CN105274504B - One kind is in expanded graphite process for copper coating on surface - Google Patents
One kind is in expanded graphite process for copper coating on surface Download PDFInfo
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Abstract
It is a kind of in expanded graphite process for copper coating on surface, first in expanded graphite chemical nickel plating on surface, form dispersed nickel activation point.In chemical nickel plating using iron blender or nickel blender and expanded graphite plating at the same time, and carry out mechanical agitation, oxidation corrosion occurs in the plating solution using metallic iron or nickel, discharge electronics, pass through the contact with expanded graphite, electronics is transmitted to expanded graphite surface, so that the deposition reaction of nickel occur on expanded graphite surface, dispersed nickel activation point is formed on expanded graphite surface.Then expanded graphite that Dispersion on surface to nickel activation point is put into the plating solution of electroless copper, carries out the electroless copper of second step.For the nickel activation point that the first step is formed on expanded graphite surface using as the catalytic active center of second step electroless copper, catalytic chemistry copper facing reaction, makes copper ion deposit to form copper plate on expanded graphite surface centered on this nickel activation point.
Description
Technical field
The present invention relates to a kind of expanded graphite process for copper coating on surface.
Background technology
Expanded graphite powder is that expansion obtains vermicular expanded graphite rapidly at high temperature by expansible graphite, is being passed through into one
Obtained after the pulverization process of step.Expanded graphite has high electrical conductivity and very big surface area, so that expanded graphite
With many excellent performances.The composite material of expanded graphite copper coating is due to good mechanics and electric property, together
When with good thermal conductivity and lubricity etc., be widely used in national economy.In the powder metallurgy process system of use
During standby graphite-copper based composites, since the wetability of liquid copper and graphite is bad, interface bond strength is low, often results in stone
The extraction of black reinforcement, peel off, therefore copper coated graphite powder and copper then are mixed and made into stone in graphite surface electroless copper first
Ink-Cu-base composites.When graphite is added to carrier fluid as filler, since graphite surface is hydrophobic in nature, often adopt
Surface modification is carried out to graphite with the method for chemical plating.Due to the chemical bond key between the atom of expanded graphite for covalent bond and
Molecular link, and the chemical bond key of metal copper atom is metallic bond so that golden in expanded graphite coating surface using chemical plating
When belonging to copper, metal copper-base is not easy to deposit to copper coating on expanded graphite surface.For this reason, chemical plating is being utilized on expanded graphite surface
, it is necessary to which expanded graphite is positioned over PdCl in advance during metal lining copper2-SnCl2Expanded graphite surface is sensitized in solution,
Activation process so that expanded graphite surface forms palladium activation point, then carries out electroless copper.Due to PdCl2It is expensive, use
Plating effect is poor when measuring less, can increase cost when usage amount is big again, and the preprocessing process processing step is various, and process is multiple
It is miscellaneous.
The content of the invention：
Palladium bichloride need to be used during the purpose of the present invention is for expanded graphite Electroless copper to expanded graphite surface
Carry out activation process and cause production cost to rise problem, propose a kind of expanded graphite process for copper coating on surface.The present invention
Activation process is carried out to expanded graphite surface without using palladium bichloride, so as to reduce being produced into for expanded graphite Electroless copper
This, while reduce the production process of electroless copper.
The purpose of the present invention is realized by following technical proposals.
The present invention by expanded graphite chemical nickel plating, forms dispersed nickel activation point first.Used in chemical nickel plating
Iron blender or nickel blender and expanded graphite plating at the same time, are carried out at the same time mechanical agitation, using metallic iron or nickel in the plating solution
Generation oxidation corrosion, discharges electronics, by the contact with expanded graphite, electronics is transmitted to expanded graphite surface, so that swollen
The deposition reaction of nickel occurs for swollen graphite surface.Dispersed nickel activation point is formed on expanded graphite surface, then by surface point
The expanded graphite for dissipating nickel activation point is put into the plating solution of electroless copper, carries out the electroless copper of second step.The first step is expanding
The nickel activation point that graphite surface is formed replaces using as the catalytic active center of second step electroless copper and catalytic chemistry copper facing is anti-
Should, copper ion is deposited centered on this nickel activation point on expanded graphite surface, form copper plate.
