CN105127197A - Preparation method for multi-layer metal/graphene composite electrode thin strip - Google Patents

Abstract

The invention provides a preparation method for a multi-layer metal/graphene composite electrode thin strip. The preparation method comprises the following process steps: (1) carrying out primary thinning on a metal material by adopting a synchronous cold rolling process; (2) grinding and cleaning metal thin strips; (2) coating the surfaces of the metal thin strips with graphene paint; (4) tightly laminating upper and lower surfaces of 2-20 metal/graphene thin strips; (5) carrying out synchronous cold rolling on multiple metal/graphene thin strips; (6) carrying out synchronous cold rolling or asynchronous cold rolling on a multi-layer metal/graphene composite thin plate; (7) carrying out asynchronous cold rolling on the multi-layer metal/graphene composite thin plate; and (8) carrying out negative roll-gap asynchronous cold rolling on the multi-layer metal/graphene composite thin plate, thereby obtaining an extremely thin strip. According to the method disclosed by the invention, atomic-scale combination of graphene and metal is achieved; the preparation process is low in requirements on production equipment; the production energy sources are saved; emission of carbon dioxide is reduced; and mass production for the multi-layer metal/graphene composite thin plate with a thickness of 1-4 [mu]m is easy to realize.

Description

A kind of preparation method of multi-layer metal/graphene composite ultra-thin ribbon

technical field

The invention belongs to the technical field of metal materials, and in particular relates to a preparation method of a multilayer metal/graphene composite ultra-thin strip.

Background technique

Graphene is a new two-dimensional single-layer carbon atom material, composed of sp ² hybridized carbon atoms densely packed, with a surface area of up to 2630mm ² /g. Graphene has excellent properties such as mechanics, thermal conductivity, charge transport, optics, and gas permeability. For example, Young's modulus is 1100GPa, fracture strength is 125GPa, thermal conductivity is as high as 5300W/m K, and electron mobility at room temperature exceeds 15000cm ² /V·s, while the resistivity is only about 1Ω·m, only absorbs 2.3% of light, and is almost completely transparent. Taking advantage of the above-mentioned excellent characteristics of graphene, through compounding with other metal materials, such as copper, aluminum, molybdenum, nickel, titanium, steel and other metals, new materials can be endowed with more excellent performance. At present, the composite methods of metal materials and graphene mainly include electrochemical deposition, ball milling and sintering. However, due to the complicated preparation process and the high probability of graphene agglomeration, the dispersion of graphene in the matrix is not uniform, which is serious. Affect the performance of metal materials after composite. In addition, there is no report on the preparation of multi-layer metal/graphene composite ultra-thin strips by using cold rolling to composite metal and graphene. Compared with hot rolling, the cold rolling temperature is lower, which can effectively avoid the metal matrix Favorable phase transitions for bonding, microstructural changes, and formation of brittle intermediate compounds. The composite material prepared by the cold-rolling composite process has uniform thickness, high surface finish, and no defects such as oxide layer. The bonding strength between metal and graphene is high, graphene has no oxidation phenomenon, and the product performance is stable. The process is flexible, and it can be combined with a single sheet, or it can be rolled into a coil automatically, which is conducive to stable and high production.

Contents of the invention

Aiming at the problems existing in the prior art and combining the advantages of the cold rolling process, the present invention provides a method for preparing a multilayer metal/graphene composite ultra-thin strip. In the preparation method, the graphene is evenly coated on the surface of the metal sheet by a roller brush or CVD process, and then a multi-layer metal graphene composite thin strip is prepared by a synchronous rolling cold rolling process, and finally prepared by asynchronous rolling cold rolling process The multi-layer metal/graphene composite ultra-thin strip has good engineering application prospects in the fields of communication, electronics, micro-manufacturing, micro-system and medical treatment. Technical scheme of the present invention is:

A method for preparing a multilayer metal/graphene composite extremely thin strip is carried out according to the following process steps:

(1) Prepare a metal material with a thickness of 1~20mm and a width of 50~500mm, adopt the synchronous cold rolling process, and thin the metal material to 0.3~0.9mm after 4~10 passes, and the synchronous cold rolling process parameters are: roll The diameter is 100~180mm, the rolling speed is 0.5~3m/min, the pass reduction rate is 10~20%, the rolling process is controlled by micro tension, and the tension value is 1/5~ of the tensile strength of metal materials with equal thickness. 1/3;

