ATBECHDEDKESFRGBGRITLILUNLSEMCPTIESILTLVFIROMKCYALTRBGCZEEHUPLSKBAHRIS..MTNORSMESMMAKHTNMD..........
J
BDM Ver 2.0.16 (1th of February 2022) - 1100000/0
Amended claims in accordance with Rule 137(2) EPC.
4148165
EUROPEAN PATENT APPLICATION
A1
20230315
EP
21199008.0
20210924
20210924
en
en
en
202111020365
20210908
CN
20230315
202311
20230315
202311
C25D 3/38 20060101AFI20220401BHEP
C25D 5/10 20060101ALI20220401BHEP
C25D 5/54 20060101ALI20220401BHEP
C25D 5/54 20130101 FI20220329BHEP
C25D 3/38 20130101 LI20220329BHEP
C25D 5/10 20130101 LI20220329BHEP
C25D 5/48 20130101 LI20220630BHEP
de
VERFAHREN ZUR HERSTELLUNG EINER WÄRMEABLEITENDEN, AUS GRAPHIT- ODER GRAPHENMATERIAL HERGESTELLTEN KOMPONENTE MIT HOHER FLEXIBILITÄT
en
METHOD FOR PREPARING HEAT DISSIPATION COMPONENT WITH HIGH FLEXIBILITY MADE OF GRAPHITE OR GRAPHENE MATERIAL
fr
PROCÉDÉ DE PRÉPARATION D'UN COMPOSANT DE DISSIPATION DE CHALEUR AVEC UNE GRANDE FLEXIBILITÉ EN MATÉRIAU DE GRAPHITE OU DE GRAPHÈNE
Suzhou Ontap Precision Electronic Co., Ltd.
101917342
SZRG-EPP1212340
F3-4,Bldg 16,No.518 Tangdong Rd. Wuzhong Economic Development Zone
Suzhou City Jiangsu
CN
Pang, Meixing
Suzhou City
CN
Cleanthous, Marinos
101964535
4 Prometheus Street, 3 Floor
1065 Nicosia
CY
AL
AT
BE
BG
CH
CY
CZ
DE
DK
EE
ES
FI
FR
GB
GR
HR
HU
IE
IS
IT
LI
LT
LU
LV
MC
MK
MT
NL
NO
PL
PT
RO
RS
SE
SI
SK
SM
TR
BA
ME
KH
MA
MD
TN
The present disclosure disclose a method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material, which includes that follow steps: 1) plasma cleaning a graphite or graphene raw material; 2) taking preparation materials of an activator including the following components in percentage by weight: 10-20% of sulfuric acid, 0.05-1% of an OP-10 surfactant, 0.05-1% of sodium dodecyl sulfate, and the balance of water; 3) continually cleaning the graphite or graphene raw material with the activator; 4) cleaning the graphite or graphene raw material with deionized water; 5) conducting a electroplating process on a surface of the graphite or graphene raw material to form a copper film layer; 6) continually cleaning the graphite or graphene raw material with deionized water; 7) forming a protective film on the graphite or graphene raw material by soaking; and 8) drying the graphite or graphene raw material electroplated with the copper film layer. Compared with the prior art, in the present disclosure, the surface of graphite or graphene treated with the activator has a uniform copper film layer with good binding quality during electroplating, and the flexibility of the prepared heat dissipation component is enhanced.

TECHNICAL FIELD
The present disclosure belong to the field of preparation of parts made of a graphite or graphene material, and particularly relate to a method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material.

BACKGROUND
Graphite is a two-dimensional carbon nanomaterial presented with hexagonal honeycomb lattices and composed of carbon atoms in sp2 hybrid orbitals. Graphite has a very good thermal conduction performance. The pure and defect-free single-layer graphite has thermal conductivity up to 5300 W/mK, and is the carbon material with the highest thermal conductivity so far, and its thermal conductivity is higher than those of a single-walled carbon nanotube (3500 W/mK) and a multi-walled carbon nanotube (3000 W/mK). When it is used as a carrier, the thermal conductivity can also reach 600 W/MK. Furthermore, the ballistic thermal conductivity of graphite can lower the lower limit of the ballistic thermal conductivity of a carbon nanotube of unit circumference and length.
