CN109334155B - Graphene-copper composite heat dissipation film and preparation method and application thereof - Google Patents
Graphene-copper composite heat dissipation film and preparation method and application thereof Download PDFInfo
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- CN109334155B CN109334155B CN201811246638.8A CN201811246638A CN109334155B CN 109334155 B CN109334155 B CN 109334155B CN 201811246638 A CN201811246638 A CN 201811246638A CN 109334155 B CN109334155 B CN 109334155B
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- 230000017525 heat dissipation Effects 0.000 title claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 35
- 239000010949 copper Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011889 copper foil Substances 0.000 claims abstract description 12
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004945 emulsification Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005096 rolling process Methods 0.000 claims abstract description 6
- 238000010008 shearing Methods 0.000 claims abstract description 6
- 238000004891 communication Methods 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 16
- 238000005520 cutting process Methods 0.000 description 10
- 239000000428 dust Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000003678 scratch resistant effect Effects 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- DWDGSKGGUZPXMQ-UHFFFAOYSA-N OPPO Chemical compound OPPO DWDGSKGGUZPXMQ-UHFFFAOYSA-N 0.000 description 1
- 241000935974 Paralichthys dentatus Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2551/00—Optical elements
Abstract
The invention relates to a graphene-copper composite heat dissipation film and a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, pretreating natural graphite, and then sequentially carrying out high-speed shearing, ultrasonic stripping and emulsification to obtain graphene; mixing graphene, preparing a film, drying to obtain a graphene film, heating the graphene film at a preset temperature to prepare a micro-airbag, and mechanically rolling the micro-airbag under a preset pressure to prepare a micro-wrinkle; and compacting the graphene film and the copper foil, and then adhering the heat-conducting black film to the other side of the copper foil to obtain the graphene-copper composite heat-dissipation film. According to the preparation method of the graphene-copper composite heat dissipation film, the point-like heat source is balanced to the surface, and then is dissipated longitudinally, so that heat dissipation is accelerated, the protection effect of product components is achieved, and the heat dissipation effect of the graphene-copper composite heat dissipation film is superior to that of graphite sheets and artificial graphite sheets in the traditional process.
Description
Technical Field
The invention belongs to the field of material processing and preparation, and particularly relates to a graphene-copper composite heat dissipation film and a preparation method and application thereof.
Background
Graphene (Graphene) is a planar film with hexagonal honeycomb lattice of carbon atoms with sp2 hybrid orbitals, and has a thickness of only one carbon atom. Graphene is the thinnest and the hardest nano material in the world at present, is almost completely transparent, and only absorbs 2.3% of light; the heat conductivity coefficient is as high as 5300W/m.K, higher than that of carbon nano tube and diamond, and its electron mobility is over 15000cm at normal temp2The resistivity of the material is only about 10-8 omega m, lower than that of copper or silver, and the material has the minimum resistivity in the world. Electronic appliances generate heat when working, and efficient heat management is needed to ensure normal operation of the electronic appliances. The new generation of devices also requires bendability. Thus, it is possible to provideThe research on high-heat-conductivity and high-flexibility materials is very important. However, the high thermal conductivity and high flexibility of the existing macroscopic materials are the contradiction that a pair of fish and bear paw are difficult to obtain. The appearance of graphene provides theoretical possibilities for solving this contradiction. It is a honeycomb planar monolayer two-dimensional macromolecule formed by carbon atoms in an sp2 hybridization manner. The bonding structure with light atomic weight, simplicity and strong force endows the material with ultrahigh thermal conductivity; meanwhile, the thickness of the monoatomic layer enables the monoatomic layer to have better flexibility. Unfortunately, the existing exfoliated graphene sheets are small and have many defects, and the thermal conductivity and flexibility of a macroscopic material assembled by the graphene sheets are poor.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene-copper composite heat dissipation film.
