CN107245729B - Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof - Google Patents

Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof Download PDF

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CN107245729B
CN107245729B CN201710478157.9A CN201710478157A CN107245729B CN 107245729 B CN107245729 B CN 107245729B CN 201710478157 A CN201710478157 A CN 201710478157A CN 107245729 B CN107245729 B CN 107245729B
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carbon fiber
composite
pbo
particle
anode material
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CN107245729A (en
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陈步明
郭忠诚
黄惠
李学龙
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KUNMING HENDERA SCIENCE AND TECHNOLOGY Co Ltd
Kunming University of Science and Technology
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KUNMING HENDERA SCIENCE AND TECHNOLOGY Co Ltd
Kunming University of Science and Technology
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Abstract

Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof, the anode material include carbon fiber substrate (1), the α-PbO for introducing nano-graphene particle for being compounded in carbon fiber substrate surface2Composite deposite (2) is compounded in α-PbO2Composite deposite (2) surface introduces SiO2β-the PbO of particle2Composite deposite (3) is covered in β-PbO2Composite deposite (3) surface introduces RuO2β-the MnO of particle2Composite coating (4).Carbon fiber-based graded composite anode material electro catalytic activity prepared by the present invention is good, tank voltage is low, long service life, at low cost, electric effect are high.

Description

Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof
Technical field
The present invention relates to a kind of manganese electrodeposition anode material and preparation method thereof technical fields.
Background technique
Metallurgical industry is still big power consumer in industrial production, and production energy consumption is high, and main specific energy consumption average specific is external Advanced level is high by 40%.In the smelting process of manganese metal, 90% or more manganese is extracted by hydrometallurgical technology, electrolyzing gold The current efficiency for belonging to manganese is low, generally only reaches 75% or so, and the nearly 7500kWh of electrolysis manganese product power consumption per ton, is famous Electricity-eating tiger, if in terms of 2,000,000 tons of domestic production manganese ingot in 2016, by the energy consumption of needs close to 15,000,000,000 degree electricity.Electrolytic metal Although the production technology of manganese is a mature production technology, but still have very big potentiality that can dig.For the development of electrolytic manganese anode, Anode plate is present cold rolling type from initial cast moulding development, and alloying component is also existing from initial lead silver bianry alloy development Lead silver tin antimony arsenic multicomponent alloy, using the time from 4-6 months 18-22 till now months, it should say and make rapid progress.But It is that, with the fast development in recent years of electrolytic manganese industry, scale constantly expands, and most domestic manganese resource has started gradually Failure, although and domestic existing more biggish still undeveloped manganese ore and partial Ore Imported grade are higher, It is a kind of challenge for current domestic production technology but because chlorine contained in ore, fluorine element are relatively high.Existing production work Chlorine therein, fluorine element can not be effectively removed in skill, in electrolytic process, chlorine, fluorine element form chlorine, fluorine ion just in the electrolytic solution It can seriously be more than normal value, and generate chemical reaction with metal sun plate, form lead chloride and lead fluoride crystallization, significantly damage lead The service life of alloy anode.
Carbon fiber phosphorus content ratio is high, and (carbon fibrous body resistivity is 1.2 × 10 to good conductivity-3Ω cm), specific surface area It greatly, is a kind of good electrochemical reactor.Carbon fiber composite resin material not only has good electric conductivity, also has both Excellent mechanical performance, carbon fiber composite resin material have good corrosion resistance, resist especially in high chloride ion environment Corrosivity is excellent.However, being also easy to produce consumption when separately as anode since carbon fiber is a kind of microcrystalline graphite material.Tradition The lead silver alloy anode corrosion resistance used is not strong, and lead can be dissolved on a small quantity in anode is electrolysed the molten middle impurity for increasing cathode product, Reduce product quality.Therefore conductive good, corrosion-resistant, high-intensitive, long-life, the novel inertia of low cost Mn electrodeposition are further developed Composite anode materials, it is very necessary.
Summary of the invention
The purpose of the invention is to overcome the above-mentioned prior art there are the shortcomings that, provide a kind of electro catalytic activity it is good, Manganese electrodeposition carbon fiber-based graded composite anode material and its preparation side that tank voltage is low, long service life, at low cost, electric effect are high Method.
