CN111573661A - Preparation method and equipment of graphene slurry - Google Patents
Preparation method and equipment of graphene slurry Download PDFInfo
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- CN111573661A CN111573661A CN202010501716.5A CN202010501716A CN111573661A CN 111573661 A CN111573661 A CN 111573661A CN 202010501716 A CN202010501716 A CN 202010501716A CN 111573661 A CN111573661 A CN 111573661A
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Abstract
The invention provides a preparation method of graphene slurry and equipment thereof, wherein the preparation method of the graphene slurry comprises the following steps: preparing graphene oxide aqueous slurry; drying the graphene oxide aqueous slurry to obtain a graphene oxide dry material; crushing the graphene oxide dry material to obtain a graphene oxide dry material; putting the graphene oxide dry powder into a tunnel furnace for reduction stripping treatment to obtain graphene powder, wherein the tunnel furnace comprises a plurality of temperature areas, and the temperature ranges of the temperature areas are 80-950 ℃; and placing the graphene powder in a heat treatment device for heat treatment to obtain graphene slurry, wherein the working temperature range of the heat treatment device is 20-3750 ℃. The graphene slurry with high purity, high conductivity and thin sheet layers can be obtained.
Description
Technical Field
The invention relates to the technical field of preparation of conductive agents, in particular to a preparation method and equipment of graphene slurry.
Background
In the 21 st century, with the rapid development of new green energy, lithium ion batteries, as a representative of the current new green energy, have the advantages of high energy density, excellent cycle performance, low self-discharge rate and the like, and are widely applied to the fields of energy storage, electric vehicles, electronic products and the like. With the further development of electric vehicle technology, a great demand is placed on high-capacity high-power-density high-performance power batteries and the like. As a two-dimensional nanomaterial with high conductivity, graphene is considered as one of key materials of a high-performance conductive agent for a power battery, and is widely applied to positive electrode conductive agent slurry at present, so that the conductivity of the battery is further improved.
At present, a plurality of methods for preparing graphene are available, and the methods mainly applied to the market in large scale include a mechanical stripping method and a redox method.
The graphene stripped by the mechanical stripping method has the defects of relatively high conductivity, relatively thick thickness and more layers; in addition, a mechanical stripping method is adopted, the raw material is crystalline flake graphite or expandable graphite or expanded worm graphite, and when the physical mechanical stripping preparation is carried out by using a liquid phase or other methods, a large amount of sulfur elements are contained in the material, and a large amount of residual elements such as iron, cobalt, nickel, manganese, potassium, calcium and the like in the material are contained in the material, the content of the elements seriously exceeds the standard, and the performance of the battery is greatly influenced.
The graphene material manufactured by the redox method has very thin thickness and high single-layer rate, but the oxidation process causes great damage to the graphene substrate, can generate cavities and other functional groups, and introduces a large amount of sulfur element, iron, cobalt, nickel, manganese and other metal impurities, thereby greatly influencing the conductivity and the battery performance.
Disclosure of Invention
In order to solve the problems, the graphene slurry with high purity, high conductivity and thin sheet layers can be obtained by the preparation method and the equipment of the graphene slurry.
In a first aspect, the present invention provides a method for preparing graphene slurry, including:
preparing graphene oxide aqueous slurry;
drying the graphene oxide aqueous slurry to obtain a graphene oxide dry material;
crushing the graphene oxide dry material to obtain a graphene oxide dry material;
putting the graphene oxide dry powder into a tunnel furnace for reduction stripping treatment to obtain graphene powder, wherein the tunnel furnace comprises a plurality of temperature areas, and the temperature ranges of the temperature areas are 80-950 ℃;
and placing the graphene powder in a heat treatment device for heat treatment to obtain graphene slurry, wherein the working temperature range of the heat treatment device is 20-3750 ℃.
Alternatively, the preparing of the graphene oxide aqueous slurry comprises:
mixing sulfuric acid, flake graphite, sodium nitrate, potassium permanganate, pure water and hydrogen peroxide, and performing heat treatment through a heating device to obtain a first mixture;
filtering and deslagging the first mixture to obtain a second mixture;
refluxing the second mixture to a heating device, and carrying out heating treatment to enable the second mixture to be in a boiling state;
cooling the second mixture in the boiling state;
centrifuging the cooled second mixture to obtain a third mixture;
heating the third mixture and hydrochloric acid, and then washing with pure water to obtain a fourth mixture;
and centrifuging the fourth mixture to obtain graphene oxide aqueous slurry.
Optionally, mixing sulfuric acid, flake graphite, sodium nitrate, potassium permanganate, pure water, and hydrogen peroxide, and performing heat treatment by using a heating device to obtain a first mixture, including:
injecting 98% sulfuric acid of x1L into the low-temperature reaction kettle, and starting a low-temperature water cooler to circularly cool the sulfuric acid in the reaction kettle;
starting a stirring paddle of the low-temperature reaction kettle, and adding 1000-mesh high-purity crystalline flake graphite of a1kg and sodium nitrate of b1kg into the low-temperature reaction kettle;
when the temperature in the low-temperature reaction kettle is reduced to 8-10 ℃, starting a feeder, and adding potassium permanganate into the low-temperature reaction kettle, wherein the feeding mode of the potassium permanganate is as follows: adding potassium permanganate c1-d1g every time, and adding potassium permanganate e1kg at an interval of 3-5 min;
after the potassium permanganate is added, reacting for at least f1 hours to obtain a first a-class mixture;
transferring the first a-type mixture into a medium-temperature reaction kettle, and starting a stirrer and a circulating cooling water device of the medium-temperature reaction kettle;
adding water into the medium-temperature reaction kettle in a mode of: 0-a2L pure water, adding water at the speed of b2ml/min-c2 ml/min; d2L-e2L pure water, adding water at the speed of f2ml/min-g2 ml/min; adding water into the residual h2L pure water at a speed of i2L/min-j2L/min, wherein the temperature in the kettle is maintained at 30-40 ℃ in the water adding process;
after the water is added, a first b-type mixture is obtained;
transferring the first b-type mixture into a high-temperature reaction kettle, starting a stirrer of the high-temperature reaction kettle, setting the temperature in the high-temperature reaction kettle to be 98 ℃, setting the oil temperature of heat conducting oil in the high-temperature reaction kettle to be 240 ℃, and heating;
keeping the temperature in the high-temperature reaction kettle for at least 2 hours after the temperature in the high-temperature reaction kettle reaches 98 ℃ to obtain a first c-type mixture;
after the high-temperature reaction, transferring the materials into a high-temperature cooling kettle, and adding hydrogen peroxide of a3kg after the temperature is reduced to 50-60 ℃ at the speed of: b3L/min-c 3L/min; and reacted for at least 1 hour to obtain a first mixture.