The preparation method of the graphene-copper composite heat dissipation film comprises the following steps: s101: firstly, pretreating natural graphite, and then sequentially carrying out high-speed shearing, ultrasonic stripping and emulsification to obtain graphene; s102: mixing the graphene obtained in the step S101, preparing a film, drying to obtain a graphene film, heating the graphene film at a preset temperature to prepare a micro-airbag, and mechanically rolling the micro-airbag under a preset pressure to prepare a micro-wrinkle; s103: and (4) compacting the graphene film processed in the step (S102) and a copper foil, and then adhering the heat-conducting black film to the other side of the copper foil to obtain the graphene-copper composite heat dissipation film.
According to the preparation method of the graphene-copper composite heat dissipation film, the point-like heat source is balanced to the surface, and then the heat is dissipated longitudinally, so that the heat dissipation is accelerated, and the protection effect of a product assembly is achieved. The heat dissipation effect is superior to that of graphite flakes and artificial graphite flakes in the traditional process. The graphene nanometer heat dissipation layer is highly compact, scratch-resistant, alcohol-resistant and solvent-resistant, die-cutting is simple, yield is high, edge covering and covering film adding are not needed, and heat dissipation performance is more outstanding. The product has good flexibility, can be processed and repaired; EMI shielding and absorption to protect sensitive electronic components; solvent resistance, antistatic ability, resistance of 103 ohm/square inch; the product can be molded and cut into any shape, does not drop dust and does not need edge wrapping; the point heat source can be quickly converted into a surface heat source through conduction heat dissipation, convection heat dissipation and radiation heat dissipation; the temperature of the electronic product can be reduced, electronic components can be protected, and the service life of the electronic product can be prolonged; the self-developed low-acid heat radiation soaking glue does not corrode electronic components; the material has excellent conductive performance; the edges are neat after die cutting without dust; compared with a natural graphite film or an artificial graphite film, dust is left after die cutting, and the danger of circuit short circuit is possibly generated on internal electronic components of products such as mobile phones and tablet computers; the copper is used as the base material, so that the die cutting is convenient, the cracking is avoided, and the yield is high; both natural graphite and artificial graphite have no copper base layer and are easy to damage in the die cutting process and the pasting process; is favorable for machine repair and can be used again.
In addition, the preparation method of the graphene-copper composite heat dissipation film of the invention can also have the following additional technical characteristics:
further, the thickness of the graphene-copper composite heat dissipation film is 25-150 μm.
Further, in the step S102, the preset temperature is 2900 ℃ to 3100 ℃.
Further, in the step S102, the preset pressure is 290MPa to 310 MPa.
The invention also aims to provide the graphene-copper composite heat dissipation film prepared by the method.
The invention further aims to provide application of the graphene-copper composite heat dissipation film in the fields of intelligent terminals, LEDs, communication industries and new energy.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
Example 1
Embodiment 1 provides a graphene-copper composite heat dissipation film, and a preparation method thereof, including the steps of:
s101: firstly, pretreating natural graphite, and then sequentially carrying out high-speed shearing, ultrasonic stripping and emulsification to obtain graphene.
S102: and (2) mixing the graphene obtained in the step (S101), preparing a film, drying to obtain a graphene film, heating the graphene film at 2900 ℃ to prepare a micro-airbag, and mechanically rolling the micro-airbag under the pressure of 310MPa to prepare a micro-wrinkle.
S103: and (4) compacting the graphene film processed in the step (S102) and a copper foil, and then adhering the heat-conducting black film to the other side of the copper foil to obtain the graphene-copper composite heat dissipation film with the thickness of 25 microns.
Example 2
Embodiment 2 provides a graphene-copper composite heat dissipation film, and a preparation method thereof, including the steps of:
s101: firstly, pretreating natural graphite, and then sequentially carrying out high-speed shearing, ultrasonic stripping and emulsification to obtain graphene.
S102: and (2) mixing the graphene obtained in the step (S101), preparing a film, drying to obtain a graphene film, heating the graphene film at 3100 ℃ to prepare a micro-airbag, and mechanically rolling the micro-airbag under 290MPa to prepare a micro-wrinkle.