(2) Grind the upper and lower surfaces of the thin metal strip, and then clean it with ultrasonic vibration. The parameters are set to ultrasonic water temperature 30-50°C, the cleaning time is 5-10 minutes, and then air-dried;

(3) Evenly coat the graphene coating on the surface of the metal strip in step (2), the thickness of the graphene coating is 5-50 μm, and then place it in the air to dry for 10-30 minutes to obtain the metal/graphene strip blank ;

(4) The upper and lower surfaces of 2~20 pieces of metal/graphene thin strip blanks are tightly bonded together;

(5) Roll the multi-sheet metal/graphene thin strips in step (4) by adopting the synchronous cold rolling process, the process parameters are: the diameter of the roll is 100~180mm, the rolling speed is 0.5~3m/min, The reduction rate is 30~70%, and the second pass reduction rate is 20~50%. The rolling process adopts micro-tension rolling, and the tension value is 1/5~1/3 of the tensile strength of metal materials with equal thickness. Obtain a multi-layer metal/graphene composite sheet with a thickness of 0.5~1mm;

(6) Use synchronous cold rolling or asynchronous cold rolling to thin the multi-layer metal/graphene composite sheet to 80~200μm. When synchronous rolling is used, the process parameters are: roll diameter 30~50mm, rolling speed 10~ 50mm/s, the tension value is 1/5~1/3 of the tensile strength of metal materials with equal thickness, the pass reduction rate is 10~15%, and it is thinned to the target thickness after 10~15 passes;

When using asynchronous rolling, the process parameters are: roll diameter 30~50mm, rolling speed 10~60mm/s, different speed ratio 1.05~1.2, tension value 1/5~1 of the tensile strength of metal materials with equal thickness /3, the pass reduction rate is 8~15%, and it is thinned to the target thickness after 2~4 passes;

(7) Using asynchronous cold rolling process, the multi-layer metal/graphene composite thin strip in step (6) is thinned to 15-25 μm after 3-7 passes. The process parameters are: roll diameter 30-50 mm, rolling speed 10~50mm/s, variable speed ratio 1.1~1.4, tension value less than 1/2 of the tensile strength of metal materials with equal thickness, pass reduction rate 10~40%, and total deformation rate greater than 80%;

(8) Thinning the multi-layer metal/graphene metal composite thin strip in step (7) to 1-4 μm by negative roll gap asynchronous cold rolling process, the process parameters are: roll diameter 30-50mm, rolling speed 10- 50mm/s, different speed ratio 1.3~1.6, tension value is less than 1/2 of the tensile strength of metal materials with equal thickness, pass reduction rate is 10~40%, rolling 6~10 passes, total deformation rate is greater than 80 %, the multilayer metal/graphene metal composite extremely thin strips with a thickness of 1-4 μm were prepared.

The metal materials in the step (1) are copper, aluminum, molybdenum, nickel, titanium and steel.

The graphene coating in the step (3) is a water-based graphene solution with a mass concentration of 4%, an oily graphene solution with a mass concentration of 4%, and graphene powder.

There are two ways to uniformly coat graphene on the surface of the metal strip in the step (3): the first way is to evenly roll the graphene slurry or graphene powder with a mass concentration of 4% on the surface of the metal strip The second way is to use the CVD method, that is, to use methane as a carbon source, and grow graphene through pyrolysis on the surface of the metal substrate, so as to uniformly deposit graphene on the surface of the thin strip.

The bonding methods in the step (4) include welding, strong metal glue or rivets.

The negative roll gap asynchronous cold rolling process in the step (8) is that the two work rolls are fully pressed against each other at room temperature, and large elastic flattening occurs, and the asynchronous rolling process of the metal composite thin strip is carried out in this state.

The advantages and beneficial effects that the present invention has are:

(1) The method of the present invention adopts the method of depositing a graphene layer on the surface of the thin strip by means of a roller brushing graphene coating or a CVD method, so that the graphene can be evenly dispersed on the metal surface, and the content of graphene in the graphene-metal composite strip can be controlled.