Optionally, before the filtering and deslagging the first mixture, the method further comprises:
injecting pure water of a4-b4L into the standing tank, and starting a stirring paddle in the standing tank;
transferring the first mixture into a standing tank, and closing a stirring paddle in the standing tank after the first mixture is uniformly mixed with the pure water;
after standing for 10-12 hours, opening a drain valve of the standing tank to drain the supernatant after precipitation, wherein the water discharge amount is as follows: c4-d 4L.
Optionally, the refluxing the second mixture to a heating device and performing a heating treatment includes:
stirring the second mixture uniformly;
transferring the second mixture into a reflux reaction kettle, starting a heating device for heating, setting the temperature in the reflux reaction kettle to be 100 ℃, and setting the temperature of the electrically-heated heat conduction oil of the reflux reaction kettle to be 240 ℃;
keeping the temperature in the kettle at 100 ℃ for at least 15 min;
the second mixture in the cooled boiling state comprising:
after keeping for at least 15min, transferring the materials in the reflux reaction kettle into a reflux cooling kettle for cooling;
waiting for the temperature of the materials in the reflux cooling kettle to be reduced to below 50 ℃.
Optionally, the third mixture is subjected to a heating treatment with hydrochloric acid, and then washed with pure water, so as to obtain a fourth mixture, including:
injecting x2L hydrochloric acid into the purification reaction kettle, and injecting a5-b5L pure water into the purification plastic tank;
transferring the material in the first centrifugal buffer tank into a purification reaction kettle, starting a heating device for heating, setting the temperature in the purification reaction kettle to be 80 ℃, and setting the temperature of electrically heated heat conduction oil to be 200 ℃;
keeping the temperature in the purification reaction kettle for at least 2 hours when the temperature reaches 80 ℃;
after keeping for at least 2 hours, c5L pure water is injected into the purification reaction kettle, and the purification reaction kettle is transferred into a purification plastic tank after being stirred uniformly, and is stirred in the purification plastic tank for at least 10 min.
And after standing for 10-12h, opening a drain valve of the purification plastic tank to drain the supernatant after precipitation, wherein the water discharge amount is d5-e5L, and obtaining a fourth mixture.
Alternatively, x 1: a 1: b 1: c 1: d 1: e 1: f1 ═ 80: 2: 1: 80: 100: 2.8: 0.8;
b1：a2：b2：c2：d2：e2：f2：g2：h2：i2：j2＝1：30：24：26：30：74：30：32：16：0.5：0.6；
b1：a3：b3：c3＝1：7.4：0.3：0.5；
b1：a4：b4：c4：d4＝1：0.8：0.84：0.6：0.64；
b1：x2：a5：b5：c5：d5：e5＝1：20：0.7：0.8：60：0.5：0.6；
the slag removal centrifugal machine is a 45L steel-lined plastic corrosion-resistant centrifugal machine and is additionally provided with a filter screen of 150-200 meshes;
the centrifuge of the second centrifugal buffer tank is a 45L steel-lined plastic anti-corrosion centrifuge and is additionally provided with a 1000-mesh filter screen;
the concentration of the hydrochloric acid is 27% -33%.
Optionally, the drying the graphene oxide aqueous slurry to obtain a graphene oxide dry material includes:
and placing the graphene oxide aqueous slurry in an oven to be dried for 24 to 30 hours to obtain a graphene oxide dry material, wherein the working temperature range of the oven is 70 to 75 ℃.
Optionally, the crushing the graphene oxide dry material to obtain a graphene oxide dry material includes:
and (3) putting the dry graphene oxide material into a grinder for grinding treatment to obtain dry graphene oxide material, wherein a screen of the grinder is a 100-mesh screen.
Optionally, the tunnel furnace comprises: a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, a fifth temperature zone, a sixth temperature zone, a seventh temperature zone, and an eighth temperature zone;
the temperature of the first temperature zone is 80 ℃, the temperature of the second temperature zone is 300 ℃, the temperature of the third temperature zone is 300 ℃, the temperature of the fourth temperature zone is 500 ℃, the temperature of the fifth temperature zone is 600 ℃, the temperature of the sixth temperature zone is 800 ℃, the temperature of the seventh temperature zone is 950 ℃, and the temperature of the eighth temperature zone is 950 ℃;
the method for reducing and stripping the graphene oxide dry powder in the tunnel furnace to obtain the graphene powder comprises the following steps:
and putting the graphene oxide dry powder into the tunnel furnace for reduction stripping treatment, so that the graphene oxide dry powder sequentially passes through a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, a fifth temperature zone, a sixth temperature zone, a seventh temperature zone and an eighth temperature zone to obtain graphene powder.
Optionally, the placing the graphene powder in a heat treatment device for heat treatment to obtain a graphene slurry includes:
putting the graphene powder into a graphite container;
placing the graphite container in a heat treatment device for heat treatment for 1 to 50 days to obtain graphene slurry;
the graphite container includes: a cup body and a top cover;
the inner wall of the cup body is provided with a first internal thread at a position located at the opening, a first external thread is arranged on the periphery of the top cover, and the top cover is used for placing the graphene powder through clearance fit of the first external thread and the first internal thread and formation of a closed cavity by the cup body.
Optionally, the graphite container further comprises: a screw;
the top cover is provided with a through hole;
the week side of screw rod is provided with the second external screw thread, the top cap is located the inner wall of through-hole department is provided with the second internal thread, the screw rod passes through the second external screw thread with the internal screw thread clearance fit of second with the top cap is fixed can dismantle the connection.