S103: and (4) compacting the graphene film processed in the step (S102) and a copper foil, and then adhering the heat-conducting black film to the other side of the copper foil to obtain the graphene-copper composite heat dissipation film with the thickness of 150 microns.
Example 3
Embodiment 3 provides a graphene-copper composite heat dissipation film, and a preparation method thereof, including the steps of:
s101: firstly, pretreating natural graphite, and then sequentially carrying out high-speed shearing, ultrasonic stripping and emulsification to obtain graphene.
S102: and (2) mixing the graphene obtained in the step (S101), preparing a film, drying to obtain a graphene film, heating the graphene film at 3000 ℃ to prepare a micro-airbag, and mechanically rolling the micro-airbag under 300MPa to prepare a micro-wrinkle.
S103: and (4) compacting the graphene film processed in the step (S102) and a copper foil, and then adhering the heat-conducting black film to the other side of the copper foil to obtain the graphene-copper composite heat dissipation film with the thickness of 80 microns.
Table 1: thermal black film parameters
The OPPO prototype was tested in the New Material laboratory at the foundational base of Popul area, Shanghai, by a professional FLUKE TiS65 test instrument: 1. respectively sticking a back adhesive and a double-sided adhesive to two sides of the heat dissipation film, then sticking the heat dissipation film to the inner side of a back cover of a prototype, operating the torrent yacht 2 for one hour, and selecting the maximum data of temperature difference (delta T/DEG C) within 1 hour according to the test result; 2. the test is repeated for 3 times for each sample, the maximum temperature difference value is selected, the result is equivalent to the temperature coefficient of the artificial graphite, and the product performance is obviously superior to that of the artificial graphite film after the insulating black film prepared by the method replaces the black film on the market.
The graphene-copper heat dissipation film prepared by the invention has the following characteristics:
1. the heat dissipation effect is good and is comparable to the effect of the artificial graphite film;
2. the heat dissipation and soaking device has the advantages of transverse heat dissipation and soaking and longitudinal rapid heat conduction;
3. the product has good flexibility, and is easy to process, die cut, install and use;
4. high reliability, high stability and no aging problem;
5. high cost performance.
The graphene-copper heat dissipation film prepared in the embodiment of the invention is compared with other heat dissipation materials, and the result is shown in table 2.
Table 2: comparative analysis of heat sink materials
As can be seen from comparison of table 2, the graphene-copper heat dissipation film of the present invention has significant advantages compared to other heat dissipation products:
1. the heat conductivity coefficient can be compared with that of artificial graphite;
2. the cost is only 60 percent of that of the artificial graphite;
3. the workability and the folding times are more excellent than other products.
