CN105154914A - Preparation method of carbon fiber composite anode material - Google Patents
Preparation method of carbon fiber composite anode material Download PDFInfo
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- CN105154914A CN105154914A CN201510606465.6A CN201510606465A CN105154914A CN 105154914 A CN105154914 A CN 105154914A CN 201510606465 A CN201510606465 A CN 201510606465A CN 105154914 A CN105154914 A CN 105154914A
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- Prior art keywords
- carbon fiber
- fiber composite
- resin matrix
- composite resin
- anode
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 191
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 191
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000010405 anode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000805 composite resin Substances 0.000 claims abstract description 140
- 239000011159 matrix material Substances 0.000 claims abstract description 130
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 34
- 238000007747 plating Methods 0.000 claims description 33
- 238000004070 electrodeposition Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000009713 electroplating Methods 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 14
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000005238 degreasing Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 9
- 108010010803 Gelatin Proteins 0.000 claims description 8
- -1 carbon fiber compound Chemical class 0.000 claims description 8
- 229920000159 gelatin Polymers 0.000 claims description 8
- 239000008273 gelatin Substances 0.000 claims description 8
- 235000019322 gelatine Nutrition 0.000 claims description 8
- 235000011852 gelatine desserts Nutrition 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 7
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000004080 punching Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229920006387 Vinylite Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 44
- 150000002500 ions Chemical class 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- HPOIYBGFFZRZKK-UHFFFAOYSA-N lead;methanesulfonic acid Chemical compound [Pb].CS(O)(=O)=O HPOIYBGFFZRZKK-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Cell Electrode Carriers And Collectors (AREA)
- Electroplating Methods And Accessories (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a carbon fiber composite anode material. The method comprises the following steps: preparing a carbon fiber composite resin matrix (1) and a conductive copper beam (2) into an anode material, then carrying out surface pretreatment on the carbon fiber composite resin matrix, then electrically depositing a lead or lead alloy intermediate metal layer on the surface of the carbon fiber composite resin matrix, and finally electrically depositing an active layer on the surface of the carbon fiber composite resin matrix. According to the preparation method of the carbon fiber composite anode material, the problem that the carbon anode material is easy to consume when being used as the anode can be effectively solved; the oxidation corrosion resistance of the carbon fiber composite resin material in the electrolytic process is improved; the service life of the carbon fiber composite anode material is prolonged; and the electro-catalytic activity of the carbon fiber anode material can be effectively improved.
Description
Technical field
The invention belongs to combination electrode material technical field, be specially a kind of preparation method of carbon fiber composite anode materials.
Background technology
Carbon fiber carbon content ratio is high, and (carbon fibrous body resistivity is 1.2 × 10 to good conductivity
-3Ω cm), specific surface area is large, is a kind of good electrochemical reactor.Carbon fiber composite resin material, not only has good electroconductibility, and also had excellent mechanical property concurrently, carbon fiber composite resin material has good corrosion resistance, and in high chloride ion environment, erosion resistance is excellent especially.But because carbon fiber is a kind of micro crystal graphite material, when it easily produces consumption as during anode, therefore, when doing anode material with carbon fiber composite resin material, carbon fiber is as conductive phase, and resin is as Binder Phase.Such as, in electrowinning zinc process, in electrolytic solution, there is a large amount of SO
4 2-with a small amount of ClO
-, these ions can discharge and produce oxygen on anode, cause carbon fibre anode can produce CO and CO in electrolytic process
2and occur consuming (2O
2-(cooperation)-4e+C → CO
2, under normal anodic current density, CO
2for the primary product of anode, CO can be generated under low current density).
Summary of the invention
The object of the invention is to solve existing carbon fiber composite resin material do anode material and go out Problems existing, there is provided a kind of and effectively can solve the problem of carbon anode material as easy consumption during anode, improve the antioxidant anticorrosive of carbon fiber composite resin material in electrolytic process, extend its work-ing life, also effectively can increase the preparation method of the carbon fiber composite anode materials of the electro catalytic activity of carbon fibre anode material.