(2) The final step of the method of the present invention adopts the negative roll gap cold rolling process. Compared with the traditional process, the contact area between the rolled piece and the roll is significantly increased, and combined with asynchronous rolling, the ratio of the rubbing area is greatly increased, which is more conducive to rolling. Plastic deformation of the workpiece, thereby improving the rolling efficiency, breaking through the thinning limit of the traditional rolling mill with the same roll diameter, effectively improving the thinning efficiency of the metal/graphene composite material, and at the same time, it can also improve the conductivity of the graphene metal composite ultra-thin strip Thermal conductivity and other properties.

(3) The method of the present invention can achieve the combination of graphene and metal at the atomic level. The whole preparation process has lower requirements on production equipment, saves production energy and reduces carbon dioxide emissions, and is easy to realize multilayer metal/graphene with a thickness of 1-4 μm The mass production of composite ultra-thin strips has good engineering application prospects in the fields of communication, electronics, micromanufacturing, microsystems and medical treatment.

Description of drawings

Figure 1 is a schematic diagram of the assembly of metal/graphene prepared by the method of the present invention.

Fig. 2 is a photo of the microstructure of the 1 μm multilayer copper/graphene composite ultra-thin ribbon prepared in Example 1 of the present invention.

Figure 3 is a photo of the microstructure of the 4 μm multilayer aluminum/graphene composite ultra-thin ribbon prepared in Example 2 of the present invention, where GO represents graphene, and Al represents aluminum.

Detailed ways

The model of the ultrasonic vibrator used in the embodiment of the present invention is: Jiemeng JP-010T;

The synchronous cold rolling mill that adopts in the embodiment of the present invention is a self-made product;

The asynchronous cold rolling mill adopted in the embodiment of the present invention is a self-made product, see patent CN102989765;

The tension motor model adopted in the embodiment of the present invention is: three-phase gear reduction torque motor AJC6334;

The negative roll gap asynchronous rolling cold rolling mill used in the embodiment of the present invention is a self-made product, see patent CN102989765.

Example 1

To prepare a multilayer copper/graphene composite extremely thin strip with a thickness of 1 μm, the process steps are:

(1) Prepare industrial pure copper T2 as metal raw material, the size is: thickness 2mm, width 50mm, using synchronous cold rolling process, the copper material is thinned to 0.5mm after 4 passes, and the parameters of synchronous cold rolling process are: roll diameter The rolling speed is 180mm, the rolling speed is 0.5m/min, the pass reduction rate is 5~20%, the rolling process adopts micro-tension control, and the tension value is 1/5 of the tensile strength of copper with equal thickness;

(2) Grind the upper and lower surfaces of the copper strip, and then use ultrasonic vibration to clean it. The parameters are set at an ultrasonic water temperature of 30°C, the cleaning time is 5-10 minutes, and then air-dried;

(3) Brush 4% aqueous graphene solution evenly on the surface of the copper strip in step (2). The thickness of the graphene coating is 5-50 μm, and then air-dry for 15 minutes to obtain a copper/graphene strip. with blank;

(4) The upper and lower surfaces of 6 pieces of copper/graphene thin strip blanks are tightly bonded together by welding;

(5) The multi-piece copper/graphene thin strips in step (4) are rolled by the synchronous cold rolling process. The process parameters are: the diameter of the roll is 180mm, the rolling speed is 0.5~3m/min, and the first pass The reduction rate in the second pass is 70%, and the reduction rate in the second pass is 50%. The rolling process adopts micro-tension rolling, and the tension value is 1/5 of the tensile strength of copper with equal thickness to obtain a multilayer copper/graphene composite sheet. The thickness is 0.5mm;

(6) The multi-layer copper/graphene composite sheet is thinned to 80 μm by synchronous cold rolling process. The process parameters are: roll diameter 30 mm, rolling speed 10-50 mm/s, and tension value equal to the tensile strength of the copper material of the same thickness. 1/5, the pass reduction rate is 10~15%, and it is thinned to the target thickness after 10 passes;

(7) Using asynchronous cold rolling process, the multilayer copper/graphene composite thin strip in step (6) is thinned to 15 μm after 3 passes. The process parameters are: roll diameter 30 mm, rolling speed 50 mm/s, different speed The ratio is 1.1~1.4, the tension value is 1/3 of the tensile strength of copper with equal thickness, the pass reduction rate is 10~40%, and the total deformation rate is 99%;

(8) Thin the multilayer copper/graphene composite thin strip in step (7) to 1 μm by negative roll gap asynchronous cold rolling process. The process parameters are: roll diameter 30 mm, rolling speed 10-50 mm/s, different The speed ratio is 1.3~1.6, the tension value is 1/3 of the tensile strength of copper with equal thickness, the pass reduction rate is 20~40%, rolling 6 passes, the total deformation rate is 99.9%, and the prepared thickness is 1μm Multilayer copper/graphene composite extremely thin ribbons.