The purpose of the present invention is achieved through the following technical solutions:
A kind of manganese electrodeposition carbon fiber-based graded composite anode material, including carbon fiber substrate, it is compounded in carbon fiber substrate α-the PbO for introducing nano-graphene particle on surface2Composite deposite is compounded in α-PbO2Composite deposite surface introduces SiO2β-the PbO of particle2Composite deposite is covered in β-PbO2Composite deposite surface introduces RuO2β-the MnO of particle2Compound painting Layer.
α-PbO of the present invention2Graphene particles group in composite deposite becomes 1.57~4wt%, β-PbO2Composite deposite In SiO2Particle group becomes 2.01~5wt%, β-MnO2RuO in composite coating2Particle group becomes 5~25wt%.Compound sun The overall thickness of pole material be 4~13mm, carbon fiber substrate with a thickness of 3~11mm, α-PbO2Thickness of multiple plating be 0.1~ 0.5mm, β-PbO2Thickness of multiple plating is 0.39~2mm, β-MnO2Composite coating is with a thickness of 0.01~0.2mm.
Manganese electrodeposition carbon fiber-based graded composite anode material the preparation method is as follows:
(1) carbon fiber substrate is carried out except glue, under the protection of nitrogen or argon gas, at 400~800 DEG C of heating first Reason, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage；
(2) by step (1), treated that carbon fiber substrate is placed in temperature -10~15 DEG C, mass percent concentration 25% ~60% HNO340min~2h is aoxidized in aqueous solution, and carbon fiber substrate is made striated corrosion occur；
(3) step (2) treated carbon fiber substrate surface is coated into elargol, be placed in baking oven, controlled at 60 ~180 DEG C, drying time is 2~20min；The above coating and drying process 3~8 times are repeated, carbon fiber substrate surface is obtained Uniform active nano Argent grain；
(4) after the carbon fiber substrate that surface made from step (3) is coated with active nano Argent grain being placed in ultrasonic disperse Alkaline composite plating solution in, using stainless steel as cathode, temperature be 30~60 DEG C, current density be 0.1~0.8A/dm2, It is electroplated 4~8 hours under mechanical stirring, deposits to obtain the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2It is multiple Close coating；Contain 20~40g/L of PbO, 100~160g/L of NaOH, K in the alkaline composite plating solution2Cr2O75~30g/ L, 1~4g/L of nano-graphene particle；
(5) step (4) are handled into surface obtained and is deposited with α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point In acid composite plating solution after dissipating, using titanium mesh plate as cathode, temperature is 50~90 DEG C, and current density is 6~9A/dm2, It is electroplated 2~6 hours under mechanical stirring, in α-PbO2Composite deposite surface, which deposits to obtain, introduces SiO2β-the PbO of particle2It is compound Coating；Contain Pb (NO in the acid composite plating solution3)2220~400g/L, HNO32~15g/L, 3~10g/ of NaF L, Nano-meter SiO_225~20g/L；
(6) step (5) are handled into surface obtained and is deposited with β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality In the hydrofluoric acid solution of degree 5%~30%, temperature is 0~30 DEG C, and soaking time is 5~40min, and deionization washing is dry, so Uniformly brushing ruthenium trichloride and manganese nitrate are dissolved in the quality hundred being configured in organic solvent on carbon fiber substrate surface afterwards Dividing specific concentration is 20%~50% coating liquid, then 5~25min, sky are decomposed in drying under conditions of temperature is 120~200 DEG C It is cooled to room temperature, the above coating and drying operation 3~20 times is repeated, in β-PbO2Composite deposite surface forms and introduces RuO2Particle β-MnO2Composite coating is to get manganese electrodeposition carbon fiber-based graded composite anode material.
Elargol described in above-mentioned steps (3) is the sol solutions that silver nitrate and trisodium citrate form, and silver colloidal partical size is 20nm~80nm, silver colloidal partical the preparation method is as follows: in flask be added 1L distilled water, add 0.05mmol/L~ The silver nitrate of 0.1mol/L, is heated to boiling, and is quickly added with stirring the citric acid three that solution quality percentage is 0.5~20% Sodium continues back flow reaction 10min~1h, and natural cooling stirs to room temperature, is filtered, is obtained with acetic acid nitrocellulose O.22 μm To the elargol for being in yellow green.Nano-graphene particle described in step (4) be sheet or spherical particle, partial size 10nm~ 100nm.Step (5) described Nano-meter SiO_22For spherical particle, partial size is in 60nm~100nm.Step (6) ruthenium trichloride and nitre The molal weight ratio of sour manganese is 1:20~1:5.