In a second aspect, the present invention provides a graphene slurry preparation apparatus, which is applied to the above graphene slurry preparation method, and the apparatus includes the above low-temperature reaction kettle, low-temperature water cooler, medium-temperature reaction kettle, circulating cooling water device, water feeder, high-temperature reaction kettle, high-temperature cooling kettle, standing tank, reflux reaction kettle, reflux cooling kettle, purification reaction kettle, purification plastic tank, second centrifugal buffer tank, oven, crusher, tunnel furnace and heat treatment device;
the graphite container is arranged in the heat treatment device;
the low-temperature water cooler with low temperature reation kettle connects, low temperature reation kettle is connected with medium temperature reation kettle, recirculated cooling water device with add the water machine all with medium temperature reation kettle connects, medium temperature reation kettle with high temperature cooling cauldron all with high temperature reation kettle connects, the jar of stewing all with high temperature cooling cauldron is connected, the jar of stewing with reflux reation kettle connects, reflux reation kettle with reflux cooling cauldron connects, reflux cooling cauldron with purification reation kettle connects, purification reation kettle with purification plastic tank connects, purification plastic tank with the second centrifugation buffer tank is connected.
According to the preparation method and the equipment of the graphene slurry provided by the embodiment of the invention, after the graphene oxide aqueous slurry is dried, crushed and reduced and stripped, the graphene oxide aqueous slurry is heated in a heat treatment device, the graphene structure can be reformed, a large number of oxygen-containing functional groups in the graphene structure are removed, and the thin-layer graphene material with a unique structure is obtained, and has the characteristics of high single-layer rate, high conductivity and low impurity content.
Drawings
Fig. 1 is a schematic flow chart of a method of preparing a graphene slurry according to an embodiment of the present application;
fig. 2 is a schematic flow diagram of a method of preparing an aqueous slurry of graphene oxide according to an embodiment of the present application;
FIG. 3 is a cross-sectional view of a graphite container with a cup and lid separated according to one embodiment of the present application;
fig. 4 is a schematic structural view of a graphene slurry preparation apparatus according to an embodiment of the present application;
fig. 5 is a TEM image of a graphene slurry prepared by a conventional redox method;
fig. 6 is a TEM image of graphene slurry prepared by a conventional mechanical exfoliation method;
fig. 7 is a TEM image of graphene slurry prepared by the present invention;
fig. 8 is a raman test chart of graphene slurry prepared by a conventional general redox method;
fig. 9 is a raman test chart of graphene slurry prepared by a conventional mechanical exfoliation method;
fig. 10 is a raman test chart of the graphene slurry prepared according to the present invention;
fig. 11 is a comparison graph of the graphene slurry obtained by the present invention and graphene slurries obtained by a common oxidation-reduction method and a mechanical exfoliation method, which are both used for preparing corresponding graphene conductive agent slurries for a high-rate discharge performance test.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In a first aspect, with reference to fig. 1, the present invention provides a method for preparing graphene slurry, including steps S101 to S105:
step S101: preparing graphene oxide aqueous slurry.
In this embodiment, referring to fig. 2, the preparing of the graphene oxide aqueous slurry includes steps S1011 to S1017:
step S1011: mixing sulfuric acid, flake graphite, sodium nitrate, potassium permanganate, pure water and hydrogen peroxide, and carrying out heat treatment through a heating device to obtain a first mixture.
Step S1012: and filtering and deslagging the first mixture to obtain a second mixture.
The step of filtering and deslagging the first mixture to obtain a second mixture comprises the following steps: and starting a stirring paddle in the standing tank to uniformly stir the materials in the standing tank. And transferring the material in the standing tank into a deslagging centrifuge for filtering to obtain a second mixture.
Step S1013: and refluxing the second mixture to a heating device, and carrying out heating treatment so that the second mixture is in a boiling state.
Step S1014: cooling the second mixture in the boiling state.
Step S1015: and centrifuging the cooled second mixture to obtain a third mixture.
Centrifuging the cooled second mixture to obtain a third mixture, comprising: uniformly stirring the cooled second mixture, and transferring the second mixture into a first centrifugal buffer tank; and opening the centrifugal machine of the first centrifugal buffer tank, and carrying out centrifugal treatment on the materials in the first centrifugal buffer tank to obtain a third mixture.
Step S1016: the third mixture was heat-treated with hydrochloric acid, and then washed with pure water to obtain a fourth mixture.
Step S1017: and centrifuging the fourth mixture to obtain graphene oxide aqueous slurry.
Obtaining a fourth mixture by mixing the centrifuged third mixture with hydrochloric acid and heating, and then washing with pure water; and finally, centrifuging the fourth mixture to obtain the graphene oxide aqueous slurry. Therefore, the use of pure water can be reduced, and simultaneously, the black solid of non-free manganese dioxide wrapped in the graphene oxide aqueous slurry can be converted into free divalent manganese ions, so that other metal ions can be well degraded, and the purity of the graphene oxide aqueous slurry is further improved. The interface of the graphene oxide aqueous slurry can be opened by using a reflux technique, so that the centrifugal effect of the slurry can be improved and the settling time of the slurry can be reduced. In addition, the invention can not only reduce the manganese ion content in the slurry through the high-temperature purification-separation process, but also obviously improve the filtering efficiency of the slurry compared with the currently applied vegetable membrane filtering technology, and the time for filtering one batch is about 4 hours.
Step S102: and drying the graphene oxide aqueous slurry to obtain a graphene oxide dry material.
In this embodiment, the drying the graphene oxide aqueous slurry to obtain a graphene oxide dry material includes: and placing the graphene oxide aqueous slurry in an oven to be dried for 24 to 30 hours to obtain a graphene oxide dry material, wherein the working temperature range of the oven is 70 to 75 ℃, and the oven dries the graphene oxide aqueous slurry for 24 hours at 75 ℃.
Step S103: and crushing the graphene oxide dry material to obtain the graphene oxide dry material.
In this embodiment, the crushing the graphene oxide dry material to obtain a graphene oxide dry material includes: and (3) putting the dry graphene oxide material into a grinder for grinding treatment to obtain dry graphene oxide material, wherein a screen of the grinder is a 100-mesh screen. Wherein the pulverizer is an explosion-proof and corrosion-proof pulverizer with the weight of 30-50kg/h, and is additionally provided with a 100-mesh corrosion-proof screen and a collecting bag.
Step S104: and putting the graphene oxide dry powder into a tunnel furnace for reduction stripping treatment to obtain graphene powder, wherein the tunnel furnace comprises a plurality of temperature areas, and the temperature ranges of the temperature areas are 80-950 ℃.
