CN115109568A - Graphene heat adding/dissipating composite material for new energy automobile lithium battery and preparation method thereof - Google Patents
Graphene heat adding/dissipating composite material for new energy automobile lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene heat adding/dissipating composite material for a lithium battery of a new energy automobile, which comprises the following steps: s1: taking carbon fiber bundles, and carrying out cobalt film deposition; s2: detecting the magnetism of the cobalt film deposition end; s3: placing the carbon fiber bundle in a copper hydroxide/graphene oxide suspension, and performing ultrasonic dispersion to obtain a mixed solution; s4: performing multi-stage directional arrangement on the carbon fiber bundles in the mixed solution through a magnetic attraction arrangement device; s5: the mixed solution is subjected to a bidirectional freezing gradient and freeze drying process to form a carbon fiber bundle-copper hydroxide/graphene oxide heat conduction material; s6: the carbon fiber bundles and the copper-doped graphene heat conduction material are formed by reduction, the carbon fiber bundles in the mixed solution are highly arranged in an oriented manner through multi-stage magnetic attraction arrangement, and the heat conduction coefficient of the product can be improved by more than 30%.
Description
Technical Field
The invention belongs to the technical field of new energy electric automobile accessories, and particularly relates to a heating and heat dissipation two-in-one graphene composite material for a lithium battery pack of a new energy automobile and a preparation method of the graphene composite material.
Background
The lithium battery is an energy storage device commonly used by new energy electric vehicles in the prior art, the lithium ion battery technology can provide higher (3 times) energy density than that of a lead-acid chemical battery, and the size, the weight and the like of the lithium ion battery are reduced, but in the operation process of the system, a motor can drive a motor in a stop state to reach 3000r/min within hundreds of milliseconds under the driving of a battery pack, so that the motor is driven to re-ignite, the battery pack is in a high-rate discharge state, the heat productivity is very high in the working process, the discharge capacity of the battery pack can be directly influenced by overhigh temperature, the stable operation of the whole system is reduced, meanwhile, the thermal runaway of the battery pack can be caused by overhigh temperature, and the probability of ignition and explosion can be increased, so that the heat dissipation of the lithium battery is needed; in addition, the low-temperature performance of the lithium battery is slightly inferior to that of batteries of other technical systems, low temperature has influence on the anode and cathode of lithium iron phosphate, electrolyte and the like, the electron conductivity of the anode of the lithium iron phosphate is poor, and polarization is easy to generate in a low-temperature environment, so that the capacity of the battery is reduced, and therefore, the temperature of a battery pack needs to be increased in the low-temperature environment; thus, there is a need for a high performance heat conductive material for heating/cooling lithium batteries.
At present, people are actively searching for new high-performance heat conduction materials, and taking graphene as a representative, the two-dimensional crystal structure of a novel two-dimensional crystal material with single atom thickness and unique physical properties become the research focus in recent years. Graphene has excellent thermal conductivity (5000W/(m.K)) and extraordinary specific surface area (2630m2/g), can be applied to solid surfaces and other good technological properties, and is an ideal heat dissipation material. However, as to the application problem of graphene in heat dissipation, research on the preparation method and application technique of graphene is in a rapid development stage, and how to fully and reasonably utilize the high thermal conductivity of graphene is still a technical problem to be solved in the field of heat dissipation successfully. Due to the fact that the graphene is of a two-dimensional structure, heat dissipated by the battery surface can be diffused to surrounding materials only in a horizontal mode in a heat dissipation mode, and the heat dissipation effect of the materials is weakened to a certain extent; in addition, since graphene has a very large specific surface area, it is easy to agglomerate, and when graphene agglomerates and a composite material are polymerized during preparation, the performance of the material is greatly reduced.
