CN107377618A - A kind of preparation method of multilayer carbon nanotube/copper composite strip - Google Patents
A kind of preparation method of multilayer carbon nanotube/copper composite strip Download PDFInfo
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- CN107377618A CN107377618A CN201710475037.3A CN201710475037A CN107377618A CN 107377618 A CN107377618 A CN 107377618A CN 201710475037 A CN201710475037 A CN 201710475037A CN 107377618 A CN107377618 A CN 107377618A
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- copper
- carbon nanotube
- composite strip
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- multilayer carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 56
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 55
- 239000010949 copper Substances 0.000 title claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000005498 polishing Methods 0.000 claims abstract description 13
- 238000005096 rolling process Methods 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005097 cold rolling Methods 0.000 abstract 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005554 pickling Methods 0.000 abstract 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000010008 shearing Methods 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B47/00—Auxiliary arrangements, devices or methods in connection with rolling of multi-layer sheets of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
- B21B2001/383—Cladded or coated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
- B21B2001/386—Plates
Abstract
The present invention relates to a kind of preparation method of multilayer carbon nanotube/copper composite strip, belong to technical field of composite materials.Copper or copper alloy band are carried out the present invention into pickling and polishing pre-processes, in its surface carbon nano-tube coating coating, then among to folded line asynchronous cold rolling of going forward side by side, the process for repeating polishing coating cold rolling obtains multilayer carbon nanotube/copper or copper alloy composite strip 1 ~ 8 time.The preparation method that the present invention prepares multilayer carbon nanotube/copper composite strip requires low to capacity of equipment, and technique is simple, and controllability is high, and energy consumption is small, and product purity is high, and any surface finish is smooth, is appropriate for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of multilayer carbon nanotube/copper composite strip, belong to technical field of composite materials.
Background technology
There is copper higher electrical conductivity, excellent heat conductivility, and preferably processing ductility to be widely used in electrically
Electronic applications.But copper and its alloy material far can not meet society for high combination property conduction materials such as highly conductive and high intensity
The demand of material.CNT（CNTs）Because the single or multiple lift tubular structure with uniqueness makes it small with density（Only
1.8g/cm3 about 1/6th of steel）, draw ratio is big, high elastic modulus, the good mechanical property such as higher wearability, and
And there is preferable heat conduction and electric conductivity, the physical and chemical performance of relatively low thermal coefficient of expansion, so CNT is described as
Preferable composite enhancing phase.The composite of carbon nanotube reinforced copper and its alloy has high intensity, high conductivity, wear-resisting
The excellent properties such as property.At present, preparing carbon nano tube/copper composite mainly has powder metallurgic method, electroless plating method, and molecular level mixes
It is legal, in-situ synthesis, agitating friction method, but microstructure of composite prepared by powder metallurgic method is thick, low density；Chemical plating
Method, molecular level mixing method, the complex process of in-situ synthesis, CNT are reunited seriously, can have a strong impact on composite
Performance.
Li Caiju etc. is prepared carbon and received using the method for multilayer fine aluminium sleeve structure filling carbon nano-pipe/aluminium composite granule
Mitron strengthens Cu-base composites（201610115738.1）, but be difficult to ensure that in the operation of rolling composite granule in pipe uniformly into
Type, a large amount of holes can be left, obtained composite inner defect is more.
The method that multilayer carbon nanotube/copper composite strip is prepared using asynchronous ply rolling method is there is no at present.
The content of the invention
, should in view of the deficiencies of the prior art, the present invention provides a kind of preparation method of multilayer carbon nanotube/copper composite strip
Method farthest can stack rolling using the shearing compressive plastic deformation during asymmetrical rolling and multi-pass accumulation and obtain
The accumulation equivalent true strain obtained, it can strengthen compound interface combination in limited passage on the premise of thickness of strip is kept, have
Effect avoids the reunion of CNT, the internal flaw of composite and uneven microstructure, multilayer carbon nanotube/copper of preparation
Thickness of composite material is uniform, and surface smoothness is high, and microstructure is uniform, no internal flaw.