In this embodiment, the tunnel furnace includes: the first temperature zone, the second temperature zone, the third temperature zone, the fourth temperature zone, the fifth temperature zone, the sixth temperature zone, the seventh temperature zone, and the eighth temperature zone. The temperature of the first temperature zone is 80 ℃, the temperature of the second temperature zone is 300 ℃, the temperature of the third temperature zone is 300 ℃, the temperature of the fourth temperature zone is 500 ℃, the temperature of the fifth temperature zone is 600 ℃, the temperature of the sixth temperature zone is 800 ℃, the temperature of the seventh temperature zone is 950 ℃, and the temperature of the eighth temperature zone is 950 ℃.
The method for reducing and stripping the graphene oxide dry powder in the tunnel furnace to obtain the graphene powder comprises the following steps: and putting the graphene oxide dry powder into the tunnel furnace for reduction stripping treatment, so that the graphene oxide dry powder sequentially passes through a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, a fifth temperature zone, a sixth temperature zone, a seventh temperature zone and an eighth temperature zone to obtain graphene powder.
In addition, the tunnel furnace is a high-temperature tunnel kiln with the temperature of 100-200 kg/d and is provided with a plurality of graphite saggars, collecting bags, intelligent robot feeding devices and intelligent robot collecting devices. In the process of putting the graphene oxide dry powder into a tunnel furnace, a robot feeding device drives corresponding graphite saggers to feed materials into a first temperature zone of the tunnel furnace, each graphite sagger feeds 30g of the graphene oxide dry powder, the graphene oxide dry powder in the tunnel furnace is driven to sequentially pass through the first temperature zone, the second temperature zone, the third temperature zone, the fourth temperature zone, the fifth temperature zone, the sixth temperature zone, the seventh temperature zone and the eighth temperature zone, the graphene oxide dry powder is heated for two hours in each temperature zone, and finally the obtained graphene powder is put into a collecting bag through an intelligent robot collecting device to carry out the next procedure.
Step S105: and placing the graphene powder in a heat treatment device for heat treatment to obtain graphene slurry, wherein the working temperature range of the heat treatment device is 20-3750 ℃.
In this embodiment, the placing the graphene powder in a heat treatment device for heat treatment to obtain a graphene slurry includes: putting the graphene powder into a graphite container; and placing the graphite container in a heat treatment device for heat treatment for 1 to 50 days to obtain graphene slurry.
Referring to fig. 3, the graphite container includes: a cup 100 and a top 200. The density of the cup body 100 and the top cover 200 is more than 2g/cm3Is made of the high-density graphite. The inner wall of the cup body 100 is provided with a first internal thread at the position of the opening, the bottom of the peripheral side of the top cover 200 is provided with a first external thread, and the top cover 200 forms a closed cavity with the cup body 100 through the clearance fit of the first external thread and the first internal thread, so as to be used for placing the graphene powder.
In an alternative embodiment, the graphite container further comprises: a screw 300. The top cover 200 is provided with a through hole 201. The week side of screw rod 300 is provided with the second external screw thread, top cap 200 is located the inner wall of through-hole 201 department is provided with the second internal thread, screw rod 300 passes through the second external screw thread with the clearance fit of second internal thread with top cap 200 is fixed can dismantle the connection.
In this embodiment, first, a bottom layer of silicon carbide of 1m height is laid on the bottom in the heat treatment apparatus for sealing; then, arranging graphite containers of the graphene powder above bottom-layer carborundum, wherein the interval between adjacent graphite containers is 50-100 cm; then, laying upper-layer carborundum with the thickness of 10mm to 1000mm and the grain diameter of 1mm to 10mm for sealing; and finally, paving diamond blocks with the thickness of 100mm to 2000mm and the grain diameter of 10mm to 100mm above the upper layer of carborundum for sealing.
In an alternative embodiment, the placing the graphene powder in a heat treatment device for heat treatment to obtain a graphene slurry includes:
putting the graphene powder into a graphite container; and (3) placing the graphite container in a heat treatment device at 20 ℃ for 2 days to obtain graphene slurry. Or putting the graphene powder into a graphite container; and (3) placing the graphite container in a heat treatment device at 3000 ℃ for 20 days to obtain graphene slurry. Or putting the graphene powder into a graphite container; and (3) placing the graphite container in a heat treatment device at 3750 ℃ for 5 days to obtain graphene slurry.
Preferably, the graphene powder is put into a graphite container; and (3) placing the graphite container in a heat treatment device at 3000 ℃ for 20 days to obtain graphene slurry.
In an alternative embodiment, the mixing sulfuric acid, flake graphite, sodium nitrate, potassium permanganate, pure water, and hydrogen peroxide, and performing heat treatment by a heating device to obtain a first mixture, includes:
injecting 98% sulfuric acid of x1L into the low-temperature reaction kettle, and starting a low-temperature water cooler to circularly cool the sulfuric acid in the reaction kettle.
Starting a stirring paddle of the low-temperature reaction kettle, and adding 1000-mesh high-purity crystalline flake graphite of a1kg and sodium nitrate of b1kg into the low-temperature reaction kettle.
When the temperature in the low-temperature reaction kettle is reduced to 8-10 ℃, starting a feeder, and adding potassium permanganate into the low-temperature reaction kettle, wherein the feeding mode of the potassium permanganate is as follows: adding potassium permanganate c1-d1g each time at an interval of 3-5min, and adding potassium permanganate e1kg altogether.
After the potassium permanganate addition was complete, the reaction was carried out for at least f1 hours to give a first class a mixture.
And transferring the first a-type mixture into a medium-temperature reaction kettle, and starting a stirrer and a circulating cooling water device of the medium-temperature reaction kettle.
Adding water into the medium-temperature reaction kettle in a mode of: 0-a2L pure water, water is added at a rate of b2ml/min-c2 ml/min. d2L-e2L pure water, water is added at a rate of f2ml/min-g2 ml/min. Adding water into the residual h2L pure water at a speed of i2L/min-j2L/min, wherein the temperature in the kettle is maintained at 30-40 ℃ during the water adding process.
After the addition of water was complete, a first class b mixture was obtained.
And transferring the first b-type mixture into a high-temperature reaction kettle, starting a stirrer of the high-temperature reaction kettle, setting the temperature in the high-temperature reaction kettle to be 98 ℃, setting the oil temperature of heat conducting oil in the high-temperature reaction kettle to be 240 ℃, and heating.
After the temperature in the high-temperature reaction kettle reaches 98 ℃, keeping for at least 2 hours to obtain a first class c mixture.