In order to realize foregoing invention object, the technical scheme that the present invention takes is as follows:
A preparation method for carbon fiber composite anode materials, comprises the steps:
A () makes anode material: respectively by carbon fiber composite resin matrix and the punching of conduction Tongliang County, and with copper rivet through the hole on compound resin matrix and conduction Tongliang County, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam to the pouring of conduction Tongliang County is plumbous, carbon fiber composite resin base bottom insulation firm banking is fixed;
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin body portion of anode material step (a) made puts into NaOH and Na
2cO
3compound alkaline degreasing liquid in 30 ~ 60min, after oil removing, by washed with de-ionized water 1 ~ 3 time, then carbon fiber composite resin matrix aqueous etching oxidation style and anonizing are carried out surface preparation, after having processed, by washed with de-ionized water 1 ~ 3 time;
Plumbous or the lead alloy intermediate metal layer of (c) carbon fiber composite resin matrix surface galvanic deposit: pretreated for step (b) carbon fiber composite resin matrix is placed in lead or lead alloy composite plating solution as negative electrode, pure stereotype is anode, direct current electrode position, makes carbon fiber composite resin matrix surface galvanic deposit one deck lead or lead alloy intermediate metal layer;
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: galvanic deposit carbon fiber composite resin matrix washed with de-ionized water that is plumbous or lead alloy intermediate metal layer is clean will to process through step (c) surface obtained, composite reactive layer electroplate liquid is placed in as anode, using stainless steel as negative electrode, direct current electrode position, makes the active coating of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness.
Carbon fiber composite resin matrix in step (a) of the present invention is tabular or bar-shaped carbon fiber reinforced resin material, and tabular carbon fiber composite resin matrix thickness is 3 ~ 8mm, and rod carbon fiber compound resin base diameter is 10 ~ 30mm.
Described carbon fiber reinforced resin material is one or more in carbon-fibre reinforced epoxy resin, fibre reinforced Vinylite, fibre reinforced unsaturated polyester resin.
One or more in graphite, conductive polyaniline, Graphene are added with in described carbon fiber reinforced resin material.
Described NaOH and Na of step (b)
2cO
3the mass concentration scope of compound alkaline degreasing liquid be 60 ~ 100g/LNaOH and 15 ~ 30g/LNa
2cO
3.
Aqueous etching oxidation style described in step (b) be carbon fiber composite resin matrix is placed in temperature 20 ~ 60 DEG C, mass percent concentration is 5% ~ 20%HNO
3the aqueous solution in oxidation 5 ~ 30min; Described anonizing refers to and carbon fiber composite resin matrix is placed in electrolyzer as anode, be oxidized as negative electrode with graphite, and in electrolyzer, electrolytic solution is the NH of mass percent 5% ~ 10%
4hCO
3the aqueous solution, the current density of electrolysis is 10 ~ 80A/m
2, electrolyte temperature is 20 ~ 40 DEG C, oxidization time is 2 ~ 10min.
The described lead of step (c) or lead alloy composite plating solution are that 150 ~ 200mL/L methylsulphonic acid is plumbous or 0.2 ~ 1g/L methylsulphonic acid is silver-colored and the mixed solution of 0.5g/L gelatin, electroplating technical conditions is as negative electrode using carbon fiber composite resin matrix, pure stereotype is anode, the current density 1 ~ 10A/m of plating
2, plating time is 1 ~ 12h, and temperature is 20 ~ 40 DEG C, and be plumbous or pb-ag alloy at the lead of carbon fiber composite resin matrix surface galvanic deposit or lead alloy intermediate metal layer, thickness is 20 ~ 60 μm.
Step (d) described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 50 ~ 200g/LPb (NO
3)
2, the initial HNO of 0 ~ 0.5mol/LNaF and 5 ~ 10g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 40 ~ 90 DEG C, anodic current density is 30 ~ 70mA/cm
3, electrodeposition time 1 ~ 3h; Be β-PbO at the active coating of the microhardness of carbon fiber composite resin matrix surface galvanic deposit
2active coating, its thickness 2 ~ 3mm, microhardness>=400Hv.