The present invention to expanded graphite surface when carrying out electroless copper, without using PdCl2-SnCl2Solution is to expanded graphite
Surface carries out preactivated sensitized treatment, reduces the production cost of expanded graphite Electroless copper, eliminates expanded graphite
The pretreatment process such as the activation sensitization of Electroless copper, washing, dispergation.
The present invention's comprises the following steps that：
The first step：Pretreatment
1.1 surface degreasing：Expanded graphite powder is placed in NaOH alkaline solutions, the magnetic agitation at a temperature of 30~100 DEG C
20~50min, is cleaned to neutrality repeatedly with deionized water, stand-by after being dried at a temperature of 80~100 DEG C to constant weight.
1.2 roughening treatment：Expanded graphite powder after oil removing is placed in coarsening solution, the electromagnetism at 30~40 DEG C of temperature range
Stirring, coarsening time is 5~30min.Coarsening solution component is：150~200g/L (NH4)2S2O8(ammonium peroxydisulfate), 50~
100mL/L H2SO4, H2SO4Density be 1.84g/cm3；It is washed with deionized water after roughening to neutrality, at a temperature of 80~100 DEG C
It is stand-by after drying to constant weight；
Second step：Chemical nickel plating
2.1 configuration chemical nickel-plating solutions：Chemical plating fluid is by six hydration nickel sulfate, sodium citrate, ammonium chloride, ortho phosphorous acid
Sodium, ammonium hydroxide and deionized water composition.Dosage：10~30g/L of six hydration nickel sulfate, 10~30g/L of sodium citrate, ammonium chloride 10
~35g/L, 10~30g/L of sodium hypophosphite, it is 8~10 that ammonium hydroxide, which adjusts pH value,；
2.2 chemical nickel plating：Pretreated expanded graphite is placed in chemical nickel-plating solution prepared by step 2.1, at the same time
Electrode potential is less than to the metal of nickel, such as iron, or the metallic nickel that itself has catalytic activity to be placed in chemical nickel-plating solution, is utilized
Oxidation corrosion occurs in the plating solution for metal, discharges electronics, by the contact with expanded graphite, electronics is transmitted to expanded graphite table
Face, so that the deposition reaction of nickel occur on expanded graphite surface, forms dispersed nickel activation point on expanded graphite surface.This
Invention is carried out at the same time stirring using iron blender or nickel blender and expanded graphite plating at the same time, and mixing speed 300r/min~
1000r/min, reaction temperature are 40~80 DEG C, 30~150min of reaction time.Take out the expanded graphite after reaction be placed in 80~
Dry 5~10h, obtains the expanded graphite powder after nickel plating in 120 DEG C of vacuum drying chamber.
3rd step：Electroless copper
3.1 prepare chemical copper plating solution：Chemical plating fluid is by cupric sulfate pentahydrate, disodium ethylene diamine tetraacetate, sodium hydroxide, first
Aldehyde, bipyridyl etc. form.Dosage：10~20g/L of cupric sulfate pentahydrate, 10~30g/L of disodium ethylene diamine tetraacetate, sodium hydroxide 5
~10g/L, 5~20mL/L of formaldehyde, bipyridyl are micro.
3.2 electroless copper：Expanded graphite through second step nickel plating is placed in chemical copper plating solution prepared by step 3.1,
Using mechanical agitation, mixing speed 300r/min~1000r/min, it is 40~80 DEG C to adjust reaction temperature, the reaction time 30~
150min.The expanded graphite after reaction is taken out to be cleaned up with deionized water.