After the high-temperature reaction, transferring the materials into a high-temperature cooling kettle, and adding hydrogen peroxide of a3kg after the temperature is reduced to 50-60 ℃ at the speed of: b3L/min-c 3L/min. And reacted for at least 1 hour to obtain a first mixture.
In an alternative embodiment, before said filtering deslagging said first mixture, said method further comprises:
the pure water of a4-b4L was poured into the standing tank, and the stirring paddle in the standing tank was turned on.
The first mixture was transferred to a standing tank, and after the first mixture was uniformly mixed with pure water, the stirring paddle in the standing tank was closed.
After standing for 10-12 hours, opening a drain valve of the standing tank to drain the supernatant after precipitation, wherein the water discharge amount is as follows: c4-d 4L.
In an alternative embodiment, the refluxing the second mixture to the heating device and performing the heating treatment includes:
the second mixture was stirred well.
And transferring the second mixture into a reflux reaction kettle, starting a heating device to heat, setting the temperature in the reflux reaction kettle to be 100 ℃, and setting the temperature of the electrically-heated heat conduction oil of the reflux reaction kettle to be 240 ℃.
Keeping the temperature in the kettle at 100 ℃ for at least 15 min.
The second mixture in the cooled boiling state comprising:
after holding for at least 15min, the contents of the reflux reaction vessel were transferred to a reflux cooling vessel for cooling.
Waiting for the temperature of the materials in the reflux cooling kettle to be reduced to below 50 ℃.
In an alternative embodiment, the third mixture is heated with hydrochloric acid, and then washed with pure water to obtain a fourth mixture, which comprises:
the purification reactor was filled with x2L hydrochloric acid and the purification plastic tank was filled with pure water from a5-b 5L.
Transferring the material in the first centrifugal buffer tank into a purification reaction kettle, starting a heating device for heating, setting the temperature in the purification reaction kettle to be 80 ℃, and setting the temperature of the electrically-heated heat-conducting oil to be 200 ℃.
When the temperature in the purification reaction kettle reaches 80 ℃, the temperature is maintained for at least 2 hours.
After keeping for at least 2 hours, c5L pure water is injected into the purification reaction kettle, and the purification reaction kettle is transferred into a purification plastic tank after being stirred uniformly, and is stirred in the purification plastic tank for at least 10 min.
And after standing for 10-12h, opening a drain valve of the purification plastic tank to drain the supernatant after precipitation, wherein the water discharge amount is d5-e5L, and obtaining a fourth mixture.
In an alternative embodiment, x 1: a 1: b 1: c 1: d 1: e 1: f1 ═ 80: 2: 1: 80: 100: 2.8: 0.8. b 1: a 2: b 2: c 2: d 2: e 2: f 2: g 2: h 2: i 2: j2 ═ 1: 30: 24: 26: 30: 74: 30: 32: 16: 0.5: 0.6. b 1: a 3: b 3: c3 ═ 1: 7.4: 0.3: 0.5. b 1: a 4: b 4: c 4: d4 ═ 1: 0.8: 0.84: 0.6: 0.64. b 1: x 2: a 5: b 5: c 5: d 5: e5 ═ 1: 20: 0.7: 0.8: 60: 0.5: 0.6. the slag removal centrifuge is a 45L steel-lined plastic corrosion-resistant centrifuge and is additionally provided with a filter screen of 150-200 meshes. The centrifuge of first centrifugation buffer tank is 45L steel lining plastic anticorrosive centrifuge, and subsidiary 1000 mesh filter screens. The centrifuge of the second centrifugal buffer tank is a 45L steel-lined plastic anti-corrosion centrifuge and is additionally provided with a 1000-mesh filter screen. The concentration of the hydrochloric acid is 27% -33%.
In a second aspect, the present invention provides a method for preparing an aqueous slurry of graphene oxide, comprising:
400L of 98 percent sulfuric acid is injected into the low-temperature reaction kettle, and a low-temperature water cooler is started to circularly cool the sulfuric acid in the reaction kettle. Wherein the low-temperature reaction kettle is a 500L glass lining reaction kettle, and the low-temperature water cooler is a low-temperature circulating water cooler at the temperature of minus 6 ℃.
And starting a stirring paddle of the low-temperature reaction kettle, and adding 10kg of 1000-mesh high-purity crystalline flake graphite and 5kg of sodium nitrate into the low-temperature reaction kettle.
When the temperature in the low-temperature reaction kettle is reduced to 8-10 ℃, starting a feeder, and adding potassium permanganate into the low-temperature reaction kettle, wherein the feeding mode of the potassium permanganate is as follows: each time, 500g of potassium permanganate is added, the interval is 3-5min, and 14kg of potassium permanganate is added in total.
After the potassium permanganate addition is completed, the reaction is carried out for at least 4 hours to obtain a first class a mixture.
And transferring the first a-type mixture into a medium-temperature reaction kettle, and starting a stirrer and a circulating cooling water device of the medium-temperature reaction kettle. Wherein the medium temperature reaction kettle is a 1000L glass lining reaction kettle.
Adding water into the medium-temperature reaction kettle in a mode of: 0-150L of pure water, and adding water at the speed of 120-130 ml/min; 150L-370L of pure water, and adding water at the speed of 150ml/min-160 ml/min; adding water into the rest 80L of pure water at a speed of 2.5-3L/min, wherein the temperature in the kettle is maintained at 30-40 ℃ during the water adding process.
After the addition of water was complete, a first class b mixture was obtained.
Transferring the first b-type mixture into a high-temperature reaction kettle, starting a stirrer of the high-temperature reaction kettle, setting the temperature in the high-temperature reaction kettle to be 98 ℃, setting the oil temperature of heat conducting oil in the high-temperature reaction kettle to be 240 ℃, and heating;
after the temperature in the high-temperature reaction kettle reaches 98 ℃, keeping for at least 2 hours to obtain a first class c mixture.
After the high-temperature reaction, transferring the materials into a high-temperature cooling kettle, and adding 37kg of hydrogen peroxide after the temperature is reduced to 50-60 ℃ at the speed of: 1.5L/min-2.5L/min. And reacted for at least 1 hour to obtain a first mixture. Wherein the high-temperature reaction kettle is a 1000L steel-lined polytetrafluoroethylene electric heating reaction kettle, the high-temperature cooling kettle is a 1000L glass lining reaction kettle, and the hydrogen peroxide is industrial hydrogen peroxide with the concentration of 27%.