The multilayer copper/graphene composite ultra-thin strip prepared in this embodiment has high surface finish, good flatness, uniform thickness, and no defects such as oxide layers and cracks. The dispersion of graphene in the copper matrix is good, the sheet area is large, there is no agglomeration phenomenon, and the degree of bonding with the matrix is high, as shown in Figure 2.

Example 2

To prepare a multilayer aluminum/graphene composite extremely thin strip with a thickness of 4 μm, the process steps are:

(1) Prepare industrial pure aluminum A1060 as the metal raw material, the size is: thickness 20mm, width 500mm, using synchronous cold rolling process, the aluminum material is thinned to 0.9mm after 10 passes, and the parameters of synchronous cold rolling process are: roll diameter The rolling speed is 100mm, the rolling speed is 0.5~3m/min, the pass reduction rate is 20%, the rolling process adopts micro-tension control, and the tension value is 1/3 of the tensile strength of aluminum with equal thickness;

(2) Grind the upper and lower surfaces of the aluminum strip, and then use ultrasonic vibration to clean it. The parameters are set at an ultrasonic water temperature of 50°C, the cleaning time is 6-10 minutes, and then air-dried;

(3) Brush the graphene powder evenly on the surface of the aluminum strip in step (2), the coating thickness of the graphene is 5-50 μm, and obtain the aluminum/graphene strip blank;

(4) The upper and lower surfaces of two aluminum/graphene thin strip blanks are tightly bonded together by welding;

(5) The multi-piece aluminum/graphene thin strips in step (4) are rolled by the synchronous cold rolling process. The process parameters are: the diameter of the roll is 180mm, the rolling speed is 0.5~3m/min, and the first pass is pressed The reduction rate in the second pass is 30%, and the reduction rate in the second pass is 20%. The rolling process adopts micro-tension rolling, and the tension value is 1/3 of the tensile strength of an equal-thickness aluminum material to obtain a multi-layer aluminum/graphene composite sheet. The thickness is 0.5mm;

(6) The multi-layer aluminum/graphene composite sheet is thinned to 200 μm by asynchronous cold rolling process. The process parameters are: roll diameter 50 mm, rolling speed 10-60 mm/s, speed ratio 1.05-1.2, tension value 1/3 of the tensile strength of equal-thickness aluminum, the pass reduction rate is 8~15%, and it is thinned to the target thickness after 4 passes;

(7) Using asynchronous cold rolling process, the multilayer aluminum/graphene composite thin strip in step (6) is thinned to 25 μm after 7 passes. The process parameters are: roll diameter 50mm, rolling speed 10~50mm/s, The speed ratio is 1.1~1.4, the tension value is 1/3 of the tensile strength of equal thickness aluminum material, the pass reduction rate is 10~40%, and the total deformation rate is 99.75%;

(8) Thin the multilayer aluminum/graphene composite thin strip in step (7) to 4 μm by negative roll gap asynchronous cold rolling process. The process parameters are: roll diameter 50 mm, rolling speed 10-50 mm/s, different The speed ratio is 1.3~1.6, the tension value is 1/3 of the tensile strength of aluminum with equal thickness, the pass reduction rate is 10~40%, rolling 6 passes, the total deformation rate is 99.96%, and the prepared thickness is 4μm Multilayer aluminum/graphene composite extremely thin ribbons.

The multilayer aluminum/graphene composite ultra-thin strip prepared in this example has high surface finish, good flatness, uniform thickness, and no defects such as oxide layers and cracks. The dispersion of graphene in the aluminum matrix is good, the sheet area is large, there is no agglomeration phenomenon, and the degree of combination with the matrix is high, as shown in Figure 3.