A kind of preparation method of multilayer carbon nanotube/copper composite strip, it is characterised in that concretely comprise the following steps：
（1）Copper or copper alloy are placed in 5 ~ 30min of processing in hydrochloric acid solution, cleans, dry；
（2）By step（1）Products obtained therefrom carries out surface polishing pretreatment, exposes metal structure body；
（3）Carbon nano-tube coating is coated uniformly on step（2）The surface of gained prefinished products, be dried to obtain CNT/
Copper strip；
（4）By step（3）Gained carbon nano tube/copper band is to folded, line asynchronous of going forward side by side ply rolling；
（5）By step（4）Products obtained therefrom return to step（2）Surface polishing is carried out to pre-process and carry out step successively（3）And step
（4）, circulate 1 ~ 8 step（2）~（4）Processing obtain multilayer carbon nanotube/copper composite strip；
The step（1）The thickness of middle copper or copper alloy is 0.1 ~ 2mm, and the concentration of hydrochloric acid solution is 6 ~ 12mol/L；
The step（3）Carbon nano-tube coating is carbon nanotube dust or the mixture of CNT and ethanol；
The step（3）Coating method is to close carbon nanotube dust or CNT/alcohol mixed solution roller brush in copper or copper
Surface after gold polishing, until reaching the CNT coating thickness of requirement；
The step（4）The method of asynchronous ply rolling is：A diameter of 250mm ~ the 200mm of topping roll, a diameter of 200mm of bottom roll ~
185mm, top and bottom rolls diameter is asynchronous than being 1.35 ~ 1.08, and top and bottom rolls rotating speed is identical and is 50 ~ 150 revs/min, drafts
For 50%, rolling temperature is room temperature；
The asynchronous ply rolling eliminates compound interface on the premise of thickness of strip is kept in limited passage, farthest profit
With the shearing force during asymmetrical rolling, the compound of CNT and copper or copper alloy is carried out in this condition；
The step（4）The mode for being brought into close contact two faces of carbon nano-tube coating to poststack has static pressure, rivets or beat.
Beneficial effects of the present invention：
（1）The inventive method uses cross-shear rolling, and copper or copper alloy are cut using asymmetrical rolling process larger shearing force
Shear deformation, and larger stranding rolls deformed area and CNT is fully combined in deformation process with copper or copper alloy, and energy
Distribution of the uniform carbon nanotubes in interlayer；
（2）The inventive method uses multi-pass accumulated deformation, not only with alternate more of special carbon nano tube-copper or copper alloy
Rotating fields, and the effective deformation efficiency of carbon nano tube/copper is effectively increased, make the combination of each layer CNT and copper or copper alloy
Reach atom level combination, so as to improve its mechanical property and thermal conductivity；
（3）For the inventive method compared with powder metallurgy process widely used at present, technique is simple, it is not necessary to high temperature sintering, section
About the energy and reduce the discharge of carbon dioxide；And prepare at room temperature, avoid introducing the oxidation of CNT, copper or copper alloy
Thing impurity, the carbon nano tube/copper composite prepared, purity is high, size is larger.
Brief description of the drawings
Fig. 1 is that thickness prepared by the embodiment of the present invention 1 is 0.1mm multilayer carbon nanotubes/fine copper composite strip cross-sectional scans
Figure；
Fig. 2 is that thickness prepared by the embodiment of the present invention 3 is that 2mm multilayer carbon nanotubes/CuSn4 copper alloy composite strips section is swept
Tracing.
Embodiment
The present invention is described in further detail with reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1：A kind of preparation method of multilayer carbon nanotube/copper composite strip, it is characterised in that concretely comprise the following steps：
（1）It is 0.1mm by thickness, width is 60mm industrial pure copper（T2）Band, which is placed in hydrochloric acid solution, handles 5min, wherein
The concentration of hydrochloric acid solution is 6mol/L, cleans, is air-dried in air；
（2）By step（1）Products obtained therefrom carries out surface polishing pretreatment, peels off fine copper band surface oxide layer, exposes metal
Structural body；
（3）Carbon nanotube dust is coated uniformly on step（2）The coating on the surface of gained prefinished products, wherein CNT
Thickness is 5 μm, is dried to obtain carbon nano tube/copper band；
（4）By step（3）Gained carbon nano tube/copper band is brought into close contact the face of carbon nano-tube coating to folded, to poststack riveting,
Line asynchronous of going forward side by side ply rolling, by CNT/pure copper material pressure rolling to 0.1mm, wherein the method for asynchronous ply rolling is：Topping roll diameter
For 200mm, a diameter of 185mm of bottom roll, top and bottom rolls diameter is asynchronous than being 1.08, top and bottom rolls rotating speed it is identical and for 50 turns/
Minute, drafts 50%, rolling temperature is room temperature；Asynchronous ply rolling disappears on the premise of thickness of strip is kept in limited passage
Except compound interface, the shearing force during asymmetrical rolling is farthest utilized, carries out CNT and copper in this condition
It is compound；
（5）By step（4）Products obtained therefrom return to step（2）Surface polishing is carried out to pre-process and carry out step successively（3）And step
（4）Obtain multilayer carbon nanotube/copper composite strip that thickness is 0.1mm；
Thickness manufactured in the present embodiment be 0.1mm multilayer carbon nanotubes/fine copper composite strip cross-sectional scans figure as shown in figure 1, from
Fig. 1 understands that multilayer carbon nanotube manufactured in the present embodiment/fine copper composite strip surface smoothness is high, and thickness is uniform, non-oxidation layer
Or other impurities, the defects of flawless.CNT dissipates well in fine copper interlayer powder, and soilless sticking phenomenon, lamella is uniform, carbon nanometer
Pipe is well combined with fine copper interlayer compound interface.
