has not been broken through for many years. According to the invention, a fully improved PECVD method is used, and through optimization promotion in multiple aspects, a graphene material which can grow at a very high speed and keeps a three-dimensional structure is obtained, and the material has a fine nano-porous structure and high-quality graphene nanosheets, so that the problem of a large difficulty in the field of three-dimensional graphene research is solved.
The conductive agent is used as an indispensable material in the lithium ion battery, and plays a significant role in improving the conductivity of the material, constructing a conductive network, providing a rapid channel for electron transmission and ensuring that active substances are fully utilized. At present, point contact exists between the commercial carbon black and the active substance, and the point contact exists between the carbon nano tubes, so that a complete conductive network structure is not formed. The graphene has excellent conductivity and has great advantages in constructing a large-area conductive network. The contact mode of the graphene is point-to-surface contact, the surfaces of active materials can be connected to form a large-area conductive network as a main body, but because the graphene only conducts electrons and does not conduct ions, the migration of lithium ions is hindered by the large-sheet two-dimensional graphene in the practical application process. Although the problem of lithium ion migration resistance can be solved to a certain extent by reducing the size of the two-dimensional graphene particles, the two-dimensional graphene particles with small particle size are more prone to agglomeration in the actual application process due to the pi-pi conjugation effect, and in addition, a good conductive network can be formed in the electrode only by adding more graphene particles after the graphene particle size is reduced. According to the invention, by utilizing the characteristics that the three-dimensional graphene is not easy to agglomerate, holes are rich to provide channels for lithium ion migration, and the conductive polymer is used as a flexible bridge for connecting graphene particles, the graphene is prepared into the high-dispersion-state graphene composite slurry by using the three-dimensional graphene and conductive polymer composite technology, and the technology not only solves the problem that the small-particle-size graphene is easy to agglomerate, but also solves the problems of lithium ion diffusion and conductive network integrity during use.
As described above, the present inventors have adopted that the present invention has at least the following advantages:
1) The embodiment of the invention provides a graphene nanosheet material capable of being rapidly grown, and compared with the conventional PECVD method, the production rate of the graphene nanosheet material is increased by several times to several tens of times.
2) The high-speed growth is realized, and simultaneously, the obtained graphene nanosheet is maintained at a high quality.
3) The material obtained has a fine three-dimensional mesoporous structure while realizing high-speed growth.
4) The method of the invention is simple and easy to operate, and can be applied to large-scale industrial production.
5) The invention provides a composite conductive slurry based on a graphene nanosheet material.
Example 1
Growing a graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate and taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. Introducing the mixed gas into a PECVD reactor, controlling the power of PECVD to be 5kW, and rapidly growing graphene nanosheets on a metal Cu substrate by a PECVD method, wherein the growth time is controlled to be 60 minutes, so that a graphene nanosheet material is obtained, the growth rate of the graphene nanosheet material is 250 mu m/h, and the specific surface area is 750m 2 G, porosity 3.9cm 3 (ii) in terms of/g. The graphene nanosheet material obtained in the embodiment has a large specific surface area and a large porosity, which indicates that the finally obtained graphene nanosheet material well maintains a porous three-dimensional structure.