3.3 passivation：The copper facing expanded graphite rinsed well is added to the disodium ethylene diamine tetraacetate that mass fraction is 5%
In passivating solution, 15min is stirred, then deionization cleans up, and is placed in 80~120 DEG C of vacuum drying chamber dry 5~10h,
Obtain copper facing expanded graphite powder.
The second step chemical nickel plating forms dispersed nickel activation point on expanded graphite surface.
The beneficial effects of the invention are as follows：Reduce the use to precious metal palladium, reduce the production cost of electroless copper, save
The preactivated sensitized treatment of electroless copper is removed：The processes such as washing, dispergation.
Brief description of the drawings
Fig. 1 is the flow chart of the method for the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of expanded graphite chemical nickel plating；
Fig. 3 is the energy spectrum diagram of expanded graphite chemical nickel plating；
Fig. 4 is the scanning electron microscope (SEM) photograph of expanded graphite electroless copper；
Fig. 5 is the energy spectrum diagram of expanded graphite electroless copper；
Fig. 6 is the scanning electron microscope (SEM) photograph of expanded graphite electroless copper；
Fig. 7 is the scanning electron microscope (SEM) photograph of expanded graphite electroless copper；
Fig. 8 is the scanning electron microscope (SEM) photograph of expanded graphite electroless copper.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Embodiment 1
The first step：Pretreatment
1.1 surface degreasing：3g expanded graphite powder is weighed to be placed in the NaOH alkaline solutions that 100ml mass fractions are 10%,
The magnetic agitation 30min at a temperature of 70 DEG C, is cleaned to neutrality repeatedly with deionized water, is treated after being dried at a temperature of 80 DEG C to constant weight
With.
1.2 roughening treatment：Expanded graphite powder after oil removing is placed in 200ml coarsening solutions, the electromagnetic agitation at 30 DEG C
30min.Coarsening solution component is：200g/L(NH4)2S2O8(ammonium peroxydisulfate), 100mL/LH2SO4, H2SO4Density is 1.84g/
cm3；It is washed with deionized water after roughening to neutrality, it is stand-by after being dried at a temperature of 80 DEG C to constant weight；
Second step：Chemical nickel plating
2.1 configuration chemical nickel-plating solutions：Chemical plating fluid is by six hydration nickel sulfate, sodium citrate, ammonium chloride, ortho phosphorous acid
Sodium, ammonium hydroxide and deionized water composition.Dosage：Six hydration nickel sulfate 30g/L, sodium citrate 15g/L, ammonium chloride 30g/L, secondary Asia
Sodium phosphate 30g/L, it is 9.5 that ammonium hydroxide, which adjusts pH value,；
2.2 chemical nickel plating：Pretreated expanded graphite is placed in 500ml chemical nickel-plating solutions, using iron blender
It is stirred, mixing speed 500r/min, it is 60 DEG C to adjust reaction temperature, reaction time 100min.Take out the expansion after reaction
Graphite is placed in 80 DEG C of vacuum drying chamber dry 10h, obtains the expanded graphite powder after nickel plating.
As shown in Fig. 2, scanned electron microscopic observation, expanded graphite surface forms dispersed nickel after chemical nickel plating
Grain, power spectrum are shown in Fig. 3.Catalytic deposition center using this nickel particle as electroless copper carries out follow-up electroless copper.
3rd step：Electroless copper
3.1 configuration chemical copper plating solutions：Chemical plating fluid is by cupric sulfate pentahydrate, disodium ethylene diamine tetraacetate, sodium hydroxide, first
Aldehyde, bipyridyl etc. form.Dosage：Cupric sulfate pentahydrate 20g/L, disodium ethylene diamine tetraacetate 30g/L, sodium hydroxide 7g/L, quality
Fraction is 37% formaldehyde 12mL/L, bipyridyl 0.1g/L.