The present invention has the advantages that compared with prior art
1, carbon fiber surface covers nano silver, greatly improves the electric conductivity of anode, keeps carbon fiber bad with electric conductivity α-PbO2Layer will not generate interface resistance.
2, composite electrodeposition α-PbO2Potassium bichromate is added in plating solution, prevents that lead is precipitated on cathode, reduces lead in solution The concentration polarization of ion, and avoid red Pb3O4The generation of substance.
3, nano-graphene particle introduces α-PbO2The internal stress in coating is reduced in coating, avoids coating crackle It generates, and greatly improves the electric conductivity and corrosion resistance of composite deposite, extend the service life of anode.
4, composite electrodeposition β-PbO at higher current densities2, so that coating is more evenly distributed in porous state, introduce nanometer SiO 2 powder is able to maintain the high hardness of coating, improves β-PbO2Inoxidizability and thermal shock resistance, make coating high At a temperature of will not decompose.
5, the β-MnO that thermal decomposition method obtains2With middle layer β-PbO2Coating forms solid solution, and conducting is high-efficient, and β- MnO2-RuO2Catalytic activity with higher can reduce the overpotential that oxygen is analysed in electrolytic process as composite anode.
6, carbon fiber substrate is not easy to be passivated, long service life, because carbon fiber is the super good conductor material of a corrosion resistance Material, therefore be on service life more than using lead as one times of the anode plate service life or more of representative；Containing chloride ion and fluoride solution Middle operation, have good corrosion resistance, lead-free high-grade manganese dioxide and metal manganese product can be made, this be lead electrode not It is likely to be breached.
Carbon fiber-based graded composite anode material prepared by the present invention is not changing compared with traditional lead-based multi-component alloy On the basis of cell construction, electrolyte composition and working specification, electric conductivity is significantly improved, and tank voltage can reduce by 12%, material Cost reduces by 20%, and current efficiency improves 3-6%.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of carbon fiber-based graded composite anode material；
Each label in figure are as follows: 1- carbon fiber substrate, 2- α-PbO2Composite deposite, 3- β-PbO2Composite deposite, 4- β-MnO2It is multiple Close coating.
Specific embodiment
The method of the present invention is described in further detail below by embodiment, but the scope of the present invention is not limited to institute State content.
Embodiment 1
As shown in Figure 1, manganese electrodeposition carbon fiber-based graded composite anode material of the invention includes carbon fiber substrate 1, answers Close the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite 2 is compounded in α-PbO2Composite deposite 2 surfaces introduce SiO2β-the PbO of particle2Composite deposite 3 is covered in β-PbO23 surface of composite deposite introduces RuO2? β-the MnO of grain2Composite coating 4.
α-PbO described in the present embodiment2Graphene particles group in composite deposite 2 becomes 2wt%, β-PbO2In composite deposite 3 SiO2Particle group becomes 3.5wt%, β-MnO2RuO in composite coating 42Particle group becomes 15wt%.Composite anode materials Overall thickness is 8mm, carbon fiber substrate with a thickness of 4.8mm, α-PbO2Thickness of multiple plating is 0.5mm, β-PbO2Composite Coatings thickness Degree is 1mm, β-MnO2Composite coating is with a thickness of 0.1mm.