All kinds of electronic elements in electronic products need to dissipate heat. When traditional graphite or graphene is applied for heat dissipation of the electronic elements, it mainly fixes a metal layer on the surface of graphite or graphene, and in particular the metal layer is fixed onto graphite or graphene by bonding or electroplating, wherein electroplating is better than bonding in heat conduction efficiency.
In order to ensure the electroplating quality of the metal layer on the surface of graphite or graphene, it is usually necessary to subject the surface of graphite or graphene to multiple passes of cleaning processes before electroplating. During the cleaning process, after the surface of graphite or graphene is treated with an OP-10 surfactant, the smoothness of the surface of graphite or graphene is general, which leads to poor binding effect and uneven thickness of the metal layer electroplated on the surface of graphite or graphene, and thus affects the flexibility of the prepared heat dissipation component, and the surface of the heat dissipation component is easy to generate creases.

SUMMARY
An objective of the present disclosure is to provide a method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material, which includes the following steps: firstly, plasma cleaning a surface of graphite or graphene, and then treating the surface of graphite or graphene with an activator compounded by sulfuric acid, an OP-10 surfactant and sodium dodecyl sulfate, so that the surface of the material has good smoothness, and it ensures a copper film layer electroplated on the surface of graphite or graphene has good binding quality and uniform, and enhances the flexibility of the prepared heat dissipation component, and the surface of the heat dissipation component is not easy to generate creases.
In order to achieve the aforementioned objective, the present disclosure adopts the following technical solution: a method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material, including the following steps:
1. 1) plasma cleaning a graphite or graphene raw material;
2. 2) taking preparation materials of an activator including the following components in percentage by weight: 10-20% of sulfuric acid, 0.05-1% of an OP-10 surfactant, 0.05-1% of sodium dodecyl sulfate, and the balance of water;
3. 3) mixing the aforementioned components of the activator to prepare the activator, and continually cleaning the graphite or graphene raw material with the activator;
4. 4) continually cleaning the graphite or graphene raw material with deionized water;
5. 5) conducting a electroplating process on a surface of the graphite or graphene raw material to form a copper film layer;
6. 6) continually cleaning the graphite or graphene raw material electroplated with the copper film layer on the surface thereof with deionized water;
7. 7) forming a protective film on the graphite or graphene raw material by soaking; and
8. 8) drying the graphite or graphene raw material electroplated with the copper film layer.
As a further description of the aforementioned technical solution:
In the step 1), the graphite or graphene raw material is placed in a plasma cleaning machine for cleaning.
As a further description of the aforementioned technical solution:
In the step 2), the activator includes the following components in percentage by weight: 12-16% of sulfuric acid, 0.05-0.5% of an OP-10 surfactant, 0.05-0.5% of sodium dodecyl sulfate, and the balance of water.
As a further description of the aforementioned technical solution:
in the step 2), the activator includes the following components in percentage by weight: 15% sulfuric acid, 0.1% of the OP-10 surfactant, 0.1% of sodium dodecyl sulfate, and the balance of water.
As a further description of the aforementioned technical solution:
in the step 5), the graphite or graphene raw material is subjected to the electroplating process twice with an electroplating potion, and the electroplating potion includes the following components in percentage by weight: 5% of copper ions; 14% of sulfuric acid; 0.8% of a brightener; 0.06% of an adjuvant; 0.06% of a leveling agent; and the balance of water.
As a further description of the aforementioned technical solution:
when the graphite or graphene raw material is electroplated with the electroplating potion for the first time, the temperature is 40 celsius degrees and the time is 20 minutes; and when the graphite or graphene raw material is electroplated with the electroplating potion for the second time, the temperature is 40 celsius degrees and the time is 15 minutes.
As a further description of the aforementioned technical solution:
in the step 6), the graphite or graphene raw material is firstly soaked in a 5 g/L methyl benzotriazole solution for 20-30 seconds to form a first layer of protective film, and then put into a 0.5 g/ L cetylpyridinium bromide solution for 20-30 seconds to form a second layer of protective film.
In view of the above, by employing the aforementioned technical solution, the present disclosure has the following beneficial effects.
1. 1. in the present disclosure, the graphite or graphene raw material is firstly placed in a plasma cleaning machine for plasma cleaning, and then the surface of graphite or graphene is treated with an activator compounded by sulfuric acid, the OP-10 surfactant and sodium dodecyl sulfate. Sulphuric acid can wash away oil stains from the graphite or graphene raw material, the OP-10 surfactant improves the smoothness of the surface of the graphite or graphene raw material, and sodium dodecyl sulfate increases the dispersibility of graphite or graphene and further increases the smoothness of the surface of the graphite or graphene raw material, so that the electroplated copper film layer has good binding quality and is uniform, which enhances the flexibility of the prepared heat dissipation component, and the surface of the heat dissipation component is not easy to generate creases, and the heat dissipation and acid and alkali resistance performances of the heat dissipation component are improved.