3.2 electroless copper：1g nickel plating expanded graphites are placed in 500ml chemical copper plating solutions, mixing speed 500r/min,
It is 65 DEG C to adjust reaction temperature, reaction time 60min.The expanded graphite after reaction is taken out to be cleaned up with deionized water.
3.3 passivation：The copper facing expanded graphite that will be rinsed well, adds the disodium ethylene diamine tetraacetate that mass fraction is 5%
In passivating solution, 15min is stirred, is then cleaned up with deionized water, be placed in 80 DEG C of vacuum drying chamber dry 10h, obtain
Copper facing expanded graphite powder.
As shown in figure 4, scanned electron microscopic observation, after electroless copper expanded graphite surface coated one layer it is complete, fine and close
Metal copper coating, Fig. 5 show the energy spectrum diagram of the expanded graphite sample.
Embodiment 2
The first step：Pretreatment
1.1 surface degreasing：3g expanded graphite powder is weighed to be placed in the NaOH alkaline solutions that 100ml mass fractions are 10%,
The magnetic agitation 50min at a temperature of 30 DEG C, is cleaned to neutrality repeatedly with deionized water, is treated after being dried at a temperature of 90 DEG C to constant weight
With.
1.2 roughening treatment：Expanded graphite powder after oil removing is placed in 200ml coarsening solutions, the electromagnetic agitation at 40 DEG C
15min.Coarsening solution component is：150g/L(NH4)2S2O8(ammonium peroxydisulfate), 100mL/LH2SO4, H2SO4Density is 1.84g/
cm3；It is washed with deionized water after roughening to neutrality, it is stand-by after being dried at a temperature of 90 DEG C to constant weight；
Second step：Chemical nickel plating
2.1 configuration chemical nickel-plating solutions：Chemical plating fluid is by six hydration nickel sulfate, sodium citrate, ammonium chloride, ortho phosphorous acid
Sodium, ammonium hydroxide and deionized water composition.Dosage：Six hydration nickel sulfate 20g/L, sodium citrate 30g/L, ammonium chloride 30g/L, secondary Asia
Sodium phosphate 20g/L, it is 8 that ammonium hydroxide, which adjusts pH value,；
2.2 chemical nickel plating：Pretreated expanded graphite is placed in 500ml chemical nickel-plating solutions, using iron blender
It is stirred, mixing speed 300r/min, it is 40 DEG C to adjust reaction temperature, reaction time 150min.Take out the expansion after reaction
Graphite is placed in 100 DEG C of vacuum drying chamber dry 7h, obtains the expanded graphite powder after nickel plating.
Expanded graphite surface forms dispersed nickel particle after chemical nickel plating, using this nickel particle urging as electroless copper
Change depocenter and carry out follow-up electroless copper.
3rd step：Electroless copper
3.1 configuration chemical copper plating solutions：Chemical plating fluid is by cupric sulfate pentahydrate, disodium ethylene diamine tetraacetate, sodium hydroxide, first
Aldehyde, bipyridyl etc. form.Dosage：Cupric sulfate pentahydrate 15g/L, disodium ethylene diamine tetraacetate 10g/L, sodium hydroxide 5g/L, quality
Fraction is 37% formaldehyde 15mL/L, bipyridyl 0.1g/L.
3.2 electroless copper：1g nickel plating expanded graphites are placed in 500ml chemical copper plating solutions, mixing speed 300r/min,
It is 40 DEG C to adjust reaction temperature, reaction time 150min.The expanded graphite after reaction is taken out to be cleaned up with deionized water.
3.3 passivation：The copper facing expanded graphite that will be rinsed well, adds the disodium ethylene diamine tetraacetate that mass fraction is 5%
In passivating solution, 15min is stirred, is then cleaned up with deionized water, be placed in 100 DEG C of vacuum drying chamber dry 10h, obtain
Copper facing expanded graphite powder.
As shown in fig. 6, scanned electron microscopic observation, after electroless copper expanded graphite surface coated one layer it is complete, fine and close
Metal copper coating.