Manganese electrodeposition carbon fiber-based graded composite anode material the preparation method is as follows:
(1) carbon fiber substrate 1 is carried out except glue, under the protection of nitrogen or argon gas, at 400~600 DEG C of heating first Reason, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage；
(2) by step (1) treated carbon fiber substrate is placed in -5 DEG C of temperature, the HNO that mass percent concentration is 50%3 1h is aoxidized in aqueous solution, and carbon fiber substrate is made striated corrosion occur；
(3) step (2) treated carbon fiber substrate surface is coated into elargol, be placed in baking oven, controlled at 60 DEG C, drying time 20min；The above coating and drying process 5 times are repeated, so that carbon fiber substrate surface is obtained uniform activity and receives Rice Argent grain.The elargol is the sol solutions that silver nitrate and trisodium citrate form, and silver colloidal partical size is 20nm~50nm, Silver colloidal partical the preparation method is as follows: in flask be added 1L distilled water, add the silver nitrate of 0.08mol/L, be heated to boiling It rises, is quickly added with stirring the trisodium citrate that solution quality percentage is 10%, continue back flow reaction 30min, natural cooling Stirring is filtered with acetic acid nitrocellulose O.22 μm, obtains the elargol in yellow green to room temperature；
(4) after the carbon fiber substrate that surface made from step (3) is coated with active nano Argent grain being placed in ultrasonic disperse Alkaline composite plating solution in, using stainless steel as cathode, temperature be 60 DEG C, current density 0.5A/dm2, in mechanical stirring Lower plating 8 hours, deposits to obtain the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite 2；Institute Contain lead monoxide PbO 30g/L, sodium hydroxide NaOH 100g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7 15g/L, nano-graphene particle 3g/L；The nano-graphene particle is sheet-like particle, and partial size is in 80nm~100nm；
(5) step (4) are handled into surface obtained and is deposited with α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point In acid composite plating solution after dissipating, using titanium mesh plate as cathode, temperature is 50~60 DEG C, current density 9A/dm2, in machine Tool stirring lower plating 4 hours, in α-PbO22 surface of composite deposite, which deposits to obtain, introduces SiO2β-the PbO of particle2Composite deposite 3；Contain plumbi nitras Pb (NO in the acid composite plating solution3)2300g/L, nitric acid HNO310g/L, sodium fluoride NaF8g/ L, nano silica SiO215g/L；The nano silica is spherical particle, and partial size is in 60nm~80nm；
(6) step (5) are handled into surface obtained and is deposited with β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality In the hydrofluoric acid solution of degree 30%, temperature is 20 DEG C, soaking time 30min, and deionization washing is dry, then in carbon fiber Uniformly brushing ruthenium trichloride and manganese nitrate are dissolved in the mass percent concentration being configured in organic solvent and are on matrix surface 30% coating liquid, then 25min is decomposed in drying under conditions of temperature is 150 DEG C, is air-cooled to room temperature, is repeated the above coating and is dried Dry run 10 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4 is to get manganese electrodeposition With carbon fiber-based graded composite anode material.The molal weight of the ruthenium trichloride and manganese nitrate ratio is 1:20.
With carbon fiber-based graded composite anode material in manganese electrolyte, electrolytic condition is manganese electrodeposition manufactured in the present embodiment Catholyte manganese ion concentration is 40g/L, and ammonium sulfate concentrations 120g/L, electrolysis temperature is 30 DEG C, pH 6.50, anode electricity Solution liquid manganese ion concentration is 20g/L, ammonium sulfate concentrations 120g/L, is less than 100mg/L fluoride, 600mg/L C1-Ion, sulphur Acid is 30g/L, and electrolysis temperature is 30 DEG C, using anion membrane electrolytic bath electrodeposit metals manganese, the electricity effect of the graded composite anode 4% is improved than traditional lead silver alloy anode plate, the low 180mV of tank voltage, the service life extends 1 times.
Embodiment 2
The manganese electrodeposition of the present embodiment is with carbon fiber-based graded composite anode material structure with embodiment 1.α-the PbO2It is multiple The graphene particles group closed in coating 2 becomes 1.57wt%, β-PbO2SiO in composite deposite 32Particle group becomes 5wt%, β- MnO2RuO in composite coating 42Particle group becomes 10wt%.The overall thickness of composite anode materials is 13mm, carbon fiber substrate With a thickness of 11mm, α-PbO2Thickness of multiple plating is 0.3mm, β-PbO2Thickness of multiple plating is 0.5mm, β-MnO2Composite coating With a thickness of 0.2mm.