Example 3

To prepare a multilayer nickel/graphene composite extremely thin strip with a thickness of 4 μm, the process steps are:

(1) Prepare industrial pure nickel as the metal raw material, the size is: thickness 2mm, width 50mm, using synchronous cold rolling process, the thickness of nickel material is reduced to 0.3mm after 4 passes, and the parameters of synchronous cold rolling process are: roll diameter is 180mm, the rolling speed is 0.5m/min, the pass reduction rate is 10~20%, the rolling process adopts micro-tension control, and the tension value is 1/5 of the tensile strength of nickel with equal thickness;

(2) Grind the upper and lower surfaces of the nickel thin strip, and then use ultrasonic vibration to clean it. The parameters are set at an ultrasonic water temperature of 30°C, the cleaning time is 5-10 minutes, and then air-dried;

(3) Graphene was deposited on nickel thin strips by CVD method, and the parameters were as follows: carbon source: methane; temperature: 700°C; cooling method: air cooling, and nickel/graphene thin strip blanks were obtained.

(4) The upper and lower surfaces of 20 pieces of nickel/graphene thin strip blanks are tightly bonded together by strong metal glue;

(5) The multi-piece nickel/graphene thin strips in step (4) are rolled by the synchronous cold rolling process. The process parameters are: the diameter of the roll is 180mm, the rolling speed is 0.5~3m/min, and the first pass The reduction rate in the second pass is 70%, and the reduction rate in the second pass is 40%. The rolling process adopts micro-tension rolling, and the tension value is 1/5 of the tensile strength of copper with equal thickness to obtain a multilayer copper/graphene composite sheet. The thickness is 0.9mm;

(6) The multi-layer nickel/graphene composite sheet is thinned to 80μm by synchronous cold rolling process, the process parameters are: roll diameter 30mm, rolling speed 10~50mm/s, tension value equal to the tensile strength of nickel material 1/4, the pass reduction rate is 10~15%, and it is thinned to the target thickness after 15 passes;

(7) Using asynchronous cold rolling process, the multi-layer nickel/graphene composite thin strip in step (6) is thinned to 15 μm after 3 passes. The process parameters are: roll diameter 30 mm, rolling speed 50 mm/s, different speed The ratio is 1.1~1.4, the tension value is 1/3 of the tensile strength of nickel material with equal thickness, the pass reduction rate is 10~40%, and the total deformation rate is 99%;

(8) Thin the multilayer nickel/graphene composite thin strip in step (7) to 4 μm by negative roll gap asynchronous cold rolling process. The process parameters are: roll diameter 30 mm, rolling speed 10-50 mm/s, different The speed ratio is 1.3~1.6, the tension value is 1/3 of the tensile strength of copper with equal thickness, the pass reduction rate is 20~40%, rolling 6 passes, the total deformation rate is 99.9%, and the prepared thickness is 4μm Multilayer nickel/graphene composite extremely thin ribbons.

The multilayer nickel/graphene composite ultra-thin strip prepared in this embodiment has high surface finish, good flatness, uniform thickness, and no defects such as oxide layers and cracks. Graphene has a good dispersion in the nickel matrix, a large sheet area, no agglomeration, and a high degree of bonding with the matrix.

Example 4

To prepare a multilayer molybdenum/graphene composite extremely thin strip with a thickness of 3 μm, the process steps are:

(1) Prepare industrial pure molybdenum as metal raw material, the size is: thickness 2mm, width 50mm, using synchronous cold rolling process, the copper material is thinned to 0.5mm after 4 passes, and the parameters of synchronous cold rolling process are: roll diameter is 180mm, the rolling speed is 3m/min, the pass reduction rate is 10~20%, the rolling process adopts micro-tension control, and the tension value is 1/5 of the tensile strength of copper with equal thickness;

(2) Grind the upper and lower surfaces of the molybdenum thin strip, and then clean it with ultrasonic vibration. The parameters are set at an ultrasonic water temperature of 30°C, and the cleaning time is 5-10 minutes, and then air-dried;

(3) Brush 4% oily graphene solution evenly on the surface of the molybdenum strip in step (2). with blank;

(4) The upper and lower surfaces of 6 pieces of molybdenum/graphene thin strip blanks are tightly bonded together by welding;