Embodiment 3
The first step：Pretreatment
1.1 surface degreasing：2g expanded graphite powder is weighed to be placed in the NaOH alkaline solutions that 100ml mass fractions are 10%,
The magnetic agitation 20min at a temperature of 100 DEG C, is cleaned to neutrality repeatedly with deionized water, after being dried at a temperature of 100 DEG C to constant weight
It is stand-by.
1.2 roughening treatment：Expanded graphite powder after oil removing is placed in 200ml coarsening solutions, the electromagnetic agitation at 40 DEG C
5min.Coarsening solution component is：175g/L(NH4)2S2O8(ammonium peroxydisulfate), 75mL/LH2SO4, H2SO4Density is 1.84g/cm3；
It is washed with deionized water after roughening to neutrality, it is stand-by after being dried at a temperature of 100 DEG C to constant weight；
Second step：Chemical nickel plating
2.1 configuration chemical nickel-plating solutions：Chemical plating fluid is by six hydration nickel sulfate, sodium citrate, ammonium chloride, ortho phosphorous acid
Sodium, ammonium hydroxide and deionized water composition.Dosage：Six hydration nickel sulfate 10g/L, sodium citrate 10g/L, ammonium chloride 30g/L, secondary Asia
Sodium phosphate 10g/L, it is 10 that ammonium hydroxide, which adjusts pH value,；
2.2 chemical nickel plating：Pretreated expanded graphite is placed in 500ml chemical nickel-plating solutions, using iron blender
It is stirred, mixing speed 700r/min, it is 80 DEG C to adjust reaction temperature, reaction time 30min.Take out the expansion stone after reaction
Ink is placed in 120 DEG C of vacuum drying chamber dry 5h, obtains the expanded graphite powder after nickel plating.
Expanded graphite surface forms dispersed nickel particle after chemical nickel plating.Using this nickel particle urging as electroless copper
Change depocenter and carry out follow-up electroless copper.
3rd step：Electroless copper
3.1 configuration chemical copper plating solutions：Chemical plating fluid is by cupric sulfate pentahydrate, disodium ethylene diamine tetraacetate, sodium hydroxide, first
Aldehyde, bipyridyl etc. form.Dosage：Cupric sulfate pentahydrate 10g/L, disodium ethylene diamine tetraacetate 15g/L, sodium hydroxide 8g/L, formaldehyde
(37%) 20mL/L, bipyridyl 0.1g/L.
3.2 electroless copper：0.5g nickel plating expanded graphites are placed in 500ml chemical copper plating solutions, mixing speed 600r/
Min, it is 80 DEG C to adjust reaction temperature, reaction time 30min.Expanded graphite after taking-up reaction is cleaned dry with deionized water
Only.
3.3 passivation：The copper facing expanded graphite that will be rinsed well, adds the disodium ethylene diamine tetraacetate that mass fraction is 5%
In passivating solution, 15min is stirred, is then cleaned up with deionized water, be placed in 100 DEG C of vacuum drying chamber dry 8h, obtain
Copper facing expanded graphite powder.
As shown in fig. 7, scanned electron microscopic observation, after electroless copper expanded graphite surface coated one layer it is complete, fine and close
Metal copper coating.
Embodiment 4
The first step：Pretreatment
1.1 surface degreasing：2g expanded graphite powder is weighed to be placed in the NaOH alkaline solutions that 100ml mass fractions are 10%,
The magnetic agitation 40min at a temperature of 30 DEG C, is cleaned to neutrality repeatedly with deionized water, is treated after being dried at a temperature of 80 DEG C to constant weight
With.