Disclosure of Invention
The invention aims to provide a graphene heat-dissipation composite material for a lithium battery of a new energy automobile and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problem, the technical scheme of the invention is as follows:
the preparation method of the graphene heat addition/dissipation composite material for the lithium battery of the new energy automobile comprises the following steps:
s1: taking a carbon fiber bundle, wrapping a layer of aluminum foil on the carbon fiber bundle and exposing an exposed end, and performing cobalt film deposition on the exposed end by adopting pulse laser vapor deposition equipment;
s2: detecting the magnetism of the cobalt film deposition end on the carbon fiber bundle; if the magnetism is not enough, the cobalt film deposition operation is performed again, and if the magnetism meets the requirement, the step S3 is executed;
s3: preparing a copper hydroxide/graphene oxide suspension; placing the carbon fiber bundle obtained in the step S2 in a copper hydroxide/graphene oxide suspension, and performing ultrasonic dispersion to obtain a mixed solution;
s4: performing multi-stage directional arrangement on the carbon fiber bundles in the mixed solution through a magnetic attraction arrangement device; after the carbon fiber bundles are arranged in an oriented way, the top ends of the carbon fiber bundles penetrate out of the top surface of the mixed liquid;
s5: the mixed solution is subjected to a bidirectional freezing gradient and freeze drying process to form a carbon fiber bundle-copper hydroxide/graphene oxide heat conduction material;
s6: and reducing the carbon fiber bundle-copper-doped graphene oxide heat conduction material at the heating temperature of 1000 ℃ under the argon protection environment to form the carbon fiber bundle-copper-doped graphene oxide heat conduction material.
Preferably, the length of the exposed end of the carbon fiber bundle is 1.5 mm;
preferably, in step S3, the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 16;
preferably, the method for preparing the copper hydroxide/graphene oxide suspension comprises the following steps:
dissolving graphene oxide in water, performing ultrasonic dispersion to obtain a graphene oxide suspension for later use, dripping sodium hydroxide into a copper nitrate solution to obtain liquid copper hydroxide, adding the copper hydroxide dissolved in the water into the graphene oxide suspension under a stirring condition, performing ultrasonic oscillation, and embedding the copper hydroxide into the graphene oxide through a hydrogen bond; and obtaining the copper hydroxide/graphene oxide suspension.
Preferably, the molar ratio of the graphene oxide to the copper element is 1: 1.6;
according to the invention, copper oxide/graphene oxide particles are adsorbed on the carbon fiber material, and graphene is uniformly adsorbed on the carbon fiber material after reduction, so that the excellent heat conductivity of the graphene is matched with the continuous heat conduction path of the carbon fiber, and the heat conductivity of the material is greatly improved; and the copper hydroxide modified graphene material is adopted, so that the graphene oxide has better hydrophilic performance and is more uniformly dispersed and adsorbed on the carbon fiber material.
Preferably, the magnetic attraction arrangement device comprises a plurality of electromagnet units which are in telescopic sleeve connection, each electromagnet unit forms a working area, and the outer container is arranged on the working area; the outer contour of the electromagnet unit is superposed with the outer edge of the working area, and each electromagnet unit is connected with an independent magnetic switch control system to form a multi-stage magnetic attraction arrangement area;
the method for directionally arranging the carbon fiber bundles in the mixed liquid by the magnetic attraction arrangement device comprises the following substeps:
s41: starting the electromagnet units positioned on the periphery, and adsorbing the carbon fiber bundles on the outer ring of the bottom surface of the container through magnetic force by the electromagnet units on the periphery;
s42: stirring the mixed solution to ensure that the carbon fiber bundles in the mixed solution which are insufficiently magnetically absorbed are separated from the outer ring of the inner bottom surface of the container;
s43: lifting the electromagnet unit in the middle to be on the same plane with the electromagnet units on the periphery, and opening the electromagnet units to enable the separated carbon fiber bundles to be adsorbed at the center of the inner bottom surface of the container again;
s44: and continuously stirring the mixed solution to ensure that the carbon fiber bundles with insufficient magnetic attraction in the mixed solution are separated from the inner bottom surface of the container and then are arranged and adsorbed again.
According to the invention, the carbon fiber bundles in the mixed solution are arranged in a highly directional array in advance through the magnetic attraction arrangement device, so that the heat conduction paths of the heat conduction materials from the bottom to the top are continuous, and the heat conduction performance of the material is greatly improved.