Comparative examples 1 to 1
Growing a three-dimensional graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate and taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 Gas to nitrogen, argon and hydrogen volumetric ratios were 1. Introducing the mixed gas into a PECVD reactor, controlling the power of PECVD to be 1kW, and growing a three-dimensional graphene nanosheet on a metal Cu substrate by a PECVD method, wherein the growth time is controlled to be 60 minutes, so as to obtain a graphene nanosheet material, wherein the growth rate of the graphene nanosheet material is 10 mu m/h. The specific surface area is 400m 2 Per g, porosity 1.9cm 3 /g。
Example 2
Growing a graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate, taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. Introducing the mixed gas into a PECVD reactor, and controlling the power of PECVD to be 5kW; a static magnetic field is added in the direction perpendicular to the gas flow at both ends of the plasma, and the strength of the magnetic field is 5 μ T. Growing the graphene nanosheet on the metal Cu substrate by a PECVD method, controlling the growth time to be 60 minutes, and obtaining the graphene nanosheet material with the height of 350 mu m and the specific surface area of 750m 2 G, porosity 4.2cm 3 /g。
Comparative example 2 to 1
Growing a graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate and taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. The mixed gas is introduced into a PECVD reactor, the power of inductive coupling is controlled to be 5kW, a static magnetic field is added in the direction vertical to the gas flow and positioned at the two ends of the plasma, and the strength of the magnetic field is 0.1 mu T. Growing the graphene nanosheet on the metal Cu substrate by a PECVD method, controlling the growth time to be 60 minutes, and obtaining the graphene nanosheet material with the height of 250 mu m and the specific surface area of 750m 2 G, porosity 3.9cm 3 /g。
Comparative examples 2 to 2
Growing a three-dimensional graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Plasma of gas as precursor, with Cu metal as baseBottom, using hydrogen, nitrogen and argon as auxiliary gases, adding CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. The mixed gas is introduced into a PECVD reactor, the power of PECVD is controlled to be 5kW, a static magnetic field is added in the direction vertical to the gas flow and positioned at the two ends of the plasma, and the strength of the magnetic field is 100 mu T. At the moment, the concentration of the plasma is disturbed by an extremely strong magnetic field, so that the concentration of the plasma is not uniformly distributed in the reaction cavity and is concentrated in the central area of the magnetic field, and the growth cannot be normally carried out. Growing the graphene nanosheet on the metal Cu substrate by a PECVD method, controlling the growth time to be 60 minutes, and obtaining a three-dimensional graphene nanosheet material with the height of 3 mu m and the specific surface area of 300m 2 G, porosity 1.5cm 3 /g。
Comparing the results of example 2, example 1, comparative example 2-1, and comparative example 2-2, it is understood that increasing the static magnetic field of appropriate intensity in the direction perpendicular to the gas flow at both ends of the plasma is advantageous in increasing the production speed. For example, the magnetic field strength may be set to 1. Mu.T to 10. Mu.T, preferably 3 to 6. Mu.T, more preferably 5. Mu.T. If the magnetic field strength is too small, the effect is not significant, for example, in comparative example 2-1, the magnetic field of 0.1 μ T is added on the basis of example 1, and the preparation speed is hardly changed; if the magnetic field strength is too high, the plasma concentration may be unevenly distributed in the reaction chamber (e.g., concentrated in the central region of the magnetic field) such that growth does not proceed properly.
Example 3
Growing a graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate and taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. Introducing the mixed gas into a PECVD reactor, and controlling the power of PECVDA voltage of-12V versus the plasma potential was applied to the metallic Ni substrate at 5kW. The negative bias on the metal substrate causes more positive ions to migrate toward the substrate, increasing the plasma concentration at the surface of the metal substrate. Growing the graphene nanosheet on the metal Cu substrate by a PECVD method, controlling the growth time to be 60 minutes, and obtaining the graphene nanosheet material with the height of 420 mu m and the specific surface area of 800m 2 G, porosity 4.5cm 3 /g。
Comparative example 3-1
Growing a graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate and taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. The aforementioned mixed gas was introduced into a PECVD reactor, the power of PECVD was controlled at 5kW, and a voltage of-3V with respect to the plasma potential was applied to the metallic Cu substrate. Growing the graphene nanosheet on the metal Cu substrate by a PECVD method, controlling the growth time to be 60 minutes, and obtaining the graphene nanosheet material with the height of 270 mu m and the specific surface area of 750m 2 G, porosity 3.9cm 3 /g。
Comparative examples 3 and 2
Using Plasma Enhanced Chemical Vapor Deposition (PECVD) method to remove CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate and taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. The aforementioned mixed gas was introduced into a PECVD reactor, the power of PECVD was controlled at 5kW, and a voltage of-50V relative to the plasma potential was applied to the metallic Cu substrate. Growing on a metal Cu substrate by a PECVD method, controlling the growth time to be 60 minutes, not obtaining the graphene nanosheet material, and growing to obtain the similar materialParticulate amorphous carbon.