(5) The multi-piece molybdenum/graphene thin strips in step (4) are rolled by the synchronous cold rolling process. The process parameters are: the diameter of the roll is 180mm, the rolling speed is 0.5~3m/min, and the first pass The reduction rate in the second pass is 70%, and the reduction rate in the second pass is 40%. The rolling process adopts micro-tension rolling, and the tension value is 1/5 of the tensile strength of molybdenum material with equal thickness, so as to obtain a multilayer molybdenum/graphene composite sheet. The thickness is 0.5mm;

(6) The multi-layer molybdenum/graphene composite sheet is thinned to 80 μm by synchronous cold rolling process, the process parameters are: roll diameter 30mm, rolling speed 10~50mm/s, tension value equal to the tensile strength of molybdenum material 1/4, the pass reduction rate is 10~15%, and it is thinned to the target thickness after 10 passes;

(7) Using asynchronous cold rolling process, the multi-layer molybdenum/graphene composite thin strip in step (6) is thinned to 15 μm after 3 passes. The process parameters are: roll diameter 30 mm, rolling speed 50 mm/s, different speed The ratio is 1.1~1.4, the tension value is 1/3 of the tensile strength of molybdenum material with equal thickness, the pass reduction rate is 10~40%, and the total deformation rate is 99%;

(8) Thin the multilayer molybdenum/graphene composite thin strip in step (7) to 3 μm by negative roll gap asynchronous cold rolling process, the process parameters are: roll diameter 30 mm, rolling speed 10~50 mm/s, different The speed ratio is 1.3~1.6, the tension value is 1/3 of the tensile strength of molybdenum material with equal thickness, the pass reduction rate is 20~40%, rolling 6 passes, the total deformation rate is 99.9%, and the prepared thickness is 3μm Multilayer molybdenum/graphene composite extremely thin ribbons.

The multilayer molybdenum/graphene composite ultra-thin strip prepared in this example has high surface finish, good flatness, uniform thickness, and no defects such as oxide layers and cracks. Graphene has good dispersion in the molybdenum matrix, large sheet area, no agglomeration phenomenon, and high degree of combination with the matrix.

Example 5

To prepare a multilayer titanium/graphene composite extremely thin strip with a thickness of 3 μm, the process steps are:

(1) Prepare industrially pure titanium as the metal raw material, the size is: thickness 2mm, width 50mm, using synchronous cold rolling process, the copper material is thinned to 0.5mm after 4 passes, and the parameters of synchronous cold rolling process are: roll diameter is 180mm, the rolling speed is 0.5m/min, the pass reduction rate is 10~20%, the rolling process adopts micro-tension control, and the tension value is 1/5 of the tensile strength of copper with equal thickness;

(2) Grind the upper and lower surfaces of the titanium thin strip, and then clean it with ultrasonic vibration. The parameters are set at an ultrasonic water temperature of 30°C, the cleaning time is 5-10 minutes, and then air-dried;

(3) Brush 4% aqueous graphene solution evenly on the surface of the titanium thin strip in step (2). The thickness of the graphene coating is 5-50 μm, and then air-dry for 15 minutes to obtain the titanium/graphene thin strip. with blank;

(4) The upper and lower surfaces of 6 pieces of titanium/graphene thin strip blanks are tightly bonded together by rivets;

(5) The multi-piece titanium/graphene thin strips in step (4) are rolled by the synchronous cold rolling process. The process parameters are: the diameter of the roll is 180mm, the rolling speed is 0.5~3m/min, and the first pass is pressed The reduction rate in the second pass is 70%, and the reduction rate in the second pass is 40%. The rolling process adopts micro-tension rolling, and the tension value is 1/5 of the tensile strength of titanium with equal thickness, so as to obtain a multi-layer titanium/graphene composite sheet. The thickness is 0.5mm;

(6) The multi-layer titanium/graphene composite sheet is thinned to 80 μm by synchronous cold rolling process. The process parameters are: roll diameter 30 mm, rolling speed 10-50 mm/s, tension value equal to the tensile strength of titanium material 1/4, the pass reduction rate is 10~15%, and it is thinned to the target thickness after 10 passes;

(7) Using asynchronous cold rolling process, the multilayer titanium/graphene composite thin strip in step (6) is thinned to 15 μm after 3 passes. The process parameters are: roll diameter 30 mm, rolling speed 50 mm/s, different speed The ratio is 1.1~1.4, the tension value is 1/3 of the tensile strength of titanium material with equal thickness, the pass reduction rate is 10~40%, and the total deformation rate is 99%;

(8) Thin the multilayer titanium/graphene composite thin strip in step (7) to 3 μm by negative roll gap asynchronous cold rolling process, the process parameters are: roll diameter 30 mm, rolling speed 10~50 mm/s, different The speed ratio is 1.3~1.6, the tension value is 1/3 of the tensile strength of titanium with equal thickness, the pass reduction rate is 20~40%, rolling 6 passes, the total deformation rate is 99.9%, and the prepared thickness is 3μm Multilayer titanium/graphene composite extremely thin ribbons.