Preferably, the magnetic attraction arrangement device comprises a first-level electromagnet unit, a second-level electromagnet unit and a third-level electromagnet unit which are formed in a sleeved arrangement mode, each electromagnet unit correspondingly forms a first-level magnetic attraction arrangement area, a second-level magnetic attraction arrangement area and a third-level magnetic attraction arrangement area from inside to outside on the bottom surface of the container for containing the mixed liquid, and the method for directionally arranging the carbon fiber bundles comprises the following substeps:
s411: starting the three-stage electromagnet unit, and forming magnetic force in the three-stage magnetic attraction arrangement area to adsorb the carbon fiber bundles in the three-stage magnetic attraction arrangement area on the inner bottom surface of the container;
s412: stirring the mixed solution to ensure that the carbon fiber bundles in the mixed solution with insufficient magnetic attraction are separated from the three-stage magnetic attraction arrangement area on the inner bottom surface of the container;
s413: starting the second-stage electromagnet unit, ascending to the same plane as the third-stage electromagnet unit, and forming magnetic force in the second-stage magnetic attraction arrangement area to adsorb the separated carbon fiber bundles in the second-stage magnetic attraction arrangement area on the inner bottom surface of the container;
s414: stirring the mixed solution to enable the carbon fiber bundles in the mixed solution with insufficient magnetic attraction to be separated from the three-stage magnetic attraction arrangement area and the second-stage arrangement area on the inner bottom surface of the container;
s415: and starting the primary electromagnet unit, ascending to the same plane with the secondary electromagnet unit, forming magnetic force in the primary magnetic attraction arrangement area, and adsorbing the separated carbon fiber bundles in the primary magnetic attraction arrangement area on the inner bottom surface of the container so as to form a uniformly distributed carbon fiber bundle array.
Preferably, the three-level electromagnet unit comprises an outer ring iron core, the outer ring iron core is of a hollow structure, a first coil winding area is formed on the surface of the outer ring iron core, a first coil is wound in the first coil winding area, and a first shell is arranged outside the first coil winding area; the secondary electromagnet unit comprises an inner ring iron core, the inner ring iron core is of a hollow structure, a second coil winding area is formed on the surface of the inner ring iron core, a second coil is wound in the second coil winding area, and a second shell is arranged outside the second coil winding area; the second shell is slidably connected in the outer ring iron core through a first sliding assembly; the first-stage electromagnet unit comprises a central iron core, a third coil winding area is formed on the surface of the central iron core, a third coil is wound in the third coil winding area, and a third shell is arranged outside the third coil winding area; the third shell is slidably connected in the second shell through a second sliding assembly; the first coil, the second coil and the third coil are connected with the magnetic switch control system.
Preferably, the magnetic switch control system comprises a power supply, a switch, a transformer and a diode which are electrically connected with the electromagnet unit, and the diode is arranged on the circuit of the electromagnet, so that after the power supply is powered off, induced current can be blocked by the diode, and the magnetism of the electromagnet disappears immediately, thereby improving the demagnetization efficiency of the electromagnet and avoiding influencing the next working cycle.
The invention also aims to provide the graphene heat adding/dissipating composite material prepared by the method.
According to the technical scheme, the invention has the beneficial effects that:
according to the invention, the carbon fiber bundles in the mixed liquid are highly and directionally arranged through the multi-stage magnetic attraction arrangement, so that a continuous heat conduction path is formed from the bottom to the top of the heat conduction material, and the carbon fiber bundles are more stable and uniform compared with the existing directional arrangement technology in the multi-stage magnetic attraction arrangement mode, and the heat conduction coefficient of the product can be improved by more than 30%; the heat conduction performance of the graphene heat conduction material is greatly improved; in addition, compared with the graphene heat conduction material prepared from unmodified graphene oxide, the graphene heat conduction material prepared from the copper hydroxide modified graphene oxide has the advantages that the graphene oxide is better in hydrophilic performance and more uniform in dispersion, the graphene oxide can be adsorbed on the surface of carbon fibers more uniformly, and the heat conduction coefficient of a product after reduction can be improved by more than 45%.
Drawings
FIG. 1 is a schematic view of a multi-stage magnetic attraction arrangement area according to embodiment 1 of the present invention;
FIG. 2 is a cross-sectional view of a magnetic attraction alignment device of the present invention;
Detailed Description
As shown in fig. 1-2, the present invention will be explained in detail by specific examples in order to further explain the technical solution of the present invention.