Embodiment 2：A kind of preparation method of multilayer carbon nanotube/copper composite strip, it is characterised in that concretely comprise the following steps：
（1）It is 1mm by thickness, width is 100mm CuZn40（H62）Copper alloy band, which is placed in hydrochloric acid solution, handles 15min,
Wherein the concentration of hydrochloric acid solution is 9mol/L, cleans, is air-dried in air；
（2）By step（1）Products obtained therefrom carries out surface polishing pretreatment, makes CuZn40（H62）Copper alloy band surface oxide layer
Peel off, expose metal structure body；
（3）Carbon nano-tube coating is coated uniformly on step（2）The surface of gained prefinished products, wherein carbon nano-tube coating are
The mixture of CNT and ethanol, the coating thickness of CNT is 10 μm, is dried to obtain CNT/CuZn40（H62）
Copper alloy band；
（4）By step（3）Gained CNT/CuZn40（H62）For copper alloy band to folded, poststack, which is beaten, makes carbon coating nanometer
The face of pipe is brought into close contact, line asynchronous of going forward side by side ply rolling, is 1mm by CuZn40 Cu alloy materials pressure rolling to thickness, wherein asynchronous ply rolling
Method be：The a diameter of 250mm of topping roll, a diameter of 200mm of bottom roll, top and bottom rolls diameter is asynchronous than being 1.25, rolls up and down
Roller rotating speed is identical and for 150 revs/min, and drafts 50%, rolling temperature is room temperature；Asynchronous ply rolling is keeping thickness of strip
Under the premise of, compound interface is eliminated in limited passage, the shearing force during asymmetrical rolling is farthest utilized, in the state
Lower progress CNT is compound with CuZn40 alloys；
（5）By step（4）Products obtained therefrom return to step（2）Surface polishing is carried out to pre-process and carry out step successively（3）And step
（4）, circulate 5 steps（2）~（4）Processing obtain thickness be 1mm multilayer carbon nanotube/CuZn40 copper alloy composite strips；
It is that 1mm multilayer carbon nanotubes/CuZn40 copper alloy composite strip cross-sectional scans figures can from thickness manufactured in the present embodiment
Know, multilayer carbon nanotube manufactured in the present embodiment/CuZn40 copper alloy composite strips surface smoothness is high, and thickness is uniform, anaerobic
Change layer or other impurities, the defects of flawless.CNT powder between CuZn40 copper alloy layers dissipates good, soilless sticking phenomenon, piece
Uniformly, compound interface is well combined layer between CNT and CuZn40 copper alloy layers.