1.2 roughening treatment：Expanded graphite powder after oil removing is placed in 200ml coarsening solutions, the electromagnetic agitation at 35 DEG C
20min.Coarsening solution component is：200g/L(NH4)2S2O8(ammonium peroxydisulfate), 50mL/LH2SO4, H2SO4Density is 1.84g/
cm3；It is washed with deionized water after roughening to neutrality, it is stand-by after being dried at a temperature of 80 DEG C to constant weight；
Second step：Chemical nickel plating
2.1 configuration chemical nickel-plating solutions：Chemical plating fluid is by six hydration nickel sulfate, sodium citrate, ammonium chloride, ortho phosphorous acid
Sodium, ammonium hydroxide and deionized water composition.Dosage：Six hydration nickel sulfate 25g/L, sodium citrate 20g/L, ammonium chloride 30g/L, secondary Asia
Sodium phosphate 30g/L, it is 9.0 that ammonium hydroxide, which adjusts pH value,；
2.2 chemical nickel plating：Pretreated expanded graphite is placed in 500ml chemical nickel-plating solutions, using nickel blender
It is stirred, mixing speed 1000r/min, it is 65 DEG C to adjust reaction temperature, reaction time 70min.Take out the expansion after reaction
Graphite is placed in 80 DEG C of vacuum drying chamber dry 10h, obtains the expanded graphite powder after nickel plating.
Expanded graphite surface forms dispersed nickel particle after chemical nickel plating.Using this nickel particle urging as electroless copper
Change depocenter and carry out follow-up electroless copper.
3rd step：Electroless copper
3.1 configuration chemical copper plating solutions：Chemical plating fluid is by cupric sulfate pentahydrate, disodium ethylene diamine tetraacetate, sodium hydroxide, first
Aldehyde, bipyridyl etc. form.Dosage：Cupric sulfate pentahydrate 15g/L, disodium ethylene diamine tetraacetate 20g/L, sodium hydroxide 10g/L, formaldehyde
(37%) 17mL/L, bipyridyl 0.1g/L.
3.2 electroless copper：2g nickel plating expanded graphites are placed in 500ml chemical copper plating solutions, mixing speed 1000r/
Min, it is 60 DEG C to adjust reaction temperature, reaction time 100min.Expanded graphite after taking-up reaction is cleaned dry with deionized water
Only.
3.3 passivation：The copper facing expanded graphite that will be rinsed well, adds the disodium ethylene diamine tetraacetate that mass fraction is 5%
In passivating solution, 15min is stirred, is then cleaned up with deionized water, be placed in 120 DEG C of vacuum drying chamber dry 8h, obtain
Copper facing expanded graphite powder.
As shown in figure 8, scanned electron microscopic observation, after electroless copper expanded graphite surface coated one layer it is complete, fine and close
Metal copper coating.
Claims (2)
1. one kind is in expanded graphite process for copper coating on surface, it is characterised in that the method comprises the following steps：
The first step：Pretreatment
1.1 surface degreasing：Expanded graphite powder is placed in NaOH alkaline solutions, at a temperature of 30~100 DEG C magnetic agitation 20~
50min, is cleaned to neutrality repeatedly with deionized water, stand-by after being dried at a temperature of 80~100 DEG C to constant weight；
1.2 roughening treatment：Expanded graphite powder after oil removing is placed in coarsening solution, electromagnetism stirs at 30~40 DEG C of temperature range
Mix, coarsening time is 5~30min；Coarsening solution component is：150~200g/L (NH4)2S2O8(ammonium peroxydisulfate), 50~
100mL/LH2SO4, H2SO4Density be 1.84g/cm3；It is washed with deionized water after roughening to neutrality, at a temperature of 80~100 DEG C
It is stand-by after drying to constant weight；
Second step：Chemical nickel plating
2.1 configuration chemical nickel-plating solutions：Chemical plating fluid is by six hydration nickel sulfate, sodium citrate, ammonium chloride, sodium hypophosphite, ammonia