Example 1
The preparation method of the graphene heat addition/dissipation composite material for the lithium battery of the new energy automobile comprises the following steps:
s1: taking a carbon fiber bundle, cutting the carbon fiber bundle into a required size by using a cutter, wrapping a layer of aluminum foil on the carbon fiber bundle and exposing an exposed end, taking the exposed end as a substrate with the exposed end facing upwards, taking high-purity cobalt (99%) as a target, and performing cobalt film deposition on the exposed end by using pulsed laser vapor deposition equipment; in this embodiment, the pulse frequency is 4Hz, and the background air pressure is 5 Pa; the length of the exposed end of the carbon fiber bundle is 0.5 mm;
s2: adopting a magnet to carry out magnetic attraction on the carbon fiber bundle to detect whether the exposed end is uniformly deposited with the cobalt film or not, or adopting an amplifying device to detect the color of the exposed end, wherein the exposed end deposited with the cobalt film is silver gray to detect whether the cobalt film is uniformly deposited or not, and entering step S3 after the detection is finished;
s3: preparing a copper hydroxide/graphene oxide suspension: dissolving graphene oxide in water, performing ultrasonic dispersion to obtain a graphene oxide suspension for later use, and dripping sodium hydroxide into a copper nitrate solution, wherein the molar ratio of the graphene oxide to the copper nitrate solution is 1: 1, reacting for 45min to obtain liquid copper hydroxide, adding the copper hydroxide dissolved in water into the graphene oxide suspension under the stirring condition, and ensuring that the molar ratio of the graphene oxide to the copper element is 1: 1.2, stirring at room temperature for 24 hours, and ultrasonically oscillating; obtaining copper hydroxide/graphene oxide suspension; the graphene oxide contains a large amount of polar oxygen-containing functional groups, has the characteristics of good hydrophilicity and mechanical properties, and is combined with copper hydroxide containing hydroxyl groups through hydrogen bonds, so that the hydrophilicity of the graphene oxide is improved, and the dispersion is more stable. Placing the carbon fiber bundle obtained in the step S2 in a copper hydroxide/graphene oxide suspension, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 11;
s4: adding the mixed solution into a bidirectional freezing mould, and performing multi-stage directional arrangement on the carbon fiber bundles in the mixed solution through a magnetic attraction arrangement device; after the carbon fiber bundles are arranged in an oriented way, the top ends of the carbon fiber bundles penetrate out of the top surface of the mixed liquid;
the magnetic attraction arrangement device comprises a primary electromagnet unit, a secondary electromagnet unit and a tertiary electromagnet unit which are formed in a sleeved arrangement mode, each electromagnet unit correspondingly forms a primary magnetic attraction arrangement area, a secondary magnetic attraction arrangement area and a tertiary magnetic attraction arrangement area on the bottom surface of a container for containing mixed liquid from inside to outside, and the method for directionally arranging the carbon fiber bundles comprises the following substeps: s411: starting the three-stage electromagnet unit, forming magnetic force in the three-stage magnetic absorption arrangement area to absorb the carbon fiber bundles in the three-stage magnetic absorption arrangement area on the inner bottom surface of the container, wherein the pressurized voltage is 14.5V, and the duration is 10s, and then carrying out the next step; s412: stirring the mixed solution to ensure that the carbon fiber bundles in the mixed solution with insufficient magnetic attraction are separated from the three-stage magnetic attraction arrangement area on the inner bottom surface of the container; s413: starting the second-stage electromagnet unit, ascending to the same plane as the third-stage electromagnet unit, and forming magnetic force in the second-stage magnetic attraction arrangement area to adsorb the separated carbon fiber bundles in the second-stage magnetic attraction arrangement area on the inner bottom surface of the container; at this time, the voltage for pressurization was 15.5V, and the duration was 10s, and then the next step was performed; s414: stirring the mixed solution to enable the carbon fiber bundles in the mixed solution with insufficient magnetic attraction to be separated from the three-stage magnetic attraction arrangement area and the second-stage arrangement area on the inner bottom surface of the container; s415: and starting the primary electromagnet unit, ascending to the same plane as the primary electromagnet unit, forming magnetic force in the primary magnetic attraction arrangement area, and adsorbing the separated carbon fiber bundles in the primary magnetic attraction arrangement area on the inner bottom surface of the container, wherein the pressurizing voltage is 16.5V, the duration is 10S, and then forming a uniformly distributed carbon fiber bundle array to perform step S5.
S5: the mixed solution is subjected to a bidirectional freezing gradient and freeze drying process to form a carbon fiber bundle-copper hydroxide/graphene oxide heat conduction material; the specific method comprises the following steps: pouring the mixture into a bidirectional freezing mould, freezing for 6 hours at-70 ℃, and then performing vacuum freeze drying (the vacuum degree is 0.1-2 Pa, and the drying time is 72 hours) to obtain the product;
s6: and under the argon protection environment, heating at 1000 ℃ for 7h, and reducing the carbon fiber bundle-copper-doped graphene oxide heat conduction material to form the carbon fiber bundle-copper-doped graphene oxide heat conduction material.