The carbon fiber composite anode materials adopting the present invention to obtain efficiently solves the problem of carbon anode material as easy consumption during anode, improves work-ing life, also effectively increases the electro catalytic activity of carbon fibre anode material.The carbon fiber composite anode materials obtained by the inventive method not only has good electroconductibility, has had excellent mechanical property concurrently, in high chloride ion environment, has had good corrosion resistance, effectively can reduce energy consumption as during anode.
Accompanying drawing explanation
Fig. 1 is the structural representation of carbon fiber composite anode materials of the present invention.
Embodiment
Embodiment 1
A preparation method for carbon fiber composite anode materials, comprises the steps:
A () makes anode material: be punch in tabular carbon fiber composite resin matrix 1 and conduction Tongliang County 2 of 8mm respectively by thickness, and with copper rivet 5 through the hole on compound resin matrix and conduction Tongliang County, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam 3 to the pouring of conduction Tongliang County is plumbous, carbon fiber composite resin base bottom insulation firm banking 4 is fixed.Described carbon fiber reinforced resin material is carbon-fibre reinforced epoxy resin.Graphite and conductive polyaniline is added with in carbon fiber reinforced resin material.
The resin that carbon fiber compound is different, can make carbon fiber composite anode materials can be applied to multiple solution system.By adding inorganic or organic conductive powder in resin, not only can improve the electroconductibility of carbon fiber composite anode materials, the electrochemical activity of matrix can also be improved.Therefore, carbon fiber composite resin matrix has higher physical strength and excellent conductivity, and quality is light and type design is strong.
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin body portion of anode material step (a) made puts into the NaOH of mass concentration 80g/L and the Na of mass concentration 20g/L
2cO
3compound alkaline degreasing liquid in oil removing 60min, by washed with de-ionized water 3 times, then carbon fiber composite resin matrix aqueous etching oxidation style is carried out surface preparation to it, processing condition are for being 10%HNO at mass percent concentration
3the aqueous solution in be oxidized 5min, temperature controls at 40 DEG C, after having processed, by washed with de-ionized water 3 times.
Carbon fiber composite resin matrix, hydrophobic and the residual a lot of greasy dirt of its smooth surface, to follow-up in carbon fiber composite resin matrix surface galvanic deposit active surface layer process, between coating and base material Van der Waals force and mechanical interlock effect more weak, if the improper meeting of carbon fiber composite resin matrix surface pre-treatment makes active surface uneven, bonding force is bad, easily peels off.The destruction of active surface, not only can reduce the electro catalytic activity of electrode materials, and carbon fiber composite resin matrix also can be made exposed, accelerates its corrosion consumption process, reduces the work-ing life of anode.
(c) carbon fiber composite resin matrix surface galvanic deposit lead or lead alloy intermediate metal layer: pretreated for step (b) carbon fiber composite resin matrix is placed in composite plating solution as negative electrode, pure stereotype is anode, direct current electrode position, makes the plumbous intermediate metal layer of carbon fiber composite resin matrix surface galvanic deposit one deck; Described composite plating solution is the mixed solution of 200mL/L methylsulphonic acid lead and 0.5g/L gelatin, and electroplating technical conditions is using carbon fiber composite resin matrix as negative electrode, and pure stereotype is the current density 2A/m of anode, plating
2, plating time is 3h, and temperature is 40 DEG C, obtains the plumbous intermediate metal layer that thickness is 25 μm.
At the certain thickness lead of carbon fiber composite resin matrix surface galvanic deposit or lead alloy intermediate metal layer, not only can improve electroconductibility and the surface anti-solion erosion-corrosion performance of carbon fiber composite anode materials, the bonding force on carbon fiber composite resin matrix and surface electrical position activity top layer can also be improved.