Manganese electrodeposition carbon fiber-based graded composite anode material the preparation method is as follows:
(1) carbon fiber substrate 1 is carried out except glue, under the protection of nitrogen or argon gas, at 700~800 DEG C of heating first Reason, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage；
It (2) is 60% by step (1) treated carbon fiber substrate is placed in -10 DEG C of temperature, mass percent concentration HNO340min is aoxidized in aqueous solution, and carbon fiber substrate is made striated corrosion occur；
(3) step (2) treated carbon fiber substrate surface is coated into elargol, be placed in baking oven, controlled at 100 DEG C, drying time 10min；The above coating and drying process 3 times are repeated, so that carbon fiber substrate surface is obtained uniform activity and receives Rice Argent grain.The elargol is the sol solutions that silver nitrate and trisodium citrate form, and silver colloidal partical size is 50nm~80nm, Silver colloidal partical the preparation method is as follows: in flask be added 1L distilled water, add the silver nitrate of 0.05mmol/L, be heated to boiling It rises, is quickly added with stirring the trisodium citrate that solution quality percentage is 20%, continue back flow reaction 1h, natural cooling stirring To room temperature, is filtered with acetic acid nitrocellulose O.22 μm, obtain the elargol in yellow green；
(4) after the carbon fiber substrate that surface made from step (3) is coated with active nano Argent grain being placed in ultrasonic disperse Alkaline composite plating solution in, using stainless steel as cathode, temperature be 40 DEG C, current density 0.8A/dm2, in mechanical stirring Lower plating 6 hours, deposits to obtain the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite 2；Institute Contain lead monoxide PbO 20g/L, sodium hydroxide NaOH 150g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7 30g/L, nano-graphene particle 4g/L；The nano-graphene particle is spherical particle, and partial size is in 10nm~40nm；
(5) step (4) are handled into surface obtained and is deposited with α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point In acid composite plating solution after dissipating, using titanium mesh plate as cathode, temperature is 60~80 DEG C, current density 7A/dm2, in machine Tool stirring lower plating 6 hours, in α-PbO22 surface of composite deposite, which deposits to obtain, introduces SiO2β-the PbO of particle2Composite deposite 3；Contain plumbi nitras Pb (NO in the acid composite plating solution3)2220g/L, nitric acid HNO315g/L, sodium fluoride NaF3g/ L, nano silica SiO25g/L；The nano silica is spherical particle, and partial size is in 80nm~100nm；
(6) step (5) are handled into surface obtained and is deposited with β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality In the hydrofluoric acid solution of degree 20%, temperature is 0 DEG C, soaking time 40min, and deionization washing is dry, then in carbon fiber-based Uniformly brushing ruthenium trichloride and manganese nitrate are dissolved in the mass percent concentration being configured in organic solvent and are on body surface face 50% coating liquid, then 20min is decomposed in drying under conditions of temperature is 120 DEG C, is air-cooled to room temperature, is repeated the above coating and is dried Dry run 3 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4 is to get manganese electrodeposition use Carbon fiber-based graded composite anode material.The molal weight of the ruthenium trichloride and manganese nitrate ratio is 1:10.
With carbon fiber-based graded composite anode material in manganese electrolyte, electrolytic condition is manganese electrodeposition manufactured in the present embodiment Catholyte manganese ion concentration is 40g/L, and ammonium sulfate concentrations 120g/L, electrolysis temperature is 40 DEG C, pH 6.50, anode electricity Solution liquid manganese ion concentration is 20g/L, ammonium sulfate concentrations 120g/L, is less than 100mg/L fluoride, 800mg/L Cl-Ion, sulphur Acid is 30g/L, and electrolysis temperature is 30 DEG C, using anion membrane electrolytic bath electrodeposit metals manganese, the electricity effect of the graded composite anode 4% is improved than traditional lead silver alloy anode plate, the low 240mV of tank voltage, the service life extends 2 times.
Embodiment 3
The manganese electrodeposition of the present embodiment is with carbon fiber-based graded composite anode material structure with embodiment 1.α-the PbO2It is multiple The graphene particles group closed in coating 2 becomes 4wt%, β-PbO2SiO in composite deposite 32Particle group becomes 2.01wt%, β- MnO2RuO in composite coating 42Particle group becomes 25wt%.The overall thickness of composite anode materials is 4mm, the thickness of carbon fiber substrate Degree is 3mm, α-PbO2Thickness of multiple plating is 0.1mm, β-PbO2Thickness of multiple plating is 0.39mm, β-MnO2Composite coating is thick Degree is 0.01mm.