Specifically, the method comprises the following steps: the three-level electromagnet unit comprises an outer ring iron core 100 which is of a hollow structure, a first coil winding area 101 is formed on the surface of the outer ring iron core, a first coil 102 is wound in the first coil winding area, and a first shell 103 is arranged outside the first coil winding area; the secondary electromagnet unit comprises an inner ring iron core 104 which is of a hollow structure, a second coil winding area 105 is formed on the surface of the inner ring iron core, a second coil 106 is wound in the second coil winding area, and a second shell 107 is arranged outside the second coil winding area; the second housing is slidably connected within the outer ring core by a first slide assembly (first cylinder 108); the primary electromagnet unit comprises a central iron core 109, a third coil winding area 110 is formed on the surface of the central iron core, a third coil 111 is wound in the third coil winding area, and a third shell 112 is arranged outside the third coil winding area; the third shell is slidably connected in the second shell through a second sliding assembly (a second air cylinder 113); the secondary electromagnet unit and the electromagnet unit are respectively pushed to move up and down by the first cylinder and the second cylinder, wherein the first shell, the second shell and the third shell are made of ceramic materials; the first coil, the second coil and the third coil are connected with the magnetic switch control system. The switch control system is formed by assembling commercially available components, and details are not omitted herein.
Example 2
The difference from example 1 is that: in step S3, the molar ratio of graphene oxide to copper element is 1: 1.4;
example 3
The difference from example 1 is that: in step S3, the molar ratio of graphene oxide to copper element is 1: 1.6;
example 4
The difference from example 1 is that: in step S3, the molar ratio of graphene oxide to copper element is 1: 1.8;
example 5
The difference from example 3 is that: the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 14;
example 6
The difference from example 3 is that: the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 16;
example 7
The difference from example 3 is that: the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 18;
example 8
The difference from example 6 is that: in step S4, the magnetic attraction arrangement device includes a primary electromagnet unit and a secondary electromagnet unit which are sleeved and arranged, each electromagnet unit correspondingly forms a primary magnetic attraction arrangement area and a secondary magnetic attraction arrangement area from inside to outside on the bottom surface of the container for holding the mixed liquid, and the method for performing directional arrangement on the carbon fiber bundles includes the following substeps: s411: starting the secondary electromagnet unit, and forming magnetic force in the secondary magnetic attraction arrangement area to adsorb the carbon fiber bundles in the secondary magnetic attraction arrangement area on the inner bottom surface of the container; s412: stirring the mixed solution to ensure that the carbon fiber bundles in the mixed solution with insufficient magnetic attraction are separated from the secondary magnetic attraction arrangement area on the inner bottom surface of the container; s413: and starting the primary electromagnet unit, forming magnetic force in the primary magnetic attraction arrangement area to adsorb the separated carbon fiber bundles in the primary magnetic attraction arrangement area on the inner bottom surface of the container, and then forming a uniformly-distributed carbon fiber bundle array.
Example 9
The difference from example 6 is that: in step S4, the magnetic attraction arrangement device includes a primary electromagnet unit, a secondary electromagnet unit, a tertiary electromagnet unit, and a quaternary electromagnet unit, which are formed in a sleeved arrangement, and each electromagnet unit correspondingly forms a primary magnetic attraction arrangement region, a secondary magnetic attraction arrangement region, a tertiary magnetic attraction arrangement region, and a quaternary electromagnet unit from inside to outside on the bottom surface of the container for holding the mixed liquid, and the method for performing directional arrangement on the carbon fiber bundle includes the following substeps: s411: starting the four-level electromagnet unit, and forming magnetic force in the four-level magnetic absorption arrangement area to absorb the carbon fiber bundles in the four-level magnetic absorption arrangement area on the inner bottom surface of the container; s412: stirring the mixed solution to ensure that the carbon fiber bundles which are insufficiently magnetically attracted in the mixed solution are separated from a four-level magnetic attraction arrangement area on the inner bottom surface of the container; s413: starting the three-stage electromagnet unit, and forming magnetic force in the three-stage magnetic attraction arrangement area to adsorb the carbon fiber bundles in the three-stage magnetic attraction arrangement area on the inner bottom surface of the container; s414: stirring the mixed solution to ensure that the carbon fiber bundles in the mixed solution with insufficient magnetic attraction are separated from the three-stage magnetic attraction arrangement area on the inner bottom surface of the container; s415: starting the secondary electromagnet unit, forming magnetic force in the secondary magnetic attraction arrangement area, and adsorbing the separated carbon fiber bundles in the secondary magnetic attraction arrangement area on the inner bottom surface of the container; s416: stirring the mixed solution to enable the carbon fiber bundles in the mixed solution with insufficient magnetic attraction to be separated from the three-stage magnetic attraction arrangement area and the second-stage arrangement area on the inner bottom surface of the container; s417: and starting the primary electromagnet unit, forming magnetic force in the primary magnetic attraction arrangement area to adsorb the separated carbon fiber bundles in the primary magnetic attraction arrangement area on the inner bottom surface of the container, and then forming a uniformly-distributed carbon fiber bundle array.