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: after treating that lead in step (c) or lead alloy galvanic deposit complete, spend the clean carbon fiber composite resin matrix of Ion Cleaning, anode is it can be used as to be placed in composite reactive layer electroplate liquid, using stainless steel as negative electrode, direct current electrode position, makes the β-PbO of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness
2active coating.Described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 200g/LPb (NO
3)
2, the initial HNO of 0.5mol/LNaF and 5g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 40 DEG C, anodic current density is 30mA/cm
3, electrodeposition time 2h; Surperficial β-the PbO obtained
2active layer thickness 2mm, microhardness 600Hv.β-PbO
2active coating has anti-oxidant, corrosion-resistant (at strong acid H
2sO
4or HNO
3in have higher stability), oxygen overvoltage is high, electroconductibility is good, bonding force is strong, in the aqueous solution during electrolysis oxidation capacity strong, by features such as big current.Due to β-PbO
2active layer deposited and electrode surface deposit uneven and β-PbO
2the bad mechanical property of self, must control deposit thickness thus the associativity of guarantee active coating and electrode surface.
Embodiment 2
A preparation method for carbon fiber composite anode materials, comprises the steps:
A () makes anode material: the rod carbon fiber compound resin matrix and the punching of conduction Tongliang County that by diameter are 20mm respectively, and with copper rivet, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam to the pouring of conduction Tongliang County is plumbous, carbon fiber composite resin base bottom insulation firm banking is fixed.Described carbon fiber reinforced resin material is fibre reinforced Vinylite and fibre reinforced unsaturated polyester resin.Graphene is added with in carbon fiber reinforced resin material.
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin matrix of anode material step (a) made puts into the NaOH of mass concentration 60g/L and the Na of mass concentration 30g/L
2cO
3compound alkaline degreasing liquid in oil removing 40min, by washed with de-ionized water 2 times, then carbon fiber composite resin matrix anonizing is carried out surface preparation to it, be specially and carbon fiber composite resin matrix be placed in electrolyzer as anode, be oxidized as negative electrode with graphite, in electrolyzer, electrolytic solution is the NH of mass percent 5%
4hCO
3the aqueous solution, the current density of electrolysis is 10A/m
2, electrolyte temperature is 20 DEG C, oxidization time is 10min.Use washed with de-ionized water afterwards 2 times.
(c) carbon fiber composite resin matrix surface galvanic deposit lead or lead alloy intermediate metal layer: pretreated for step (b) carbon fiber composite resin matrix is placed in composite plating solution as negative electrode, pure stereotype is anode, direct current electrode position, makes the certain thickness pb-ag alloy intermediate metal layer of carbon fiber composite resin matrix surface galvanic deposit; Described composite plating solution is that 150mL/L methylsulphonic acid is plumbous, 0.2g/L methylsulphonic acid is silver-colored and the mixed solution of 0.5g/L gelatin, and electroplating technical conditions is using carbon fiber composite resin matrix as negative electrode, and pure stereotype is the current density 10A/m of anode, plating
2, plating time is 1h, and temperature is 30 DEG C, obtains the pb-ag alloy intermediate metal layer that thickness is 54 μm.
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: after treating that lead in step (c) or lead alloy galvanic deposit complete, spend the clean carbon fiber composite resin matrix of Ion Cleaning, anode is it can be used as to be placed in composite reactive layer electroplate liquid, using stainless steel as negative electrode, direct current electrode position, makes the β-PbO of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness
2active coating.Described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 100g/LPb (NO
3)
2, the initial HNO of 0.2mol/LNaF and 10g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 60 DEG C, anodic current density is 40mA/cm
3, electrodeposition time 3h; Surperficial β-the PbO obtained
2active layer thickness 2.5mm, microhardness 400Hv.
Embodiment 3
A preparation method for carbon fiber composite anode materials, comprises the steps:
A () makes anode material: the rod carbon fiber compound resin matrix and the punching of conduction Tongliang County that by diameter are 30mm respectively, and with copper rivet, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam to the pouring of conduction Tongliang County is plumbous, carbon fiber composite resin base bottom insulation firm banking is fixed.Described carbon fiber reinforced resin material is fibre reinforced Vinylite.Graphite is added with in carbon fiber reinforced resin material.