Manganese electrodeposition carbon fiber-based graded composite anode material the preparation method is as follows:
(1) carbon fiber substrate 1 is carried out except glue, under the protection of nitrogen or argon gas, at 600~700 DEG C of heating first Reason, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage；
(2) by step (1) treated carbon fiber substrate is placed in 15 DEG C of temperature, the HNO that mass percent concentration is 25%3 2h is aoxidized in aqueous solution, and carbon fiber substrate is made striated corrosion occur；
(3) step (2) treated carbon fiber substrate surface is coated into elargol, be placed in baking oven, controlled at 180 DEG C, drying time 2min；The above coating and drying process 8 times are repeated, so that carbon fiber substrate surface is obtained uniform activity and receives Rice Argent grain.The elargol is the sol solutions that silver nitrate and trisodium citrate form, and silver colloidal partical size is 60nm~80nm, Silver colloidal partical the preparation method is as follows: in flask be added 1L distilled water, add the silver nitrate of 0.1mol/L, be heated to boiling It rises, is quickly added with stirring the trisodium citrate that solution quality percentage is 0.5%, continue back flow reaction 10min, natural cooling Stirring is filtered with acetic acid nitrocellulose O.22 μm, obtains the elargol in yellow green to room temperature；
(4) after the carbon fiber substrate that surface made from step (3) is coated with active nano Argent grain being placed in ultrasonic disperse Alkaline composite plating solution in, using stainless steel as cathode, temperature be 30 DEG C, current density 0.6A/dm2, in mechanical stirring Lower plating 7 hours, deposits to obtain the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite 2；Institute Contain lead monoxide PbO 40g/L, sodium hydroxide NaOH 160g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7 5g/L, nano-graphene particle 1g/L；The nano-graphene particle is spherical particle, and partial size is in 10nm~30nm；
(5) step (4) are handled into surface obtained and is deposited with α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point In acid composite plating solution after dissipating, using titanium mesh plate as cathode, temperature is 80~90 DEG C, current density 6A/dm2, in machine Tool stirring lower plating 5 hours, in α-PbO22 surface of composite deposite, which deposits to obtain, introduces SiO2β-the PbO of particle2Composite deposite 3；Contain plumbi nitras Pb (NO in the acid composite plating solution3)2400g/L, nitric acid HNO32g/L, sodium fluoride NaF 10g/ L, nano silica SiO220g/L；The nano silica is spherical particle, and partial size is in 70nm~80nm；
(6) step (5) are handled into surface obtained and is deposited with β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality In the hydrofluoric acid solution of degree 5%, temperature is 30 DEG C, soaking time 5min, and deionization washing is dry, then in carbon fiber-based Uniformly brushing ruthenium trichloride and manganese nitrate are dissolved in the mass percent concentration being configured in organic solvent and are on body surface face 20% coating liquid, then 5min is decomposed in drying under conditions of temperature is 200 DEG C, is air-cooled to room temperature, is repeated the above coating and is dried Dry run 20 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4 is to get manganese electrodeposition With carbon fiber-based graded composite anode material, also referred to as carbon fiber/α-PbO2Graphene/β-PbO2-SiO2/β-MnO2-RuO2Ladder Spend composite inert anode material.The molal weight of the ruthenium trichloride and manganese nitrate ratio is 1:5.
Embodiment 4
The manganese electrodeposition of the present embodiment is with carbon fiber-based graded composite anode material structure with embodiment 1.α-the PbO2It is multiple The graphene particles group closed in coating 2 becomes 2.5wt%, β-PbO2SiO in composite deposite 32Particle group becomes 2.5wt%, β- MnO2RuO in composite coating 42Particle group becomes 5wt%.The overall thickness of composite anode materials is 10mm, the thickness of carbon fiber substrate Degree is 5.1mm, α-PbO2Thickness of multiple plating is 0.3mm, β-PbO2Thickness of multiple plating is 2mm, β-MnO2Composite coating thickness For 0.15mm.