Example 10
The difference from example 6 is that: the length of the exposed end of the carbon fiber bundle is 1 mm;
example 11
The difference from example 6 is that: the length of the exposed end of the carbon fiber bundle is 1.5 mm;
example 12
The difference from example 6 is that: the length of the exposed end of the carbon fiber bundle is 1.8 mm;
comparative example 1
In this example, the directional arrangement of the carbon fiber bundles in the mixed liquid is not performed by using a magnetic attraction arrangement device, and the method comprises the following steps: preparing a copper hydroxide/graphene oxide suspension: dissolving graphene oxide in water, performing ultrasonic dispersion to obtain a graphene oxide suspension for later use, and dripping sodium hydroxide into a copper nitrate solution, wherein the molar ratio of the graphene oxide to the copper nitrate solution is 1: 1, reacting for 45min to obtain liquid copper hydroxide, adding the copper hydroxide dissolved in water into the graphene oxide suspension under the stirring condition, and ensuring that the molar ratio of the graphene oxide to the copper element is 1: 1.6, stirring at room temperature for 24 hours, and ultrasonically oscillating; obtaining copper hydroxide/graphene oxide suspension; the graphene oxide contains a large amount of polar oxygen-containing functional groups, has the characteristics of good hydrophilicity and mechanical properties, and is combined with copper hydroxide containing hydroxyl groups through hydrogen bonds to improve the hydrophilicity of the graphene oxide, so that the graphene oxide is dispersed more stably for later use; placing the carbon fiber bundle in a copper hydroxide/graphene oxide suspension, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 16; adding the mixed solution into a bidirectional freezing mould; the mixed solution is subjected to a bidirectional freezing gradient and freeze drying process to form a carbon fiber bundle-copper hydroxide/graphene oxide heat conduction material; the specific method comprises the following steps: pouring the mixture into a bidirectional freezing mould, freezing for 6 hours at-70 ℃, and then performing vacuum freeze drying (the vacuum degree is 0.1-2 Pa, and the drying time is 72 hours) to obtain the product; and under the argon protection environment, heating at 1000 ℃, reacting for 7 hours, and reducing the carbon fiber bundle-copper-doped graphene oxide heat conduction material to form the carbon fiber bundle-copper-doped graphene oxide heat conduction material.
Comparative example 2
In this example, a magnetic attraction arrangement device is not used, and copper hydroxide doping is not performed on the graphene suspension, so that the carbon fiber bundles in the mixed solution are directionally arranged, and the method comprises the following steps:
preparing a graphene oxide suspension: dissolving graphene oxide in water, and performing ultrasonic dispersion to obtain a graphene oxide suspension for later use; placing the carbon fiber bundle in a copper hydroxide/graphene oxide suspension, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 16; adding the mixed solution into a bidirectional freezing mould; the mixed solution is subjected to a bidirectional freezing gradient and freeze drying process to form a carbon fiber bundle-copper hydroxide/graphene oxide heat conduction material; the specific method comprises the following steps: pouring the mixture into a bidirectional freezing mould, freezing for 6 hours at-70 ℃, and then performing vacuum freeze drying (the vacuum degree is 0.1-2 Pa, and the drying time is 72 hours) to obtain the product; and under the argon protection environment, heating at 1000 ℃ for 7h, and reducing the carbon fiber bundle-copper-doped graphene oxide heat conduction material to form the carbon fiber bundle-copper-doped graphene oxide heat conduction material.
The experimental results are as follows: the thermal conductivity was tested for the examples 1-9, and for the comparative examples 1-2, along the length of the carbon fiber;
thermal conductivity the thermal conductivity of the high thermal conductivity graphene heat sink material was tested using a C-THERM TCI instrument using the ASTM D7984 standard.
The test results are shown in table 1.