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin matrix of anode material step (a) made puts into the NaOH of mass concentration 100g/L and the Na of mass concentration 15g/L
2cO
3compound alkaline degreasing liquid in oil removing 30min, by washed with de-ionized water 1 time, then carbon fiber composite resin matrix anonizing is carried out surface preparation to it, be specially and carbon fiber composite resin matrix be placed in electrolyzer as anode, be oxidized as negative electrode with graphite, in electrolyzer, electrolytic solution is the NH of mass percent 10%
4hCO
3the aqueous solution, the current density of electrolysis is 80A/m
2, electrolyte temperature is 30 DEG C, oxidization time is 6min.Use washed with de-ionized water afterwards 2 times.
(c) carbon fiber composite resin matrix surface galvanic deposit lead or lead alloy intermediate metal layer: pretreated for step (b) carbon fiber composite resin matrix is placed in composite plating solution as negative electrode, pure stereotype is anode, direct current electrode position, makes the certain thickness plumbous intermediate metal layer of carbon fiber composite resin matrix surface galvanic deposit; Described composite plating solution is that 180mL/L methylsulphonic acid is plumbous, 0.8g/L methylsulphonic acid is silver-colored and the mixed solution of 0.5g/L gelatin, and electroplating technical conditions is using carbon fiber composite resin matrix as negative electrode, and pure stereotype is the current density 9A/m of anode, plating
2, plating time is 12h, and temperature is 35 DEG C, obtains the plumbous intermediate metal layer that thickness is 60 μm.
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: after treating that lead in step (c) or lead alloy galvanic deposit complete, spend the clean carbon fiber composite resin matrix of Ion Cleaning, anode is it can be used as to be placed in composite reactive layer electroplate liquid, using stainless steel as negative electrode, direct current electrode position, makes the β-PbO of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness
2active coating.Described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 180g/LPb (NO
3)
2, the initial HNO of 0.4mol/LNaF and 8g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 90 DEG C, anodic current density is 70mA/cm
3, electrodeposition time 1h; Surperficial β-the PbO obtained
2active layer thickness 3mm, microhardness 400Hv.
Embodiment 4
A preparation method for carbon fiber composite anode materials, comprises the steps:
A () makes anode material: the rod carbon fiber compound resin matrix and the punching of conduction Tongliang County that by diameter are 10mm respectively, and with copper rivet, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam to the pouring of conduction Tongliang County is plumbous, carbon fiber composite resin base bottom insulation firm banking is fixed.The resin material of described enhancing is carbon-fibre reinforced epoxy resin.Conductive polyaniline is added with in carbon fiber reinforced resin material.
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin matrix of anode material step (a) made puts into the NaOH of mass concentration 100g/L and the Na of mass concentration 25g/L
2cO
3compound alkaline degreasing liquid in oil removing 50min, by washed with de-ionized water 2 times, then carbon fiber composite resin matrix aqueous etching oxidation style is carried out surface preparation to it, processing condition are for being 20%HNO at mass percent concentration
3the aqueous solution in be oxidized 10min, temperature controls at 20 DEG C, after having processed, by washed with de-ionized water 1 time.
(c) carbon fiber composite resin matrix surface galvanic deposit lead or lead alloy intermediate metal layer: pretreated for step (b) carbon fiber composite resin matrix is placed in composite plating solution as negative electrode, pure stereotype is anode, direct current electrode position, makes the certain thickness plumbous intermediate metal layer of carbon fiber composite resin matrix surface galvanic deposit; Described composite plating solution is that 180mL/L methylsulphonic acid is plumbous, 1g/L methylsulphonic acid is silver-colored and the mixed solution of 0.5g/L gelatin, and electroplating technical conditions is using carbon fiber composite resin matrix as negative electrode, and pure stereotype is the current density 1A/m of anode, plating
2, plating time is 10h, and temperature is 20 DEG C, obtains the plumbous intermediate metal layer that thickness is 20 μm.