As is clear from the results of comparative examples 3, 1, 3-1 and 3-2, it is advantageous to increase the production rate by applying a negative voltage appropriate for the plasma (the relative voltage of the plasma itself is generally positive, about 10 to 20V) to the metal substrate. For example, a voltage of-5V to-30V, preferably-10V to-20V, and most preferably-15V, relative to the plasma may be applied to the substrate. If the voltage is not enough, the effect is not obvious, for example, the voltage of-3V is increased on the basis of the embodiment 1 in the comparative example 3-1, and the preparation speed is only increased in a small range; if the voltage is too large, the normal reaction process of the substrate surface can be affected, and the graphene nanosheet material cannot be grown, for example, in comparative example 3-2, the voltage of-50V is increased on the basis of example 1, only granular amorphous carbon is finally obtained, and the graphene nanosheet material cannot be obtained.
Example 4
Growing a graphene nanosheet material by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method and using CH 4 Taking gas plasma as a precursor, taking Cu metal as a substrate and taking hydrogen, nitrogen and argon as auxiliary gases, and taking CH 4 Mixing the gas, hydrogen, nitrogen and argon to form a mixed gas, wherein the CH 4 The gas to nitrogen, argon and hydrogen volume ratio was 1. The mixed gas is introduced into a PECVD reactor, and the power of PECVD is controlled to be 5kW. A voltage of-12V with respect to the plasma potential was applied to the metallic Cu substrate. A static magnetic field is added in a direction perpendicular to the gas flow at both ends of the plasma, and the strength of the magnetic field is 0.5 μ T. Growing the graphene nanosheet on the metal Cu substrate by a PECVD method, controlling the growth time to be 60 minutes, and obtaining the graphene nanosheet material with the height of 550 mu m and the specific surface area of 800m 2 G, porosity 4.5cm 3 /g。
Example 4 can consider that various means are comprehensively applied to increase the preparation speed of the graphene nanoplatelet material, including appropriately increasing the plasma concentration, increasing the magnetic field, applying a voltage to the substrate, and the like, and finally within 60 minutes, the graphene nanoplatelet material with the height of 550 μm is obtained.
The effect of varying the conditions on the preparation speed for examples 1 to 4 and for the comparative examples is shown in Table 1 below.
TABLE 1 influence of various changes in conditions on production speed in examples and comparative examples
Figure BDA0002194763540000091
Figure BDA0002194763540000101
In examples 1 to 4, the graphene nanoplatelets obtained by the rapid preparation method disclosed herein have a large specific surface area and porosity, which has demonstrated that the finally obtained graphene nanoplatelets well maintain a porous three-dimensional structure. To further illustrate the excellent properties of graphene nanoplatelets obtained according to the rapid preparation method provided herein, the following example 6 provides the use of graphene nanoplatelets prepared according to example 4 of the present invention in battery electrodes; embodiment 7 provides an application of the graphene nanosheet material prepared according to embodiment 4 of the present invention in lubrication.
Example 5
Mixing a commercial acetylene black conductive agent (Super P) as a conductive additive with a nickel-cobalt-manganese ternary positive electrode material NCM622 and a binder PVDF900 according to the mass ratio of 2 6 And assembling the electrolyte in a glove box filled with argon to obtain the CR2032 type button experiment battery. The obtained batteries were charged and discharged at different rates on a novacell battery test system, and the capacities at the different rates and the capacity retention (%) at 100 cycles at 1C were as shown in table 2 below.
Graphene prepared according to Hummers method is used as a conductive additiveMixing the agent, NCM622 and a binder PVD900F according to the mass ratio of 2 6 And assembling the electrolyte in a glove box filled with argon to obtain the CR2032 type button experiment battery. The obtained batteries were charged and discharged at different rates on a novacell battery test system, and the capacities at the different rates and the capacity retention (%) at 100 cycles at 1C were as shown in table 2 below.