Manganese electrodeposition carbon fiber-based graded composite anode material the preparation method is as follows:
(1) carbon fiber substrate 1 is carried out except glue, under the protection of nitrogen or argon gas, at 500~600 DEG C of heating first Reason, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage；
(2) by step (1) treated carbon fiber substrate is placed in 8 DEG C of temperature, the HNO that mass percent concentration is 40%3 1.5h is aoxidized in aqueous solution, and carbon fiber substrate is made striated corrosion occur；
(3) step (2) treated carbon fiber substrate surface is coated into elargol, be placed in baking oven, controlled at 150 DEG C, drying time 15min；The above coating and drying process 5 times are repeated, so that carbon fiber substrate surface is obtained uniform activity and receives Rice Argent grain.The elargol is the sol solutions that silver nitrate and trisodium citrate form, and silver colloidal partical size is 30nm~50nm, Silver colloidal partical the preparation method is as follows: in flask be added 1L distilled water, add the silver nitrate of 0.1mol/L, be heated to boiling It rises, is quickly added with stirring the trisodium citrate that solution quality percentage is 15%, continue back flow reaction 40min, natural cooling Stirring is filtered with acetic acid nitrocellulose O.22 μm, obtains the elargol in yellow green to room temperature；
(4) after the carbon fiber substrate that surface made from step (3) is coated with active nano Argent grain being placed in ultrasonic disperse Alkaline composite plating solution in, using stainless steel as cathode, temperature be 50 DEG C, current density 0.1A/dm2, in mechanical stirring Lower plating 4 hours, deposits to obtain the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite 2；Institute Contain lead monoxide PbO 25g/L, sodium hydroxide NaOH 120g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7 10g/L, nano-graphene particle 2g/L；The nano-graphene particle is sheet-like particle, and partial size is in 70nm~80nm；
(5) step (4) are handled into surface obtained and is deposited with α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point In acid composite plating solution after dissipating, using titanium mesh plate as cathode, temperature is 70~80 DEG C, current density 8A/dm2, in machine Tool stirring lower plating 2 hours, in α-PbO22 surface of composite deposite, which deposits to obtain, introduces SiO2β-the PbO of particle2Composite deposite 3；Contain plumbi nitras Pb (NO in the acid composite plating solution3)2300g/L, nitric acid HNO38g/L, sodium fluoride NaF6g/L, Nano silica SiO29g/L；The nano silica is spherical particle, and partial size is in 60nm~80nm；
(6) step (5) are handled into surface obtained and is deposited with β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality In the hydrofluoric acid solution of degree 15%, temperature is 25 DEG C, soaking time 15min, and deionization washing is dry, then in carbon fiber Uniformly brushing ruthenium trichloride and manganese nitrate are dissolved in the mass percent concentration being configured in organic solvent and are on matrix surface 40% coating liquid, then 15min is decomposed in drying under conditions of temperature is 150 DEG C, is air-cooled to room temperature, is repeated the above coating and is dried Dry run 8 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4 is to get manganese electrodeposition use Carbon fiber-based graded composite anode material.The molal weight of the ruthenium trichloride and manganese nitrate ratio is 1:15.

Claims (8)

1. manganese electrodeposition carbon fiber-based graded composite anode material, which is characterized in that the anode material includes carbon fiber substrate (1), it is compounded in α-the PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite (2) is compounded in α-PbO2 Composite deposite (2) surface introduces SiO2β-the PbO of particle2Composite deposite (3) is covered in β-PbO2Composite deposite (3) table Face introduces RuO2β-the MnO of particle2Composite coating (4).
2. manganese electrodeposition according to claim 1 carbon fiber-based graded composite anode material, it is characterised in that: α-PbO2It is multiple The graphene particles group closed in coating (2) becomes 1.57~4wt%, β-PbO2SiO in composite deposite (3)2Particle group becomes 2.01~5wt%, β-MnO2RuO in composite coating (4)2Particle group becomes 5~25wt%.
3. manganese electrodeposition according to claim 1 carbon fiber-based graded composite anode material, which is characterized in that described compound The overall thickness of anode material be 4~13mm, carbon fiber substrate with a thickness of 3~11mm, α-PbO2Thickness of multiple plating be 0.1~ 0.5mm, β-PbO2Thickness of multiple plating is 0.39~2mm, β-MnO2Composite coating is with a thickness of 0.01~0.2mm.