4-4.2L of pure water is injected into the standing tank, and a stirring paddle in the standing tank is started. The standing tank is a phi 2000 x 2000PVC cylindrical plastic tank.
The first mixture was transferred to a standing tank, and after the first mixture was uniformly mixed with pure water, the stirring paddle in the standing tank was closed.
After standing for 10-12 hours, opening a drain valve of the standing tank to drain the supernatant after precipitation, wherein the water discharge amount is as follows: 3-3.2L.
And starting a stirring paddle in the standing tank to uniformly stir the materials in the standing tank.
And transferring the material in the standing tank into a deslagging centrifuge for filtering to obtain a second mixture.
The second mixture was flowed into a cylindrical plastic tank of phi 2000 x 2000PVC and stirred uniformly within the cylindrical plastic tank of phi 2000 x 2000 PVC.
And transferring the second mixture into a reflux reaction kettle, starting a heating device to heat, setting the temperature in the reflux reaction kettle to be 100 ℃, and setting the temperature of the electrically-heated heat conduction oil of the reflux reaction kettle to be 240 ℃.
Keeping the temperature in the kettle at 100 ℃ for at least 15 min.
After holding for at least 15min, the contents of the reflux reaction vessel were transferred to a reflux cooling vessel for cooling.
Waiting for the temperature of the materials in the reflux cooling kettle to be reduced to below 50 ℃.
The cooled second mixture was transferred to a phi 2000 x 2000PVC cylindrical plastic tank and the cooled second mixture was stirred well and transferred to a first centrifugal buffer tank.
And opening the centrifugal machine of the first centrifugal buffer tank, and carrying out centrifugal treatment on the materials in the first centrifugal buffer tank to obtain a third mixture.
100L of hydrochloric acid is injected into the purification reaction kettle, and 3.5-4.0L of pure water is injected into the purification plastic tank.
Transferring the material in the first centrifugal buffer tank into a purification reaction kettle through a screw feeder, starting a heating device for heating, setting the temperature in the purification reaction kettle to be 80 ℃, and setting the temperature of electrically heated heat conduction oil to be 200 ℃. Wherein, the purification reaction kettle is a 500L steel-lined polytetrafluoroethylene electrical heating reflux reaction kettle.
When the temperature in the purification reaction kettle reaches 80 ℃, the temperature is maintained for at least 2 hours.
After keeping for at least 2 hours, 300L of pure water is injected into the purification reaction kettle, and the mixture is transferred into a purification plastic tank after being stirred uniformly and is stirred in the purification plastic tank for at least 10 min. Wherein, the purification plastic tank is a phi 2000 x 2000PVC cylindrical plastic tank.
Standing for 10-12h, opening a drain valve of the purification plastic tank to drain the supernatant after precipitation, wherein the water discharge amount is 2.5-3L, and obtaining a fourth mixture.
The fourth mixture was stirred well.
The well stirred fourth mixture was transferred to a second centrifuge buffer tank.
And opening the centrifuge of the second centrifugal buffer tank, and centrifuging the material in the second centrifugal buffer tank to obtain the graphene oxide aqueous slurry.
In a third aspect, with reference to fig. 4, the present invention provides an apparatus for preparing graphene slurry, which is applied to the method for preparing graphene slurry, and the apparatus includes the following components: the device comprises a low-temperature reaction kettle, a low-temperature water cooler, a medium-temperature reaction kettle, a circulating cooling water device, a water adding machine, a high-temperature reaction kettle, a high-temperature cooling kettle, a standing tank, a deslagging centrifugal machine, a backflow reaction kettle, a backflow cooling kettle, a first centrifugal buffer tank, a purification reaction kettle, a purification plastic tank, a second centrifugal buffer tank, an oven, a pulverizer, a tunnel melting furnace and a heat treatment device.
The graphite container is arranged in the heat treatment device.
The low-temperature water cooler is connected with the low-temperature reaction kettle, the low-temperature reaction kettle is connected with the medium-temperature reaction kettle, the circulating cooling water device and the water adding machine are connected with the medium-temperature reaction kettle, the medium-temperature reaction kettle and the high-temperature cooling kettle are connected with the high-temperature reaction kettle, the standing tank is connected with the deslagging centrifuge, the deslagging centrifuge is connected with the reflux reaction kettle, the reflux reaction kettle is connected with the reflux cooling kettle, the reflux cooling kettle is connected with the first centrifugal buffer tank, the first centrifugal buffer tank is connected with the purification reaction kettle, the purification reaction kettle is connected with the purification plastic tank, the purification plastic tank is connected with the second centrifugal buffer tank, the second centrifugal buffer tank is connected with the oven, and the oven is connected with the pulverizer, the pulverizer is connected with the tunnel furnace, and the tunnel furnace is connected with the heat treatment device. In this embodiment, the above connection mode can be understood as a material conveying path. The specific connection mode between various devices in the equipment can be direct connection, or can be transmission through a feeding mechanism, such as a conveyor belt mechanism and a spiral feeder, or the two devices are mutually separated and are manually carried, and the invention is not limited too much.
According to the preparation method and the equipment of the graphene slurry provided by the embodiment of the invention, after the graphene oxide aqueous slurry is dried, crushed and reduced and stripped, the graphene oxide aqueous slurry is heated in a heat treatment device, particularly at 3000 ℃, the graphene structure can be reformed, a large amount of oxygen-containing functional groups are removed, and the thin-layer graphene material with a unique structure is obtained.
Specific parameters of the graphene slurry obtained by the heat treatment device in the invention are shown in table one.
It can be known from the table one that, compared with a common oxidation-reduction method and a mechanical stripping process, the method provided by the invention can greatly reduce a large amount of sulfur elements and a large amount of overproof elements such as iron, cobalt, nickel, manganese, potassium, calcium and the like in the graphene, so that the purity of the graphene is further improved, and the graphene slurry obtained by the method provided by the invention is applied to a battery, so that the service life of the battery can be prolonged.