The material prepared in the embodiment 4 of the invention is used as a conductive additive, mixed with NCM622 and PVDF900 as a binder according to the mass ratio of 2 6 And assembling the electrolyte in a glove box filled with argon to obtain the CR2032 type button experiment battery. The obtained batteries were charged and discharged at different rates on a novacell battery test system, and the capacities at the different rates and the capacity retention (%) at 100 cycles at 1C were as shown in table 2 below.
Table 2 comparison of performance of commercial acetylene black conductive agent (Super P), hummers graphene, and graphene nanoplatelet material of example 4 herein as electrode conductive agent
Figure BDA0002194763540000111
As can be seen from the results in table 2 above, the electrode capacity and the cycle performance of the graphene nanosheet material of example 4 herein as an electrode conductive agent are both significantly superior to those of the commercial acetylene black conductive agent (Super P) and Hummers graphene. This shows that the graphene nanoplatelets prepared according to the preparation method provided herein have not only greatly increased preparation speed, but also excellent electrical properties.
Example 7
A graphene composite conductive slurry and a preparation method thereof comprise the following steps:
(1) Crushing a certain amount of three-dimensional graphene by using a jet mill, wherein the pressure level of the crushing airflow is 1.2MPa, and the crushing is carried out until the granularity D is reached 50 Is 1500nm. .
(2) Taking 70.56g of particle size D 50 Adding 1500nm graphene nanosheet material, 0.8g polyvinylpyrrolidone, 920g N-methylpyrrolidone and 8g polyaniline into a 2L planetary stirring dispersion machine, revolving for 25r/min, and dispersing for 7000r/min for 60min to obtain the graphene and conductive polymer composite conductive slurry.
(3) And adding 0.64g of polyvinylidene fluoride into the graphene and conductive polymer composite conductive slurry, and dispersing for 60min by using a planetary stirring dispersion machine under the revolution of 25r/min and the dispersion of 7000rmin to obtain the graphene composite conductive slurry.
(4) The viscosity of the graphene composite conductive slurry is 50000mPa.s, the fineness of the graphene composite conductive slurry is 15 micrometers, and the conductivity is 1000S/m.
(5) The cells were prepared and tested:
mixing the graphene composite conductive slurry prepared in the embodiment 1 with a binder polyvinylidene fluoride and a ternary material cathode material according to a mass ratio of 2 6 The electrolyte is assembled in a glove box filled with argon to obtain a CR2032 type button experiment battery, and the charge-discharge curves of the battery under different multiplying factors are shown in figure 3.
Fig. 4 and 5 show that Super P and common graphene are respectively used as conductive agents, and the ratio of the conductive agent: binder polyvinylidene fluoride: mixing a ternary material positive electrode material =2 6 The electrolyte was assembled in a glove box filled with argon to obtain a CR2032 type button test cell, and the charge and discharge curves of the cell at different rates are shown in fig. 4 and 5.
Example 8
A graphene composite conductive slurry and a preparation method thereof comprise the following steps:
(1) Taking a certain amount of three-dimensional graphene, crushing the three-dimensional graphene by using a ball mill, wherein the ball-material ratio is 50:1, crushing to a particle size D 50 Is 800nm.
(2) Taking 4.3g of particle size D 50 Taking 800nm graphene nanosheet material, adding 0.05g polyvinylpyrrolidone, 95g N-methylpyrrolidone and 0.6g polyaniline into a 0.5L beaker, and dispersing by using an emulsifying machine, wherein the rotating speed of the emulsifying machine is 13000r/min, and the emulsifying time is 60min, so as to obtain the graphene and conductive polymer composite conductive slurry.
(3) And adding 0.05g of polyvinylidene fluoride into the graphene and conductive polymer composite conductive slurry, and dispersing for 30min at 13000r/min by using an emulsifying machine to obtain the graphene composite conductive slurry.
(4) The viscosity of the graphene composite conductive slurry is 40000mPa.s, the fineness of the graphene composite conductive slurry is 12 micrometers, and the conductivity is 900S/m.