Embodiment 3：A kind of preparation method of multilayer carbon nanotube/copper composite strip, it is characterised in that concretely comprise the following steps：
（1）It is 2mm by thickness, width is placed in hydrochloric acid solution for 10mm CuSn4 copper alloy bands and handles 15min, wherein salt
The concentration of acid solution is 12mol/L, cleans, is air-dried in air；
（2）By step（1）Products obtained therefrom carries out surface polishing pretreatment, peels off CuSn4 copper alloy bands surface oxide layer, dew
Go out metal structure body；
（3）Carbon nano-tube coating is coated uniformly on step（2）The surface of gained prefinished products, wherein carbon nano-tube coating are
The mixture of CNT and ethanol, the coating thickness of CNT is 20 μm, is dried to obtain CNT/CuSn4 copper alloys
Band；
（4）By step（3）Gained CNT/CuSn4 copper alloy bands make carbon nano-tube coating to folding to poststack static pressure
Face is brought into close contact, line asynchronous of going forward side by side ply rolling, is 2mm by CuSn4 Cu alloy materials pressure rolling to thickness, wherein the method for asynchronous ply rolling
For：The a diameter of 250mm of topping roll, a diameter of 185mm of bottom roll, top and bottom rolls diameter is asynchronous than being 1.35, top and bottom rolls rotating speed
Identical and for 100 revs/min, drafts 50%, rolling temperature is room temperature；Asynchronous ply rolling on the premise of thickness of strip is kept,
Compound interface is eliminated in limited passage, the shearing force during asymmetrical rolling is farthest utilized, carries out in this condition
CNT is compound with CuSn4 copper alloys；
（5）By step（4）Products obtained therefrom return to step（2）Surface polishing is carried out to pre-process and carry out step successively（3）And step
（4）, circulate 8 steps（2）~（4）Processing obtain thickness be 2mm multilayer carbon nanotube/CuSn4 copper alloy composite strips；
Thickness manufactured in the present embodiment is 2mm multilayer carbon nanotubes/CuSn4 copper alloy composite strip cross-sectional scans figure such as Fig. 2 institutes
Show, as can be seen from Figure 2, multilayer carbon nanotube manufactured in the present embodiment/CuSn4 copper alloy composite strips surface smoothness is high, thickness
Uniformly, non-oxidation layer or other impurities, the defects of flawless.CNT powder between CuSn4 copper alloy layers dissipates good, soilless sticking
Phenomenon, lamella is uniform, and compound interface is well combined between CNT and CuSn4 copper alloy layers.
Claims (4)
1. a kind of preparation method of multilayer carbon nanotube/copper composite strip, it is characterised in that concretely comprise the following steps：
（1）Copper or copper alloy are placed in 5 ~ 30min of processing in hydrochloric acid solution, cleans, dry；
（2）By step（1）Products obtained therefrom carries out surface polishing pretreatment；
（3）Carbon nano-tube coating is coated uniformly on step（2）The surface of gained prefinished products, be dried to obtain CNT/
Copper strip；
（4）By step（3）Gained carbon nano tube/copper band is to folded, line asynchronous of going forward side by side ply rolling；
（5）By step（4）Products obtained therefrom return to step（2）Surface polishing is carried out to pre-process and carry out step successively（3）And step
（4）, circulate 1 ~ 8 step（2）~（4）Processing obtain multilayer carbon nanotube/copper composite strip.
2. the preparation method of multilayer carbon nanotube/copper composite strip according to claim 1, it is characterised in that：Step（1）In
The thickness of copper or copper alloy is 0.1 ~ 2mm, and the concentration of hydrochloric acid solution is 6 ~ 12mol/L.
3. the preparation method of multilayer carbon nanotube/copper composite strip according to claim 1, it is characterised in that：Step（3）Carbon
Nanotube coating is carbon nanotube dust or the mixture of CNT and ethanol.
4. the preparation method of multilayer carbon nanotube/copper composite strip according to claim 1, it is characterised in that：Step（4）It is different
Step ply rolling method be：A diameter of 250mm ~ the 200mm of topping roll, a diameter of 200mm ~ 185mm of bottom roll, top and bottom rolls diameter are different
Step is than being 1.35 ~ 1.08, and top and bottom rolls rotating speed is identical and for 50 ~ 150 revs/min, and drafts 50%, rolling temperature is room temperature.
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| CN109396188A (en) * | 2018-09-05 | 2019-03-01 | 江苏大学 | The particles reiforced metal-base composition and preparation method of imitative nacre structural matrix |
| CN111636009A (en) * | 2019-03-01 | 2020-09-08 | 清华大学 | Porous copper composite material and preparation method thereof |
| CN111640947A (en) * | 2019-03-01 | 2020-09-08 | 清华大学 | Current collector and negative electrode of lithium ion battery and preparation methods of current collector and negative electrode |
| CN112373147A (en) * | 2020-10-19 | 2021-02-19 | 西安工程大学 | Preparation method of carbon nano tube and TiC particle hybrid reinforced copper-based composite material |
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Cited By (8)
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|---|---|---|---|---|
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| CN111640947A (en) * | 2019-03-01 | 2020-09-08 | 清华大学 | Current collector and negative electrode of lithium ion battery and preparation methods of current collector and negative electrode |
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| US11575118B2 (en) | 2019-03-01 | 2023-02-07 | Tsinghua University | Current collector and anode electrode of lithium ion battery, and method for fabricating the same |
| CN112373147A (en) * | 2020-10-19 | 2021-02-19 | 西安工程大学 | Preparation method of carbon nano tube and TiC particle hybrid reinforced copper-based composite material |
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