TABLE 1
As can be seen from table 1, after the carbon fiber bundles in the mixed solution are aligned in a multi-stage orientation manner by the magnetic attraction alignment device, the thermal conductivity of the prepared carbon fiber bundle-copper-doped graphene thermal conductive material can be improved by more than 30%; the heat conduction performance of the graphene heat conduction material is greatly improved; in addition, compared with the graphene heat conduction material prepared from unmodified graphene oxide, the heat conduction coefficient of the graphene heat conduction material can be improved by more than 45%;
comparing examples 1 to 4, it can be seen that, as the molar ratio of graphene oxide to copper element decreases, the thermal conductivity of the product increases first and then decreases, which proves that the optimal molar ratio of graphene oxide to copper element is 1: 1.6, under the condition, the heat conductivity coefficient of the product is maximum;
by comparing example 3 and examples 5 to 7, it is understood that the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide decreases, and the thermal conductivity of the product increases first and then decreases, thus proving that the optimal mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 16;
comparing example 6 and examples 8 to 9, it can be seen that the thermal conductivity of the four-stage electromagnet unit is not significantly increased compared to the three-stage electromagnet unit, because the dispersion properties of the carbon fibers are not greatly different between the four-stage electromagnet unit and the three-stage electromagnet unit, and therefore, the three-stage electromagnet unit is used as the best magnetic attraction device to orient the carbon fibers.
Comparing example 6 with examples 10 to 11, it can be seen that as the length of the exposed end of the carbon fiber bundle increases, the thermal conductivity of the product increases first and then decreases; the reason is that the exposed ends of the carbon fiber bundles are too short, the magnetic attraction is insufficient and the dispersion is uneven, if the exposed ends are too long, the magnetic force is too large, and when the tail ends of the carbon fiber bundles are mutually attracted, the tail ends of the carbon fiber bundles are not easy to separate and rearrange, so that the whole arrangement effect of the product is influenced;
comparing comparative example 1 and comparative example 2, it can be known that doping the graphene suspension with copper hydroxide can improve the hydrophilic property of the graphene suspension, further improve the dispersion uniformity of the graphene suspension, enable the graphene suspension to be uniformly attached to the surface of carbon fibers, and improve the thermal conductivity by more than 10%, thereby improving the thermal conductivity.
Claims (8)
1. The preparation method of the graphene heat addition/dissipation composite material for the lithium battery of the new energy automobile is characterized by comprising the following steps of: the method comprises the following steps:
s1: taking a carbon fiber bundle, wrapping a layer of aluminum foil on the carbon fiber bundle and exposing an exposed end, and performing cobalt film deposition on the exposed end by adopting pulse laser vapor deposition equipment;
s2: detecting the magnetism of the cobalt film deposition end on the carbon fiber bundle; if the magnetism is not enough, the cobalt film deposition operation is performed again, and if the magnetism meets the requirement, the step S3 is executed;
s3: preparing a copper hydroxide/graphene oxide suspension; placing the carbon fiber bundle obtained in the step S2 in a copper hydroxide/graphene oxide suspension, and performing ultrasonic dispersion to obtain a mixed solution;
s4: performing multi-stage directional arrangement on the carbon fiber bundles in the mixed solution through a magnetic attraction arrangement device; after the carbon fiber bundles are arranged in an oriented way, the top ends of the carbon fiber bundles penetrate out of the top surface of the mixed liquid;
s5: the mixed solution is subjected to a bidirectional freezing gradient and freeze drying process to form a carbon fiber bundle-copper hydroxide/graphene oxide heat conduction material;
s6: and reducing the carbon fiber bundle-copper-doped graphene oxide heat conduction material at the heating temperature of 1000 ℃ under the argon protection environment to form the carbon fiber bundle-copper-doped graphene oxide heat conduction material.
2. The preparation method of the graphene heat-dissipation composite material for the lithium battery of the new energy automobile according to claim 1, wherein the graphene heat-dissipation composite material comprises the following steps: the length of the exposed end of the carbon fiber bundle is 1.5 mm.
3. The preparation method of the graphene heat-dissipation composite material for the lithium battery of the new energy automobile according to claim 1, wherein the graphene heat-dissipation composite material comprises the following steps: in step S3, the mass ratio of the carbon fiber bundle to the copper hydroxide/graphene oxide is 1: 16.