Example 9
A graphene composite conductive slurry and a preparation method thereof comprise the following steps:
(1) Taking a certain amount of three-dimensional graphene, crushing the three-dimensional graphene by using a mechanical crusher to obtain a particle size D 50 Is 1200nm.
(2) Taking 63g of particle size D 50 Adding 1200nm graphene nanosheet material, 0.5g polyvinylpyrrolidone, 930g N-methylpyrrolidone and 0.57g polyaniline into a 2L sand mill, revolving for 25r/min, and dispersing for 40min at 7000r/min to obtain the graphene and conductive polymer composite conductive slurry.
(3) And adding 0.8g of polyvinylidene fluoride into the graphene and conductive polymer composite conductive slurry, and dispersing for 40min at 1200r/min by using a sand mill to obtain the graphene composite conductive slurry.
(4) The viscosity of the graphene composite conductive paste is 42000mPa.s, the fineness of the graphene composite conductive paste is 13 microns, and the conductivity is 950S/m.
Example 10
A graphene composite conductive slurry and a preparation method thereof comprise the following steps:
(1) Adding 5.16g of graphene nanosheet material, 0.06g of polyvinylpyrrolidone and 94g of pure water into a 0.5L sand mill, wherein the rotation speed of the sand mill is 2300r/min, and the crushing time is 4h to obtain the particle size D 50 Is a 1000nm graphene dispersion.
(3) Adding 0.72g of polyaniline into the graphene dispersion solution, and dispersing for 30min at 1100r/min by using a sand mill to obtain graphene and conductive polymer composite conductive slurry;
(4) And adding 0.06g of sodium carboxymethyl cellulose into the graphene and conductive polymer composite conductive slurry, and dispersing for 30min at 1200r/min by using a sand mill to obtain the graphene composite conductive slurry.
(5) The viscosity of the graphene composite conductive slurry is 35000mPa.s, the fineness of the graphene composite conductive slurry is 12 micrometers, and the conductivity is 800S/m.
Example 11
A graphene composite conductive slurry and a preparation method thereof comprise the following steps:
(1) Adding 4.962g of graphene nanosheet material, 0.09g of polyvinylpyrrolidone and 94g of N-methyl pyrrolidone into a 0.5L sand mill, wherein the rotation speed of the sand mill is 2300r/min, and the crushing time is 4h to obtain the particle size D 50 Is 800nm graphene dispersion.
(3) Adding 0.9g of polyaniline into the graphene dispersion solution, and dispersing for 30min at 1000r/min by using a sand mill to obtain graphene and conductive polymer composite conductive slurry;
(4) And adding 0.048g of polyvinylidene fluoride into the graphene and conductive polymer composite conductive slurry, and dispersing for 30min at 1200r/min by using a sand mill to obtain the graphene composite conductive slurry.
(5) The viscosity of the graphene composite conductive slurry is 30000mPa.s, the fineness of the graphene composite conductive slurry is 11 microns, and the conductivity is 700S/m.
Example 12
A graphene composite conductive slurry and a preparation method thereof comprise the following steps:
(1) 3.12g of graphene nanosheet material, 0.04g of sodium dodecyl sulfateAdding 96g of water into a 0.5L sand mill, wherein the rotation speed of the sand mill is 2300r/min, the crushing time is 4h, and the particle size D is obtained 50 Is 800nm graphene dispersion.
(3) Adding 0.4g of polyaniline into the graphene dispersion solution, and dispersing for 30min at 1000r/min by using a sand mill to obtain graphene and conductive polymer composite conductive slurry;
(4) And adding 0.04g of resin into the graphene and conductive polymer composite conductive slurry, and dispersing for 30min at 1000r/min by using a sand mill to obtain the graphene composite conductive slurry.
(5) The viscosity of the graphene composite conductive slurry is 30000mPa.s, the fineness of the graphene composite conductive slurry is 10 micrometers, and the conductivity is 600S/m.