With reference to fig. 5, 6, and 7, scanning electron microscope tests performed on the graphene slurry obtained by the present invention and graphene slurries obtained by the prior art, the common redox method, and the mechanical exfoliation method respectively show that the graphene slurry obtained by the mechanical exfoliation method has a thicker lamella, and the graphene slurry obtained by the common redox method and the graphene slurry obtained by the present invention have a thinner lamella. Fig. 5 is a TEM image of graphene slurry prepared by a conventional general redox method; fig. 6 is a TEM image of graphene slurry prepared by a conventional mechanical exfoliation method; fig. 7 is a TEM image of graphene slurry prepared by the present invention.
With reference to fig. 8, 9, and 10, raman tests performed on the graphene slurry obtained by the present invention and the graphene slurries obtained by the conventional oxidation-reduction method and the mechanical exfoliation method respectively show that the graphene slurry obtained by the conventional oxidation-reduction method has a large defect, such as low conductivity, while the graphene slurry obtained by the mechanical exfoliation method and the graphene slurry obtained by the present invention have substantially no defect. Fig. 8 is a raman test chart of graphene slurry prepared by a conventional general redox method; fig. 9 is a raman test chart of graphene slurry prepared by a conventional mechanical exfoliation method; fig. 10 is a raman test chart of the graphene slurry prepared according to the present invention; in the figure, the G peak refers to a graphene characteristic peak of the graphene slurry, the D peak refers to a graphene defect peak of the graphene slurry, and the 2D peak refers to a stacking mode between graphene carbon atom layers of the graphene slurry.
With reference to fig. 11, it can be seen that when the graphene slurry obtained by the present invention and the graphene slurry obtained by the prior art, a common oxidation-reduction method and a mechanical exfoliation method are both used for preparing corresponding graphene conductive agent slurry for a high-rate discharge performance test, the conductive agent slurry prepared by using the graphene slurry obtained by the present invention is added to the positive electrode of a battery, and the high-rate discharge advantage of the conductive agent slurry is significantly higher than that of the other two materials.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (13)
1. A preparation method of graphene slurry is characterized by comprising the following steps:
preparing graphene oxide aqueous slurry;
drying the graphene oxide aqueous slurry to obtain a graphene oxide dry material;
crushing the graphene oxide dry material to obtain a graphene oxide dry material;
putting the graphene oxide dry powder into a tunnel furnace for reduction stripping treatment to obtain graphene powder, wherein the tunnel furnace comprises a plurality of temperature areas, and the temperature ranges of the temperature areas are 80-950 ℃;
and placing the graphene powder in a heat treatment device for heat treatment to obtain graphene slurry, wherein the working temperature range of the heat treatment device is 20-3750 ℃.
2. The method for preparing graphene paste according to claim 1, wherein the preparing of the graphene oxide aqueous paste comprises:
mixing sulfuric acid, flake graphite, sodium nitrate, potassium permanganate, pure water and hydrogen peroxide, and performing heat treatment through a heating device to obtain a first mixture;
filtering and deslagging the first mixture to obtain a second mixture;
refluxing the second mixture to a heating device, and carrying out heating treatment to enable the second mixture to be in a boiling state;
cooling the second mixture in the boiling state;
centrifuging the cooled second mixture to obtain a third mixture;
heating the third mixture and hydrochloric acid, and then washing with pure water to obtain a fourth mixture;
and centrifuging the fourth mixture to obtain graphene oxide aqueous slurry.
3. The method for preparing graphene slurry according to claim 2, wherein the step of mixing sulfuric acid, flake graphite, sodium nitrate, potassium permanganate, pure water and hydrogen peroxide and performing heat treatment by using a heating device to obtain a first mixture comprises:
injecting 98 percent sulfuric acid of x1L into the low-temperature reaction kettle, and starting a low-temperature water cooler to circularly cool the sulfuric acid in the reaction kettle;
starting a stirring paddle of the low-temperature reaction kettle, and adding a1kg of 1000-mesh high-purity crystalline flake graphite and b1kg of sodium nitrate into the low-temperature reaction kettle;
when the temperature in the low-temperature reaction kettle is reduced to 8-10 ℃, starting a feeder, and adding potassium permanganate into the low-temperature reaction kettle, wherein the feeding mode of the potassium permanganate is as follows: c1-d1g of potassium permanganate are added each time, the interval is 3-5min, and e1kg of potassium permanganate are added together;
after the potassium permanganate is added, reacting for at least f1 hours to obtain a first a-class mixture;
transferring the first a-type mixture into a medium-temperature reaction kettle, and starting a stirrer and a circulating cooling water device of the medium-temperature reaction kettle;
adding water into the medium-temperature reaction kettle in a mode of: 0-a2L pure water, adding water at the speed of b2ml/min-c2 ml/min; d2L-e2L pure water, adding water at the speed of f2ml/min-g2 ml/min; adding water into the residual h2L pure water at a speed of i2L/min-j2L/min, wherein the temperature in the kettle is maintained at 30-40 ℃ in the water adding process;
after the water is added, a first b-type mixture is obtained;
transferring the first b-type mixture into a high-temperature reaction kettle, starting a stirrer of the high-temperature reaction kettle, setting the temperature in the high-temperature reaction kettle to be 98 ℃, setting the oil temperature of heat conducting oil in the high-temperature reaction kettle to be 240 ℃, and heating;
keeping the temperature in the high-temperature reaction kettle for at least 2 hours after the temperature in the high-temperature reaction kettle reaches 98 ℃ to obtain a first c-type mixture;
after the high-temperature reaction, transferring the materials into a high-temperature cooling kettle, and adding a3kg of hydrogen peroxide after the temperature is reduced to 50-60 ℃ at the speed of: b3L/min-c 3L/min; and reacted for at least 1 hour to obtain a first mixture.
4. The method for preparing graphene slurry according to claim 3, wherein before the filtering and deslagging the first mixture, the method further comprises:
injecting a4-b4L of pure water into the standing tank, and starting a stirring paddle in the standing tank;
transferring the first mixture into a standing tank, and closing a stirring paddle in the standing tank after the first mixture is uniformly mixed with the pure water;
after standing for 10-12 hours, opening a drain valve of the standing tank to drain the supernatant after precipitation, wherein the water discharge amount is as follows: c4-d 4L.