2. 2. In the present disclosure, after the copper film layer is formed on the graphite or graphene raw material by electroplating, the graphite or graphene raw material electroplated with the copper film layer is first soaked in a 5 g/L methyl benzotriazole solution for 20-30 seconds to form a first layer of protective film on the copper film layer, and then put into a 0.5 g/L cetylpyridinium bromide solution for 20-30 seconds to form a second layer of protective film on the copper film layer, which effectively prevents the copper film layer from color changing.

DETAILED DESCRIPTION OF THE EMBODIMENTS
Exemplary examples of the present disclosure will be described in more detail below. Although exemplary examples of the present disclosure are shown, it should be understood that the present disclosure may be implemented in various forms, and should not be limited by the examples set forth herein. On the contrary, these embodiments are provided to enable a more thorough understanding of the present disclosure and to fully convey the scope of the disclosure to those skilled in the art.

Example 1:
This example of the present disclosure provided a method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material, including the following steps:
1. 1) placing a graphite or graphene raw material in a plasma cleaning machine for plasma cleaning, wherein the plasma cleaning machine had an air pressure of 2 MPa and a power of 550-600 W, and the time for the plasma cleaning was 30 min;
2. 2) taking preparation materials of an activator including the following components in percentage by weight: 15% of sulfuric acid, 0.1% of an OP-10 surfactant, 0.1% of sodium dodecyl sulfate, and the balance of water;
3. 3) mixing the aforementioned components of the activator to prepare the activator, and continually cleaning the graphite or graphene raw material with the activator;
4. 4) continually cleaning the graphite or graphene raw material with deionized water;
5. 5) conducting a electroplating process on a surface of the graphite or graphene raw material twice to form a copper film layer;
6. 6) continually cleaning the graphite or graphene raw material electroplated with the copper film layer on the surface thereof with deionized water;
7. 7) firstly, soaking the graphite or graphene raw material plated with the copper film layer in a 5 g/L methyl benzotriazole solution for 20-30 seconds to form a first layer of protective film on the copper film layer, and then putting into a 0.5 g/L cetylpyridinium bromide solution for 20-30 seconds to form a second layer of protective film on the copper film layer to effectively prevent the copper film from color changing;
8. 8) drying the graphite or graphene raw material electroplated with the copper film layer.
In the step 5), it included two electroplating procedures: firstly, the graphite or graphene raw material was subjected to primary electroplating with an electroplating potion; and secondly, the graphite or graphene raw material was subjected to secondary electroplating with the electroplating potion. The electroplating potion included the following components in percentage by weight: 5% of copper ions; 14% of sulfuric acid; 0.8% of a brightener; 0.06% of an adjuvant; 0.06% of a leveling agent; and the balance of water. During the electroplating process, pickling could be carried out at the same time, so that the flatness of the heat dissipation component was good.