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: after treating that lead in step (c) or lead alloy galvanic deposit complete, spend the clean carbon fiber composite resin matrix of Ion Cleaning, anode is it can be used as to be placed in composite reactive layer electroplate liquid, using stainless steel as negative electrode, direct current electrode position, makes the β-PbO of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness
2active coating.Described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 50g/LPb (NO
3)
2hNO initial with 8g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 80 DEG C, anodic current density is 50mA/cm
3, electrodeposition time 2h; Surperficial β-the PbO obtained
2active layer thickness 3mm, microhardness 500Hv.
Embodiment 5
A preparation method for carbon fiber composite anode materials, comprises the steps:
A () makes anode material: select thickness to be the tabular carbon fiber composite resin matrix of 3 ~ 6mm and conduction Tongliang County, punch respectively, and with copper rivet, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam to the pouring of conduction Tongliang County is plumbous, carbon fiber composite resin base bottom insulation firm banking is fixed.
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin matrix of anode material step (a) made puts into the NaOH of mass concentration 70g/L and the Na of mass concentration 20g/L
2cO
3compound alkaline degreasing liquid in oil removing 40min, by washed with de-ionized water 3 times, then carbon fiber composite resin matrix aqueous etching oxidation style is carried out surface preparation to it, processing condition are for being 5%HNO at mass percent concentration
3the aqueous solution in be oxidized 30min, temperature controls at 60 DEG C, after having processed, by washed with de-ionized water 1 time.
(c) carbon fiber composite resin matrix surface galvanic deposit lead or lead alloy intermediate metal layer: pretreated for step (b) carbon fiber composite resin matrix is placed in composite plating solution as negative electrode, and pure stereotype is anode, direct current electrode position; Composite plating solution is the mixed solution of 180mL/L methylsulphonic acid lead and 0.5g/L gelatin, and electroplating technical conditions is using carbon fiber composite resin matrix as negative electrode, and pure stereotype is the current density 5A/m of anode, plating
2, plating time is 8h, and temperature is 35 DEG C, obtains the plumbous intermediate metal layer that thickness is 25 μm.
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: after treating that lead in step (c) or lead alloy galvanic deposit complete, spend the clean carbon fiber composite resin matrix of Ion Cleaning, anode is it can be used as to be placed in composite reactive layer electroplate liquid, using stainless steel as negative electrode, direct current electrode position, makes the β-PbO of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness
2active coating.Described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 80g/LPb (NO
3)
2, the initial HNO of 0.1mol/LNaF and 8g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 80 DEG C, anodic current density is 40mA/cm
3, electrodeposition time 2h; Surperficial β-the PbO obtained
2active layer thickness 2.5mm, microhardness 600Hv.
Embodiment 6
A preparation method for carbon fiber composite anode materials, comprises the steps:
A () makes anode material: the tabular carbon fiber composite resin matrix and the punching of conduction Tongliang County that by thickness are 5mm respectively, and with copper rivet, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam to the pouring of conduction Tongliang County is plumbous, carbon fiber composite resin base bottom insulation firm banking is fixed.
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin matrix of anode material step (a) made puts into the NaOH of mass concentration 60g/L and the Na of mass concentration 30g/L
2cO
3compound alkaline degreasing liquid in oil removing 40min, by washed with de-ionized water 3 times, then carbon fiber composite resin matrix anonizing is carried out surface preparation to it, be specially and carbon fiber composite resin matrix be placed in electrolyzer as anode, be oxidized as negative electrode with graphite, in electrolyzer, electrolytic solution is the NH of mass percent 8%
4hCO
3the aqueous solution, the current density of electrolysis is 50A/m
2, electrolyte temperature is 40 DEG C, oxidization time is 2min.Use washed with de-ionized water afterwards 3 times.