5. The method for preparing graphene paste according to claim 4, wherein the refluxing the second mixture to a heating device and performing a heating treatment comprises:
stirring the second mixture uniformly;
transferring the second mixture into a reflux reaction kettle, starting a heating device for heating, setting the temperature in the reflux reaction kettle to be 100 ℃, and setting the temperature of the electrically-heated heat conduction oil of the reflux reaction kettle to be 240 ℃;
keeping the temperature in the kettle at 100 ℃ for at least 15 min;
the second mixture in the cooled boiling state comprising:
after keeping for at least 15min, transferring the materials in the reflux reaction kettle into a reflux cooling kettle for cooling;
waiting for the temperature of the materials in the reflux cooling kettle to be reduced to below 50 ℃.
6. The method for preparing graphene slurry according to claim 5, wherein the third mixture is subjected to heating treatment with hydrochloric acid and then washed with pure water to obtain a fourth mixture, and the fourth mixture comprises:
injecting x2L hydrochloric acid into the purification reaction kettle, and injecting a5-b5L pure water into the purification plastic tank;
transferring the material in the first centrifugal buffer tank into a purification reaction kettle, starting a heating device for heating, setting the temperature in the purification reaction kettle to be 80 ℃, and setting the temperature of electrically heated heat conduction oil to be 200 ℃;
keeping the temperature in the purification reaction kettle for at least 2 hours when the temperature reaches 80 ℃;
after keeping for at least 2 hours, c5L of pure water is injected into the purification reaction kettle, the mixture is transferred into a purification plastic tank after being uniformly stirred, and the mixture is stirred in the purification plastic tank for at least 10 min;
and standing for 10-12 hours, opening a drain valve of the purification plastic tank to drain the supernatant after precipitation, wherein the water discharge amount is d5-e5L, and obtaining a fourth mixture.
7. The method for preparing graphene paste according to claim 6, wherein the ratio of x 1: a 1: b 1: c 1: d 1: e 1: f1 ═ 80: 2: 1: 80: 100: 2.8: 0.8;
b1：a2：b2：c2：d2：e2：f2：g2：h2：i2：j2＝1：30：24：26：30：74：30：32：16：0.5：0.6；
b1：a3：b3：c3＝1：7.4：0.3：0.5；
b1：a4：b4：c4：d4＝1：0.8：0.84：0.6：0.64；
b1：x2：a5：b5：c5：d5：e5＝1：20：0.7：0.8：60：0.5：0.6；
the slag removal centrifugal machine is a 45L steel-lined plastic corrosion-resistant centrifugal machine and is additionally provided with a filter screen of 150-200 meshes;
the centrifuge of the second centrifugal buffer tank is a 45L steel-lined plastic anti-corrosion centrifuge and is additionally provided with a 1000-mesh filter screen;
the concentration of the hydrochloric acid is 27% -33%.
8. The preparation method of graphene slurry according to claim 1, wherein the drying treatment of the graphene oxide aqueous slurry to obtain a graphene oxide dry material comprises:
and placing the graphene oxide aqueous slurry in an oven to be dried for 24 to 30 hours to obtain a graphene oxide dry material, wherein the working temperature range of the oven is 70 to 75 ℃.
9. The preparation method of graphene slurry according to claim 1, wherein the crushing of the graphene oxide dry material to obtain a graphene oxide dry material comprises:
and (3) putting the dry graphene oxide material into a grinder for grinding treatment to obtain dry graphene oxide material, wherein a screen of the grinder is a 100-mesh screen.
10. The method for preparing graphene paste according to claim 1, wherein the tunnel furnace includes: a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, a fifth temperature zone, a sixth temperature zone, a seventh temperature zone, and an eighth temperature zone;
the temperature of the first temperature zone is 80 ℃, the temperature of the second temperature zone is 300 ℃, the temperature of the third temperature zone is 300 ℃, the temperature of the fourth temperature zone is 500 ℃, the temperature of the fifth temperature zone is 600 ℃, the temperature of the sixth temperature zone is 800 ℃, the temperature of the seventh temperature zone is 950 ℃, and the temperature of the eighth temperature zone is 950 ℃;
the method for reducing and stripping the graphene oxide dry powder in the tunnel furnace to obtain the graphene powder comprises the following steps:
and putting the graphene oxide dry powder into the tunnel furnace for reduction stripping treatment, so that the graphene oxide dry powder sequentially passes through a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, a fifth temperature zone, a sixth temperature zone, a seventh temperature zone and an eighth temperature zone to obtain graphene powder.
11. The method for preparing graphene slurry according to claim 1, wherein the step of placing the graphene powder in a heat treatment device for heat treatment to obtain graphene slurry comprises:
putting the graphene powder into a graphite container;
placing the graphite container in a heat treatment device for heat treatment for 1 to 50 days to obtain graphene slurry;
the graphite container includes: a cup body and a top cover;
the inner wall of the cup body is provided with a first internal thread at a position located at the opening, a first external thread is arranged on the periphery of the top cover, and the top cover is used for placing the graphene powder through clearance fit of the first external thread and the first internal thread and formation of a closed cavity by the cup body.
12. The method of preparing graphene slurry according to claim 11, wherein the graphite container further comprises: a screw;
the top cover is provided with a through hole;
the week side of screw rod is provided with the second external screw thread, the top cap is located the inner wall of through-hole department is provided with the second internal thread, the screw rod passes through the second external screw thread with the internal screw thread clearance fit of second with the top cap is fixed can dismantle the connection.
13. A graphene slurry preparation apparatus, which is applied to the graphene slurry preparation method according to any one of claims 1 to 12, wherein the apparatus comprises the low-temperature reaction kettle, the low-temperature water cooler, the medium-temperature reaction kettle, the circulating cooling water device, the water feeder, the high-temperature reaction kettle, the high-temperature cooling kettle, the standing tank, the reflux reaction kettle, the reflux cooling kettle, the purification reaction kettle, the purification plastic tank, the second centrifugal buffer tank, the oven, the pulverizer, the tunnel furnace and the heat treatment device according to claims 1 to 12;
the graphite container is arranged in the heat treatment device;
the low-temperature water cooler with low temperature reation kettle connects, low temperature reation kettle is connected with medium temperature reation kettle, recirculated cooling water device with add the water machine all with medium temperature reation kettle connects, medium temperature reation kettle with high temperature cooling cauldron all with high temperature reation kettle connects, the jar of stewing all with high temperature cooling cauldron is connected, the jar of stewing with reflux reation kettle connects, reflux reation kettle with reflux cooling cauldron connects, reflux cooling cauldron with purification reation kettle connects, purification reation kettle with purification plastic tank connects, purification plastic tank with the second centrifugation buffer tank is connected.
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