4. the preparation method of the graphene heat-dissipation composite material for the lithium battery of the new energy automobile according to claim 1, wherein the graphene heat-dissipation composite material comprises the following steps: the method for preparing the copper hydroxide/graphene oxide suspension comprises the following steps:
dissolving graphene oxide in water, performing ultrasonic dispersion to obtain a graphene oxide suspension for later use, dripping sodium hydroxide into a copper nitrate solution to obtain liquid copper hydroxide, adding the copper hydroxide dissolved in the water into the graphene oxide suspension under a stirring condition, performing ultrasonic oscillation, and embedding the copper hydroxide into the graphene oxide through a hydrogen bond; and obtaining the copper hydroxide/graphene oxide suspension.
5. The preparation method of the graphene heat-dissipation composite material for the lithium battery of the new energy automobile according to claim 4, wherein the graphene heat-dissipation composite material comprises the following steps: the molar ratio of the graphene oxide to the copper element is 1: 1.6.
6. the preparation method of the graphene heat-dissipation composite material for the lithium battery of the new energy automobile according to claim 1, wherein the graphene heat-dissipation composite material comprises the following steps: the magnetic attraction arrangement device comprises a plurality of electromagnet units which are in telescopic sleeve connection, each electromagnet unit forms a working area, and the outer container is arranged on the working area; the outer contour of the electromagnet unit is superposed with the outer edge of the working area, and each electromagnet unit is connected with an independent magnetic switch control system to form a multi-stage magnetic attraction arrangement area;
the method for directionally arranging the carbon fiber bundles in the mixed liquid by the magnetic attraction arrangement device comprises the following substeps:
s41: starting the electromagnet units positioned on the periphery, and adsorbing the carbon fiber bundles on the outer ring of the bottom surface of the container through magnetic force by the electromagnet units on the periphery;
s42: stirring the mixed solution to ensure that the carbon fiber bundles in the mixed solution which are insufficiently magnetically absorbed are separated from the outer ring of the inner bottom surface of the container;
s43: lifting the electromagnet unit in the middle to be on the same plane with the electromagnet units on the periphery, and opening the electromagnet units to enable the separated carbon fiber bundles to be adsorbed at the center of the inner bottom surface of the container again;
s44: and continuously stirring the mixed solution to ensure that the carbon fiber bundles with insufficient magnetic attraction in the mixed solution are separated from the inner bottom surface of the container and then are arranged and adsorbed again.
7. The preparation method of the graphene heat-dissipation composite material for the lithium battery of the new energy automobile according to claim 6, wherein the graphene heat-dissipation composite material comprises the following steps: the magnetic attraction arrangement device comprises a primary electromagnet unit, a secondary electromagnet unit and a tertiary electromagnet unit which are formed in a sleeved arrangement mode, each electromagnet unit correspondingly forms a primary magnetic attraction arrangement area, a secondary magnetic attraction arrangement area and a tertiary magnetic attraction arrangement area on the bottom surface of a container for containing mixed liquid from inside to outside, and the method for directionally arranging the carbon fiber bundles comprises the following substeps:
s411: starting the three-stage electromagnet unit, and forming magnetic force in the three-stage magnetic attraction arrangement area to adsorb the carbon fiber bundles in the three-stage magnetic attraction arrangement area on the inner bottom surface of the container;
s412: stirring the mixed solution to ensure that the carbon fiber bundles which are insufficiently magnetically absorbed in the mixed solution are separated from the three-stage magnetic absorption arrangement area on the inner bottom surface of the container;
s413: starting the second-stage electromagnet unit, ascending to the same plane as the third-stage electromagnet unit, and forming magnetic force in the second-stage magnetic attraction arrangement area to adsorb the separated carbon fiber bundles in the second-stage magnetic attraction arrangement area on the inner bottom surface of the container;
s414: stirring the mixed solution to enable the carbon fiber bundles in the mixed solution with insufficient magnetic attraction to be separated from the three-stage magnetic attraction arrangement area and the second-stage arrangement area on the inner bottom surface of the container;
s415: and starting the primary electromagnet unit, ascending to the same plane with the secondary electromagnet unit, forming magnetic force in the primary magnetic attraction arrangement area, and adsorbing the separated carbon fiber bundles in the primary magnetic attraction arrangement area on the inner bottom surface of the container so as to form a uniformly distributed carbon fiber bundle array.
8. The utility model provides a graphite alkene adds/heat dissipation combined material for new energy automobile lithium cell which characterized in that: prepared using the preparation process according to any one of claims 1 to 7.
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