(c) carbon fiber composite resin matrix surface galvanic deposit lead or lead alloy intermediate metal layer: pretreated for step (b) carbon fiber composite resin matrix is placed in composite plating solution as negative electrode, pure stereotype is anode, direct current electrode position, makes the certain thickness pb-ag alloy intermediate metal layer of carbon fiber composite resin matrix surface galvanic deposit; Described composite plating solution is that 150mL/L methylsulphonic acid is plumbous, 0.5g/L methylsulphonic acid is silver-colored and the mixed solution of 0.5g/L gelatin, and electroplating technical conditions is using carbon fiber composite resin matrix as negative electrode, and pure stereotype is the current density 8A/m of anode, plating
2, plating time is 6h, and temperature is 30 DEG C, obtains the pb-ag alloy intermediate metal layer that thickness is 55 μm.
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: after treating that lead in step (c) or lead alloy galvanic deposit complete, spend the clean carbon fiber composite resin matrix of Ion Cleaning, anode is it can be used as to be placed in composite reactive layer electroplate liquid, using stainless steel as negative electrode, direct current electrode position, makes the β-PbO of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness
2active coating.Described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 120g/LPb (NO
3)
2, the initial HNO of 0.2mol/LNaF and 5g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 50 DEG C, anodic current density is 40mA/cm
3, electrodeposition time 2h; Surperficial β-the PbO obtained
2active layer thickness 2.8mm, microhardness 400Hv.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, any amendment done within all spirit in invention and principle, equivalent to replace and improvement etc., all should be included within protection scope of the present invention.
The inventive method can be widely used in the fields such as plating, smelting, wastewater treatment, cathodic protection.
Claims (8)
1. a preparation method for carbon fiber composite anode materials, is characterized in that, method steps is as follows:
A () makes anode material: respectively by carbon fiber composite resin matrix (1) and conduction Tongliang County (2) punching, and with copper rivet (5) through the hole on compound resin matrix and conduction Tongliang County, carbon fiber composite resin matrix is fixed in conduction Tongliang County, then form sheath copper conducting beam (3) to the pouring of conduction Tongliang County is plumbous, insulation firm banking (4) of carbon fiber composite resin base bottom is fixed;
B () is to the pre-treatment of carbon fiber composite resin matrix surface: the carbon fiber composite resin body portion of anode material step (a) made puts into NaOH and Na
2cO
3compound alkaline degreasing liquid in 30 ~ 60min, after oil removing, by washed with de-ionized water 1 ~ 3 time, then carbon fiber composite resin matrix aqueous etching oxidation style and anonizing are carried out surface preparation, after having processed, by washed with de-ionized water 1 ~ 3 time;
Plumbous or the lead alloy intermediate metal layer of (c) carbon fiber composite resin matrix surface galvanic deposit: pretreated for step (b) carbon fiber composite resin matrix is placed in lead or lead alloy composite plating solution as negative electrode, pure stereotype is anode, direct current electrode position, makes carbon fiber composite resin matrix surface galvanic deposit one deck lead or lead alloy intermediate metal layer;
(d) carbon fiber composite resin matrix surface galvanic deposit active coating: galvanic deposit carbon fiber composite resin matrix washed with de-ionized water that is plumbous or lead alloy intermediate metal layer is clean will to process through step (c) surface obtained, composite reactive layer electroplate liquid is placed in as anode, using stainless steel as negative electrode, direct current electrode position, makes the active coating of carbon fiber composite resin matrix surface galvanic deposit one deck microhardness.
2. the preparation method of a kind of carbon fiber composite anode materials according to claim 1, it is characterized in that, carbon fiber composite resin matrix in step (a) of the present invention is tabular or bar-shaped carbon fiber reinforced resin material, tabular carbon fiber composite resin matrix thickness is 3 ~ 8mm, and rod carbon fiber compound resin base diameter is 10 ~ 30mm.
3. the preparation method of a kind of carbon fiber composite anode materials according to claim 2, it is characterized in that, described carbon fiber reinforced resin material is one or more in carbon-fibre reinforced epoxy resin, fibre reinforced Vinylite, fibre reinforced unsaturated polyester resin.
4. the preparation method of a kind of carbon fiber composite anode materials according to Claims 2 or 3, is characterized in that, is added with one or more in graphite, conductive polyaniline, Graphene in described carbon fiber reinforced resin material.