Various process parameters of Example 1 were shown in the table below:
Electroplating process | Component name | Potion concentration | Temperature | Time |
Activation | sulfuric acid | 15% | 25°C | 3 minutes
Surfactant A (OP-10) | 0.10%
sodium dodecyl sulfate | 0.10%
Washing with pure water | deionized water | 25°C | 20 seconds |
Pre-plating of copper | Copper ions | 50 g/l | 40°C | 20 minutes
sulfuric acid | 14%
Additive A (brightener) | 0.80%
Additive B (adjuvant) | 0.06%
Additive C (leveling agent) | 0.06%
Electroplating of copper | Copper ions | 50 g/l | 40°C | 15 minutes
sulfuric acid | 14%
Additive A (brightener) | 0.80%
Additive B (adjuvant) | 0.06%
Additive C (leveling agent) | 0.06%
Cleaning with pure water | deionized water | 25°C | 20 seconds
Protection 1 | methyl benzotriazole | 5g/l | 25°C | 20 seconds
Protection 2 | cetylpyridinium bromide | 0.5g/l | 25°C | 20 seconds
Drying | drying oven | 80°C | 2 minutes

Example 2
This example of the present disclosure provided a method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material, including the following steps:
1. 1) placing a graphite or graphene raw material in a plasma cleaning machine for plasma cleaning, wherein the plasma cleaning machine had an air pressure of 2 MPa and a power of 550-600 W, and the time for the plasma cleaning was 30 min;
2. 2) taking preparation materials of an activator including the following components in percentage by weight: 16% of sulfuric acid, 0.2% of an OP-10 surfactant, 0.2% of sodium dodecyl sulfate, and the balance of water;
3. 3) mixing the aforementioned components of the activator to prepare the activator, and continually cleaning the graphite or graphene raw material with the activator;
4. 4) continually cleaning the graphite or graphene raw material with deionized water;
5. 5) conducting a electroplating process on a surface of the graphite or graphene raw material twice to form a copper film layer;
6. 6) continually cleaning the graphite or graphene raw material electroplated with the copper film layer on the surface thereof with deionized water;
7. 7) firstly, soaking the graphite or graphene raw material plated with the copper film layer in a 5 g/L methyl benzotriazole solution for 20-30 seconds to form a first layer of protective film on the copper film layer, and then putting into a 0.5 g/L cetylpyridinium bromide solution for 20-30 seconds to form a second layer of protective film on the copper film layer to effectively prevent the copper film from color changing;
8. 8) drying the graphite or graphene raw material electroplated with the copper film layer.
In view of the above, compared with the prior art, the method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material as provided by the aforementioned examples has the following advantages. The graphite or graphene raw material is firstly placed in a plasma cleaning machine for plasma cleaning, and then the surface of graphite or graphene is treated with an activator compounded by sulfuric acid, the OP-10 surfactant and sodium dodecyl sulfate. Sulphuric acid can wash away oil stains from the graphite or graphene raw material, the OP-10 surfactant improves the smoothness of the surface of the graphite or graphene raw material, and sodium dodecyl sulfate increases the dispersibility of graphite or graphene and further increases the smoothness of the surface of the graphite or graphene raw material, so that the electroplated copper film layer has good binding quality and is uniform, which enhances the flexibility of the prepared heat dissipation component, and the surface of the heat dissipation component is not easy to generate creases, and the heat dissipation and acid and alkali resistance performances of the heat dissipation component are improved. After the copper film layer is formed on the graphite or graphene raw material by electroplating, the graphite or graphene raw material electroplated with the copper film layer is first soaked in a 5 g/L methyl benzotriazole solution for 20-30 seconds to form a first layer of protective film on the copper film layer, and then put into a 0.5 g/L cetylpyridinium bromide solution for 20-30 seconds to form a second layer of protective film on the copper film layer, which effectively prevents the copper film layer from color changing.
The aforementioned description is only preferred specific embodiments of the present disclosure, and the claimed scope of the present disclosure is not limited thereto. Equivalent substitutions or modifications can be made by those of skills in the art according to the technical solution and inventive concept of the present disclosure, without departing from the technical scope disclosed by the present disclosure. These substitutions or modifications all fall within the claimed scope of the present disclosure.
1. A method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material, comprising the following steps:
1) plasma cleaning a graphite or graphene raw material;
2) taking preparation materials of an activator comprising the following components in percentage by weight: 10-20% of sulfuric acid, 0.05-1% of an OP-10 surfactant, 0.05-1% of sodium dodecyl sulfate, and the balance of water;
3) mixing the aforementioned components of the activator to prepare the activator, and continually cleaning the graphite or graphene raw material with the activator;
4) continually cleaning the graphite or graphene raw material with deionized water;
5) conducting a electroplating process on a surface of the graphite or graphene raw material to form a copper film layer;
6) continually cleaning the graphite or graphene raw material electroplated with the copper film layer on the surface thereof with deionized water;
7) forming a protective film on the graphite or graphene raw material by soaking;
and
8) drying the graphite or graphene raw material electroplated with the copper film layer.
2. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 1, wherein in the step 1), the graphite or graphene raw material is placed in a plasma cleaning machine for cleaning.
3. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 1, wherein in the step 2), the activator comprises the following components in percentage by weight: 12-16% of sulfuric acid, 0.05-0.5% of the OP-10 surfactant, 0.05-0.5% of sodium dodecyl sulfate, and the balance of water.
4. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 3, wherein in the step 2), the activator comprises the following components in percentage by weight: 15% sulfuric acid, 0.1% of the OP-10 surfactant, 0. 1% of sodium dodecyl sulfate, and the balance of water.
5. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 1, wherein in the step 5), the graphite or graphene raw material is subjected to the electroplating process twice with an electroplating potion, and the electroplating potion comprises the following components in percentage by weight: 5% of copper ions; 14% of sulfuric acid; 0.8% of a brightener; 0.06% of an adjuvant; 0.06% of a leveling agent; and the balance of water.
6. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 5, wherein in the step 5), when the graphite or graphene raw material is electroplated with the electroplating potion for the first time, the temperature is 40 celsius degrees and the time is 20 minutes; and when the graphite or graphene raw material is electroplated with the electroplating potion for the second time, the temperature is 40 celsius degrees and the time is 15 minutes.
7. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 1, wherein in the step 6), the graphite or graphene raw material is firstly soaked in a 5 g/L methyl benzotriazole solution for 20-30 seconds to form a first layer of protective film, and then put into a 0.5 g/L cetylpyridinium bromide solution for 20-30 seconds to form a second layer of protective film.

Amended claims in accordance with Rule 137(2) EPC.
1. A method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material, comprising the following steps:
1) plasma cleaning a graphite or graphene raw material;
2) taking preparation materials of an activator comprising the following components in percentage by weight: 10-20% of sulfuric acid, 0.05-1% of an OP-10 surfactant, 0.05-1% of sodium dodecyl sulfate, and the balance being water;
3) mixing the aforementioned components of the activator to prepare the activator, and continually cleaning the graphite or graphene raw material with the activator;
4) continually cleaning the graphite or graphene raw material with deionized water;
5) conducting a electroplating process on a surface of the graphite or graphene raw material to form a copper film layer;
6) continually cleaning the graphite or graphene raw material electroplated with the copper film layer on the surface thereof with deionized water;
7) forming a protective film on the graphite or graphene raw material by soaking, comprising: the graphite or graphene raw material is firstly soaked in a 5 g/L methyl benzotriazole solution for 20-30 seconds to form a first layer of protective film, and then put into a 0.5 g/L cetylpyridinium bromide solution for 20-30 seconds to form a second layer of protective film; and
8) drying the graphite or graphene raw material electroplated with the copper film layer.
2. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 1, wherein in the step 1), the graphite or graphene raw material is placed in a plasma cleaning machine for cleaning.
3. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 1, wherein in the step 2), the activator comprises the following components in percentage by weight: 12-16% of sulfuric acid, 0.05-0.5% of the OP-10 surfactant, 0.05-0.5% of sodium dodecyl sulfate, and the balance being water.
4. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 3, wherein in the step 2), the activator comprises the following components in percentage by weight: 15% sulfuric acid, 0.1% of the OP-10 surfactant, 0.1% of sodium dodecyl sulfate, and the balance being water.
5. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 1, wherein in the step 5), the graphite or graphene raw material is subjected to the electroplating process twice with an electroplating solution, and the electroplating solution comprises the following components in percentage by weight: 5% of copper ions; 14% of sulfuric acid; 0.8% of a brightener; 0.06% of an adjuvant; 0.06% of a leveling agent; and the balance being water.
6. The method for preparing a heat dissipation component with high flexibility made of a graphite or graphene material according to claim 5, wherein in the step 5), when the graphite or graphene raw material is electroplated with the electroplating solution for the first time, the temperature is 40 celsius degrees and the time is 20 minutes; and when the graphite or graphene raw material is electroplated with the electroplating solution for the second time, the temperature is 40 celsius degrees and the time is 15 minutes.
P-2021-835 EP
EP
21199008.0
Suzhou Ontap Precision Electronic Co., Ltd.
DH
20220407
C25D
CN
109748267
B
ONTAP PLATING PREC ELECT CO LTD
20210514
X
1-6
A
7
* abstract *
* examples 1-5 *
* paragaph "summary of the invention" *
CN
108823615
A
JIAXING ZHONGYI CARBON TECH CO LTD
20181116
A
1-7
* abstract *
* examples 1-4 *
CN
103943281
B
UNIV ZHEJIANG
20160504
A
1-7
* abstract *
* example 1 *
Lange, Ronny
The Hague
20220329
CN
109748267
B
20210514
NONE
CN
108823615
A
20181116
NONE
CN
103943281
B
20160504
NONE