The multilayer titanium/graphene composite ultra-thin strip prepared in this example has high surface finish, good flatness, uniform thickness, and no defects such as oxide layers and cracks. Graphene has a good dispersion in the titanium matrix, a large sheet area, no agglomeration, and a high degree of bonding with the matrix.

Example 6

To prepare a multi-layer Q195/graphene composite ultra-thin strip with a thickness of 3 μm, the process steps are:

(1) Prepare industrially pure Q195 as the metal raw material, the size is: thickness 2mm, width 50mm, using synchronous cold rolling process, after 10 passes, the copper material is thinned to 0.5mm, and the parameters of synchronous cold rolling process are: roll diameter is 180mm, the rolling speed is 2m/min, the pass reduction rate is 10~20%, the rolling process adopts micro-tension control, and the tension value is 1/5 of the tensile strength of copper with equal thickness;

(2) Grind the upper and lower surfaces of the copper strip, and then use ultrasonic vibration to clean it. The parameters are set at an ultrasonic water temperature of 30°C, the cleaning time is 5-10 minutes, and then air-dried;

(3) Brush 4% aqueous graphene solution evenly on the surface of the Q195 thin strip in step (2). with blank;

(4) The upper and lower surfaces of 6 pieces of Q195/graphene thin strip blanks are tightly bonded together by welding;

(5) The multi-piece Q195/graphene thin strips in step (4) are rolled by the synchronous cold rolling process. The process parameters are: the diameter of the roll is 180mm, the rolling speed is 0.5~3m/min, and the first pass is pressed The reduction rate in the second pass is 70%, and the reduction rate in the second pass is 40%. The rolling process adopts micro-tension rolling, and the tension value is 1/5 of the tensile strength of the Q195 material with equal thickness, so as to obtain a multi-layer Q195/graphene composite sheet. The thickness is 0.5mm;

(6) The multi-layer Q195/graphene composite sheet is thinned to 80 μm by synchronous cold rolling process. The process parameters are: roll diameter 30mm, rolling speed 10~50mm/s, tension value equal to the tensile strength of Q195 material 1/4, the pass reduction rate is 10~15%, and it is thinned to the target thickness after 10 passes;

(7) Using asynchronous cold rolling process, the multi-layer Q195/graphene composite thin strip in step (6) is thinned to 15 μm after 3 passes. The process parameters are: roll diameter 30mm, rolling speed 50mm/s, different speed The ratio is 1.1~1.4, the tension value is 1/3 of the tensile strength of Q195 material with equal thickness, the pass reduction rate is 10~40%, and the total deformation rate is 99%;

(8) Thin the multi-layer Q195/graphene composite thin strip in step (7) to 3 μm by negative roll gap asynchronous cold rolling process, the process parameters are: roll diameter 30 mm, rolling speed 10~50 mm/s, different The speed ratio is 1.3~1.6, the tension value is 1/3 of the tensile strength of Q195 material with equal thickness, the pass reduction rate is 20~40%, rolling 6 passes, the total deformation rate is 99.9%, and the prepared thickness is 3μm Multilayer Q195/graphene composite extremely thin ribbons.

The multi-layer Q195/graphene composite ultra-thin strip prepared in this example has high surface finish, good flatness, uniform thickness, and no defects such as oxide layer and crack. The dispersion of graphene in the Q195 matrix is good, the sheet area is large, there is no agglomeration phenomenon, and the degree of bonding with the matrix is high.