Water and deionized water composition；Dosage：10~30g/L of six hydration nickel sulfate, 10~30g/L of sodium citrate, ammonium chloride 10~
35g/L, 10~30g/L of sodium hypophosphite, it is 8~10 that ammonium hydroxide, which adjusts pH value,；
2.2 chemical nickel plating：Pretreated expanded graphite powder is placed in chemical nickel-plating solution prepared by step 2.1, using nickel
Blender and expanded graphite plating at the same time, are carried out at the same time stirring, mixing speed 300r/min~1000r/min, reaction temperature is
40~80 DEG C, 30~150min of reaction time；Expanded graphite after taking-up reaction, which is placed in 80~120 DEG C of vacuum drying chamber, to be done
Dry 5~10h, obtains the expanded graphite powder after nickel plating；
3rd step：Electroless copper
3.1 prepare chemical copper plating solution：Chemical plating fluid by cupric sulfate pentahydrate, disodium ethylene diamine tetraacetate, sodium hydroxide, formaldehyde and
Bipyridyl forms, dosage：10~20g/L of cupric sulfate pentahydrate, 10~30g/L of disodium ethylene diamine tetraacetate, 5~10g/ of sodium hydroxide
L, 5~20mL/L of formaldehyde, bipyridyl 0.1g/L；
3.2 electroless copper：Expanded graphite through second step nickel plating is placed in chemical copper plating solution prepared by step 3.1, used
Mechanical agitation, mixing speed 300r/min~1000r/min, reaction temperature are 40~80 DEG C, 30~150min of reaction time；Take
The expanded graphite gone out after reaction is cleaned up with deionized water；
3.3 passivation：The copper facing expanded graphite rinsed well is added to the disodium ethylene diamine tetraacetate that mass fraction is 5% to be passivated
In liquid, 15min is stirred, and then deionization cleans up, and dry 5~10h is placed in 80~120 DEG C of vacuum drying chamber, is obtained
Copper facing expanded graphite powder.
2. as claimed in claim 1 in expanded graphite process for copper coating on surface, it is characterised in that：The second step
Learn nickel plating and dispersed nickel activation point is formed on expanded graphite surface.
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| CN108277480A (en) * | 2017-10-30 | 2018-07-13 | 浙江三元电子科技有限公司 | A kind of method of graphite nickel plating |
| CN107858713B (en) * | 2017-11-02 | 2019-11-05 | 中国科学院山西煤炭化学研究所 | A kind of device and method preparing expanded graphite electro-coppering |
| CN109873117B (en) * | 2017-12-01 | 2021-07-13 | 中国科学院大连化学物理研究所 | Electrode for lithium ion battery and preparation and application thereof |
| CN109136622A (en) * | 2018-08-23 | 2019-01-04 | 大同新成新材料股份有限公司 | A kind of preparation method of Material for Pantograph Slide |
| CN110183832B (en) * | 2019-05-24 | 2020-04-14 | 燕山大学 | Preparation method of nickel phosphorus/expanded graphite-polyester resin/polytetrafluoroethylene composite material |
| CN110453206B (en) * | 2019-08-08 | 2021-07-20 | 长春工业大学 | Metal-sandwiched layer flake graphite and preparation method and application thereof |
| CN111408713A (en) * | 2020-03-17 | 2020-07-14 | 苏州逸峰新材料科技有限公司 | Preparation method of nickel-coated graphite composite powder material with high coating rate |
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| CN103469182A (en) * | 2013-08-30 | 2013-12-25 | 西北工业大学 | Palladium-free chemical copper-plating method on graphite nanosheet surface |
| CN103981513A (en) * | 2014-05-30 | 2014-08-13 | 北京理工大学 | Chemical nickel plating method on carbon fiber surface |
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| CN103469182A (en) * | 2013-08-30 | 2013-12-25 | 西北工业大学 | Palladium-free chemical copper-plating method on graphite nanosheet surface |
| CN103981513A (en) * | 2014-05-30 | 2014-08-13 | 北京理工大学 | Chemical nickel plating method on carbon fiber surface |
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