5. the preparation method of a kind of carbon fiber composite anode materials according to claim 1, is characterized in that, described NaOH and Na of step (b)
2cO
3the mass concentration scope of compound alkaline degreasing liquid be 60 ~ 100g/LNaOH and 15 ~ 30g/LNa
2cO
3.
6. the preparation method of a kind of carbon fiber composite anode materials according to claim 1 or 5, it is characterized in that, the aqueous etching oxidation style described in step (b) be carbon fiber composite resin matrix is placed in temperature 20 ~ 60 DEG C, mass percent concentration is 5% ~ 20%HNO
3the aqueous solution in oxidation 5 ~ 30min; Described anonizing refers to and carbon fiber composite resin matrix is placed in electrolyzer as anode, be oxidized as negative electrode with graphite, and in electrolyzer, electrolytic solution is the NH of mass percent 5% ~ 10%
4hCO
3the aqueous solution, the current density of electrolysis is 10 ~ 80A/m
2, electrolyte temperature is 20 ~ 40 DEG C, oxidization time is 2 ~ 10min.
7. the preparation method of a kind of carbon fiber composite anode materials according to claim 1, it is characterized in that, the described lead of step (c) or lead alloy composite plating solution are that 150 ~ 200mL/L methylsulphonic acid is plumbous or 0.2 ~ 1g/L methylsulphonic acid is silver-colored and the mixed solution of 0.5g/L gelatin, electroplating technical conditions is as negative electrode using carbon fiber composite resin matrix, pure stereotype is anode, the current density 1 ~ 10A/m of plating
2, plating time is 1 ~ 12h, and temperature is 20 ~ 40 DEG C, and be plumbous or pb-ag alloy at the lead of carbon fiber composite resin matrix surface galvanic deposit or lead alloy intermediate metal layer, thickness is 20 ~ 60 μm.
8. the preparation method of a kind of carbon fiber composite anode materials according to claim 1, is characterized in that, step (d) described composite reactive layer electroplate liquid is β-PbO
2electroplate liquid, electroplating bath components is 50 ~ 200g/LPb (NO
3)
2, the initial HNO of 0 ~ 0.5mol/LNaF and 5 ~ 10g/L
3; Direct current electrode position processing condition are that negative electrode made by stainless steel using carbon fiber composite resin matrix as anode, and bath temperature is 40 ~ 90 DEG C, anodic current density is 30 ~ 70mA/cm
3, electrodeposition time 1 ~ 3h; Be β-PbO at the active coating of the microhardness of carbon fiber composite resin matrix surface galvanic deposit
2active coating, its thickness 2 ~ 3mm, microhardness>=400Hv.
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| CN114212860A (en) * | 2021-12-14 | 2022-03-22 | 宁波职业技术学院 | Method for treating wastewater by using nano-silver modified carbon paper anode to electrically activate persulfate |
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| CN109650493A (en) * | 2019-01-22 | 2019-04-19 | 陕西科技大学 | A kind of VS with hierarchical structure2The synthetic method of nano-chip arrays electrode material |
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| CN113584533A (en) * | 2021-08-12 | 2021-11-02 | 昆明理工大学 | Preparation method of carbon fiber titanium-based lead dioxide electrode |
| CN114212860A (en) * | 2021-12-14 | 2022-03-22 | 宁波职业技术学院 | Method for treating wastewater by using nano-silver modified carbon paper anode to electrically activate persulfate |
| CN114212860B (en) * | 2021-12-14 | 2023-04-25 | 宁波职业技术学院 | Method for treating wastewater by nano-silver modified carbon paper anode electro-active persulfate |
| CN115595635A (en) * | 2022-10-11 | 2023-01-13 | 昆明理工大学（Cn） | Preparation method of reticular carbon fiber sawtooth composite carbon fiber-aluminum-copper composite electrode |
| CN115595635B (en) * | 2022-10-11 | 2023-04-18 | 昆明理工大学 | Preparation method of reticular carbon fiber sawtooth composite carbon fiber-aluminum-copper composite electrode |
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