In conclusion, according to the preparation method of the graphene-copper composite heat dissipation film, the heat dissipation is accelerated by balancing the point-shaped heat source to the surface and then longitudinally dissipating the heat, so that the protection effect of the product assembly is achieved. The heat dissipation effect is superior to that of graphite flakes and artificial graphite flakes in the traditional process. The graphene nanometer heat dissipation layer is highly compact, scratch-resistant, alcohol-resistant and solvent-resistant, die-cutting is simple, yield is high, edge covering and covering film adding are not needed, and heat dissipation performance is more outstanding. The product has good flexibility, can be processed and repaired; EMI shielding and absorption to protect sensitive electronic components; solvent resistance, antistatic ability, resistance of 103 ohm/square inch; the product can be molded and cut into any shape, does not drop dust and does not need edge wrapping; the point heat source can be quickly converted into a surface heat source through conduction heat dissipation, convection heat dissipation and radiation heat dissipation; the temperature of the electronic product can be reduced, electronic components can be protected, and the service life of the electronic product can be prolonged; the self-developed low-acid heat radiation soaking glue does not corrode electronic components; the material has excellent conductive performance; the edges are neat after die cutting without dust; compared with a natural graphite film or an artificial graphite film, dust is left after die cutting, and the danger of circuit short circuit is possibly generated on internal electronic components of products such as mobile phones and tablet computers; the copper is used as the base material, so that the die cutting is convenient, the cracking is avoided, and the yield is high; both natural graphite and artificial graphite have no copper base layer and are easy to damage in the die cutting process and the pasting process; is favorable for machine repair and can be used again.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. A preparation method of a graphene-copper composite heat dissipation film is characterized by comprising the following steps:
s101: firstly, pretreating natural graphite, and then sequentially carrying out high-speed shearing, ultrasonic stripping and emulsification to obtain graphene;
s102: mixing the graphene obtained in the step S101, preparing a film, drying to obtain a graphene film, heating the graphene film at a preset temperature to prepare a micro-airbag, and mechanically rolling the micro-airbag under a preset pressure to prepare a micro-wrinkle;
s103: compacting the graphene film treated in the step S102 and a copper foil, and then adhering a heat-conducting black film to the other side of the copper foil to obtain a graphene-copper composite heat dissipation film;
the thickness of the graphene-copper composite heat dissipation film is 25-150 micrometers;
in the step S102, the preset temperature is 2900-3100 ℃;
in the step S102, the preset pressure is 290MPa to 310 MPa.
2. The graphene-copper composite heat dissipation film prepared by the method of claim 1.
3. The graphene-copper composite heat dissipation film of any one of claims 1-2 is applied to the fields of intelligent terminals, LEDs, communication industry and new energy.
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| CN204981729U (en) * | 2015-04-07 | 2016-01-20 | 上海悦达墨特瑞新材料科技有限公司 | High -efficient thermal film who contains thermal conductive adhesive |
| CN105731435A (en) * | 2016-01-25 | 2016-07-06 | 浙江碳谷上希材料科技有限公司 | High-strength flexible graphene composite heat conduction film and preparation method thereof |
| CN105731434A (en) * | 2016-01-25 | 2016-07-06 | 浙江伟星新型建材股份有限公司 | Graphene film for light efficient electromagnetic shielding and preparation method thereof |
| CN206350292U (en) * | 2017-01-13 | 2017-07-21 | 深圳市莱必德电子材料有限公司 | The graphene heat dissipation film of low cost |
| CN107555419A (en) * | 2017-10-13 | 2018-01-09 | 杭州高烯科技有限公司 | A kind of low corrugation density graphene film and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204981729U (en) * | 2015-04-07 | 2016-01-20 | 上海悦达墨特瑞新材料科技有限公司 | High -efficient thermal film who contains thermal conductive adhesive |
| CN105731435A (en) * | 2016-01-25 | 2016-07-06 | 浙江碳谷上希材料科技有限公司 | High-strength flexible graphene composite heat conduction film and preparation method thereof |
| CN105731434A (en) * | 2016-01-25 | 2016-07-06 | 浙江伟星新型建材股份有限公司 | Graphene film for light efficient electromagnetic shielding and preparation method thereof |
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Effective date of registration: 20230118 Address after: Room 1001, Floor 10, Building 2, Zone A, Lane 587, Juxian Road, Ningbo High-tech Zone, Ningbo City, Zhejiang Province Patentee after: Ningbo Fengfeng robot Co.,Ltd. Address before: 215634 room 429, building a, emerging industry education center, Zhangjiagang Free Trade Zone, Suzhou, Jiangsu Patentee before: ZHANGJIAGANG ZHANBO ELECTRONIC TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20240116 Address after: No. 1-5-52 Xiangtan Street, Longtan District, Jilin City, Jilin Province, 132000 Patentee after: Zhu Youxin Address before: Room 1001, 10th Floor, Building 2, Block A, Lane 587, Juxian Road, Ningbo High tech Zone, Ningbo City, Zhejiang Province Patentee before: Ningbo Fengfeng robot Co.,Ltd. |
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