Claims (13)

1. A rapid manufacturing method of graphene nanosheets, comprising: rapidly preparing a graphene nanosheet material by using a mixed gas of a carbon-containing gas and an auxiliary gas as a reaction gas source by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method;
in the growth process of the graphene nanosheet material, a magnetic field perpendicular to air flow is additionally applied to the plasma, and the magnetic field strength is 10 [ mu ] T;
applying a voltage of-20V relative to plasma on the substrate during the growth of the graphene nanoplatelet material;
the growth temperature range of the graphene nanosheet material grown on the functional substrate is 900-1100 ℃;
the volume ratio of the carbon-containing gas to the auxiliary gas is 1;
the volume ratio of the argon gas, the nitrogen gas and the hydrogen gas in the auxiliary gas is 10;
the carbon-containing gas comprises CH 4 、C 2 H 4 ，C 2 H 2 、C 2 F 6 。
2. A graphene nanoplatelet material manufactured according to the method of claim 1Wherein the specific surface area of the graphene nanosheet material is 800m 2 /g～900m 2 (ii)/g; the shape of the single graphene nanosheet is close to that of a petal, or is straight, or has a certain radian and is partially curled, and the shape comprises a flat shape, a wrinkled shape, an arc shape and a wave shape; the size of the graphene nanosheet material is 10 nm-30 nm;
the thickness of the nanosheet in the graphene nanosheet material is 0.33 nm-0.9 nm;
the graphene nanosheet material is porous inside, and the aperture size is 5 nm-10 nm;
the graphene nanosheet material is porous in the inside and has the porosity of 3.5cm 3 /g～4.5cm 3 /g；
The density of the graphene nanosheet material is 0.2g/cm 3 ～0.3g/cm 3 ；
The graphene nano-sheet material comprises particles formed by the graphene nano-sheets, the size of the particles is 500-1500 nm, and the shape of the particles is irregular;
a plurality of graphene nanosheets form a branched structure; a small part of the overlapping between the sheets is not more than 30%;
the graphene nanoplatelets have the appearance shown in figure 2.
3. The graphene nanoplatelet material of claim 2 wherein the graphene nanoplatelets particles have an SEM image as shown in figure 1.
4. The composite conductive paste is characterized by comprising the graphene nanosheet material as defined in claim 2 or 3, a conductive polymer, a dispersant, a stabilizer and a solvent, wherein the viscosity of the graphene nanosheet material composite conductive paste is 15000-20000mPa.s.
5. The composite conductive paste according to claim 4, wherein the fineness of the composite conductive paste is 5 μm.
6. The composite electroconductive paste according to claim 4, wherein the conductivity of the composite electroconductive paste is 300-1000S/m.
7. The composite conductive paste according to claim 4, wherein the graphene nanoplatelets comprise graphene nanoplatelet particles and graphene nanoplatelets.
8. The composite conductive paste as claimed in claim 7, wherein the powder conductivity of the graphene nanoplatelets particles is greater than 10 4 S.m -1 。
9. The composite conductive paste according to claim 4, wherein the conductive polymer is at least one of polyaniline, polythiophene and polypyrrole, and the mass of the conductive polymer accounts for 1-2% of the total mass of the paste.
10. The composite conductive paste according to claim 4, wherein the dispersant is at least one of polyvinylpyrrolidone, polyacrylamide, and sodium dodecylbenzenesulfonate; the mass of the dispersant accounts for 0.1-0.2 per mill of the total mass of the slurry.
11. The composite conductive paste according to claim 4, wherein the stabilizer is at least one of polyvinylidene fluoride, sodium carboxymethylcellulose, resin and polyacrylic acid, and the mass of the stabilizer accounts for 0.05-0.15% of the total mass of the paste.
12. The composite conductive paste according to claim 4, wherein the solvent is one of water, N-methylpyrrolidone, and alcohol.
13. The composite conductive paste according to claim 4, characterized in that the graphene particles in the graphene nanoplatelet material composite conductive paste account for 1-10% of the total mass of the paste.
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