4. the preparation method of the manganese electrodeposition carbon fiber-based graded composite anode material as described in claims 1 or 2 or 3, special Sign is that method and step is as follows:
(1) carbon fiber substrate (1) is carried out except glue, under the protection of nitrogen or argon gas, at 400~800 DEG C of heating first Reason, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage；
(2) by step (1) treated carbon fiber substrate is placed in temperature -10~15 DEG C, mass percent concentration be 25%~ 60% HNO340min~2h is aoxidized in aqueous solution, and carbon fiber substrate is made striated corrosion occur；
(3) step (2) treated carbon fiber substrate surface is coated into elargol, be placed in baking oven, controlled at 60~ 180 DEG C, drying time is 2~20min；The above coating and drying process 3~8 times are repeated, obtain carbon fiber substrate surface Even active nano Argent grain；
(4) carbon fiber substrate that surface made from step (3) is coated with active nano Argent grain is placed in the alkali after ultrasonic disperse Property composite plating solution in, using stainless steel as cathode, temperature be 30~60 DEG C, current density be 0.1~0.8A/dm2, in machinery It stirring lower plating 4~8 hours, deposits to obtain the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite Coatings Layer (2)；Contain 20~40g/L of PbO, 100~160g/L of NaOH, K in the alkaline composite plating solution2Cr2O75~30g/ L, 1~4g/L of nano-graphene particle；
(5) step (4) are handled into surface obtained and is deposited with α-PbO2After the carbon fiber substrate of composite deposite is placed in ultrasonic disperse In acid composite plating solution, using titanium mesh plate as cathode, temperature is 50~90 DEG C, and current density is 6~9A/dm2, stirred in machinery Lower plating 2~6 hours is mixed, in α-PbO2Composite deposite (2) surface, which deposits to obtain, introduces SiO2β-the PbO of particle2Composite deposite (3)；Contain Pb(NO in the acid composite plating solution3)2 220~400g/L, HNO32~15g/L, 3~10 g/ of NaF L, Nano-meter SiO_225~20g/L；
(6) step (5) are handled into surface obtained and is deposited with β-PbO2The carbon fiber substrate of composite deposite be placed in mass concentration 5%~ In 30% hydrofluoric acid solution, temperature is 0~30 DEG C, and soaking time is 5~40min, and deionization washing is dry, then in carbon fiber Uniformly brushing ruthenium trichloride and manganese nitrate are dissolved in the mass percent concentration being configured in organic solvent on dimension matrix surface For 20%~50% coating liquid, then 5~25min of drying decomposition under conditions of temperature is 120~200 DEG C, it is air-cooled to room temperature, weight The above coating and drying operation 3~20 times are answered, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2It is compound Coating (4) is to get manganese electrodeposition carbon fiber-based graded composite anode material.
5. preparation method of the manganese electrodeposition according to claim 4 with carbon fiber-based graded composite anode material, feature Be, elargol described in step (3) is the sol solutions that silver nitrate and trisodium citrate form, silver colloidal partical size be 20nm~ 80nm, silver colloidal partical the preparation method is as follows: in flask be added 1L distilled water, add 0.05mmol/L~0.1mol/L's Silver nitrate, is heated to boiling, and is quickly added with stirring the trisodium citrate that solution quality percentage is 0.5~20%, continues back Stream reaction 10min~1h, natural cooling stirs to room temperature, is filtered, is obtained in yellowish green with acetic acid nitrocellulose O.22 μm The elargol of color.
6. preparation method of the manganese electrodeposition according to claim 4 with carbon fiber-based graded composite anode material, feature It is, nano-graphene particle described in step (4) is sheet or spherical particle, and partial size is in 10nm~100nm.
7. preparation method of the manganese electrodeposition according to claim 4 with carbon fiber-based graded composite anode material, feature It is, step (5) described Nano-meter SiO_22For spherical particle, partial size is in 60nm~100nm.
8. preparation method of the manganese electrodeposition according to claim 4 with carbon fiber-based graded composite anode material, feature Be: the molal weight ratio of step (6) ruthenium trichloride and manganese nitrate is 1:20~1:5.
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