Claims (5)

1. a kind of preparation method of multilayer metal/graphene composite extremely thin band is characterized in that carrying out according to following processing steps: (1) Prepare a metal material with a thickness of 1~20mm and a width of 50~500mm, adopt the synchronous cold rolling process, and thin the metal material to 0.3~0.9mm after 4~10 passes, and the synchronous cold rolling process parameters are: roll The diameter is 100~180mm, the rolling speed is 0.5~3m/min, the pass reduction rate is 10~20%, the rolling process is controlled by micro tension, and the tension value is 1/5~ of the tensile strength of metal materials with equal thickness. 1/3; (2) Grind the upper and lower surfaces of the thin metal strip, and then clean it with ultrasonic vibration. The parameters are set to ultrasonic water temperature 30-50°C, the cleaning time is 5-10 minutes, and then air-dried; (3) Evenly coat the graphene coating on the surface of the metal strip in step (2), the thickness of the graphene coating is 5-50 μm, and then place it in the air to dry for 10-30 minutes to obtain the metal/graphene strip blank ; (4) The upper and lower surfaces of 2~20 pieces of metal/graphene thin strip blanks are tightly bonded together; (5) Roll the multi-sheet metal/graphene thin strips in step (4) by adopting the synchronous cold rolling process, the process parameters are: the diameter of the roll is 100~180mm, the rolling speed is 0.5~3m/min, The reduction rate is 30~70%, and the second pass reduction rate is 20~50%. The rolling process adopts micro-tension rolling, and the tension value is 1/5~1/3 of the tensile strength of metal materials with equal thickness. Obtain a multi-layer metal/graphene composite sheet with a thickness of 0.5~1mm; (6) Use synchronous cold rolling or asynchronous cold rolling to thin the multi-layer metal/graphene composite sheet to 80~200μm. When synchronous rolling is used, the process parameters are: roll diameter 30~50mm, rolling speed 10~ 50mm/s, the tension value is 1/5~1/3 of the tensile strength of metal materials with equal thickness, the pass reduction rate is 10~15%, and it is thinned to the target thickness after 10~15 passes; When using asynchronous rolling, the process parameters are: roll diameter 30~50mm, rolling speed 10~60mm/s, different speed ratio 1.05~1.2, tension value 1/5~1 of the tensile strength of metal materials with equal thickness /3, the pass reduction rate is 8~15%, and it is thinned to the target thickness after 2~4 passes; (7) Using asynchronous cold rolling process, the multi-layer metal/graphene composite thin strip in step (6) is thinned to 15-25 μm after 3-7 passes. The process parameters are: roll diameter 30-50 mm, rolling speed 10~50mm/s, variable speed ratio 1.1~1.4, tension value less than 1/2 of the tensile strength of metal materials with equal thickness, pass reduction rate 10~40%, and total deformation rate greater than 80%; (8) Thinning the multi-layer metal/graphene metal composite thin strip in step (7) to 1-4 μm by negative roll gap asynchronous cold rolling process, the process parameters are: roll diameter 30-50mm, rolling speed 10- 50mm/s, different speed ratio 1.3~1.6, tension value is less than 1/2 of the tensile strength of metal materials with equal thickness, pass reduction rate is 10~40%, rolling 6~10 passes, total deformation rate is greater than 80 %, the multi-layer metal/graphene metal composite extremely thin strips with a thickness of 1-4 μm were prepared. 2. The method for preparing a multilayer metal/graphene composite ultra-thin strip according to claim 1, characterized in that the metal material in the step (1) is copper, aluminum, molybdenum, nickel, titanium, or steel. 3. the preparation method of a kind of multilayer metal/graphene composite extremely thin strip according to claim 1, it is characterized in that the graphene coating of described step (3) is the aqueous graphene solution of mass concentration 4%, mass concentration 4% oily graphene solution, graphene powder. 4. The preparation method of a multilayer metal/graphene composite ultra-thin strip according to claim 1, characterized in that there are two ways to uniformly coat graphene on the surface of the metal strip in the step (3). One method: the first method is to evenly roll the graphene slurry or graphene powder with a mass concentration of 4% on the surface of the metal strip; the second method is to use the CVD method, that is, to use methane as the carbon source, and to use it on the surface of the metal substrate at a high temperature Decompose and grow graphene, so as to deposit graphene uniformly on the surface of the ribbon. 5. The method for preparing a multi-layer metal/graphene composite ultra-thin strip according to claim 1, characterized in that the bonding method in the step (4) includes welding, strong metal glue or rivets.