CN105280398A - Preparation method of anode of Pb/C super-capacitor battery - Google Patents

Preparation method of anode of Pb/C super-capacitor battery Download PDF

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CN105280398A
CN105280398A CN201410331915.0A CN201410331915A CN105280398A CN 105280398 A CN105280398 A CN 105280398A CN 201410331915 A CN201410331915 A CN 201410331915A CN 105280398 A CN105280398 A CN 105280398A
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battery positive
preparation
ultracapacitor
ratio
carbon
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林彬
吴孟强
漆长席
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Sichuan Neng Bao Power Supply Manufacturing Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention brings forward a preparation method of an anode of a Pb/C super-capacitor battery, and is aimed at providing a preparation method of an anode, which is high in active substance utilization rate, exhibits good conductivity, high chemical stability, great power properties and low leakage current and can accelerate pole piece storage and release electric energy, of a Pb/C super-capacitor battery. According to the following technical scheme, the method includes the steps: adding 5%-15% modified high specific surface functional active carbon material slurry to an agitator tank, and stirring the slurry for 10-15min; adding 70wt%-90wt% anode active substance lead powder and a 1wt%-20wt% conductive agent to the agitator tank, and stirring the mixture for 5-10min; adding 15wt% deionized water, and stirring the mixture for 15-20min; and finally adding 10%H2SO4 (6mol/L), stirring the mixture for 20min, and then preparing a substance paste body of an anode of an energy storage type or a power type super-capacitor battery. The modified high specific surface functional active carbon material, which has been cleaned by HNO3, H3PO4 and an urea solution of 90-100 DEG C in advance and which loads part of a metallic compound, has the solid content of 15wt%-35wt%.

Description

The preparation method of Pb/C ultracapacitor battery positive pole
Technical field
The present invention relates to a kind of physical storage electric charge that collects and store charge in energy storage device-ultracapacitor battery anode preparation method integrally with chemistry.
Background technology
Existing lead-acid battery positive electrode active material utilization is low, and pole piece is poor to electrolyte wettability, dehydration serious, and power density, energy density, and useful life, charge storage are all mutually far short of what is expected compared with super capacitance cell.Super capacitance cell is a kind of novel energy-storing device having high-energy-density and high power density concurrently, it carries out " difunctional " energy storage mainly through electric double layer capacitance and fake capacitance two kinds of modes, combine the advantage of lead acid accumulator and double electric layer capacitor, one of focus becoming Recent study.The research of current ultracapacitor mainly concentrates in the preparation to high performance electrode material.Because affect in all factors of chemical cell performance, the performance of electrode material plays most important effect.Pb/C super capacitance cell electrode is normally to have the carbon material with high surface activity (AC) of difunctional energy storage characteristic, Delanium (AG) and lead oxide powder for raw material, prepared by the brown lead oxide/active carbon composite positive pole adopting the method for physical mixed to prepare and Delanium/active carbon composite negative pole material.Specific area and pore size distribution are the important parameters affecting adsorbent gas storage performance.Current high-specific surface area petroleum coke matrix activated carbon, pore-size distribution great majority concentrate on below 2nm.Due to petroleum coke compact structure, degree of crystallinity is high, and activation difficulty, lacks the first hole required for activation, need be high with a large amount of production cost, and with serious pollution highly basic activates pore-forming.Therefore optimize activating process, reduce the consumption of alkali and become the key that High-specific Area Activated Carbon develops.
Summary of the invention
For improving the power density of existing lead acid accumulator, energy density, improve useful life, charge storage, solve existing lead-acid battery positive electrode active material utilization low, pole piece is poor to electrolyte wettability, the shortcomings such as dehydration is serious, the invention provides a kind of active material utilization high, good conductivity, chemical stability is high, power characteristic is good, leakage current is little, storage battery energy density, power density is large, cryogenic property is given prominence to, low temperature (-30 DEG C) efficiency for charge-discharge is greater than 60%, pole piece can be accelerated store and release electric energy, there is the Pb/C ultracapacitor active carbon anode preparation method compared with height ratio capacity and high-specific-power.
Above-mentioned purpose of the present invention can be reached by following measures, a kind of preparation method of Pb/C ultracapacitor battery positive pole, it is characterized in that comprising the steps: by weight percentage, first 5%-15% modification high-ratio surface functionalization active carbon slurry is added in agitator tank, stir 10-15min; Again the positive active material lead powder of 70wt%-90wt% and 1wt%-20wt% conductive agent, bonding agent are added in agitator tank, stir 5-10min; Then add 15wt% deionized water, stir 15-20min; Finally add the 6mol/LH of 10%d 2sO 4, stir 20min, obtained accumulation energy type or power type super capacitor battery positive electrode material lotion, wherein, in advance through HNO 3, H 3pO 4after 90-100 DEG C of temperature urea liquid cleaning, and the modification high-ratio surface functionalization absorbent charcoal material slurry solid content of loading section metal (Zn, Pb, Bi, Ba etc.) compound is 15wt%-35wt%, particle diameter 10-30um, specific area 1200-1800m 2/ g, pore-size distribution is 3-10nm, and 0.1-0.5cm is melted in hole 3/ g; Proportion 0.75-0.9g/cm 3, high surface activity carbon, bismuth oxide Bi 2o 3, lead titanates PbTiO 4ratio is: 5: 3: 2 or 5: 2.5: 2.5; High surface activity carbon is not less than 8: 1 with the ratio of tenor; Conductive agent is one or more in electrically conductive graphite, acetylene black, conductive carbon fibre, carbon nano-tube, Graphene.
Described Pb/C ultracapacitor battery positive electrode material, will in advance through HNO 3, H 3pO 4after 90-100 DEG C of temperature urea liquid cleaning, and the load modification high-ratio surface functionalization active carbon of metal (Zn, Bi, Pb etc.) compound, by weight percentage, 10wt%-15wt% modification high-ratio surface functionalization active carbon slurry is added in agitator tank, stirs 10-15min; Again the positive active material lead powder of 70wt%-85wt% and 1wt%-20wt% conductive agent, bonding agent are added in agitator tank, stir 5-10min; Then add 15wt% deionized water, stir 15-20min; Finally add 10%H 2sO 4(6mol/L), stir 20min, obtained power type super capacitor battery positive electrode material lotion, wherein, it is 1800-2200m that modification high-ratio surface functionalization absorbent charcoal material composition comprises specific surface 2high surface activity carbon, the ratio of/g are: ZnO, Bi2O3 of 7: 1.5: 1.5 or 6: 1: 3,0.5wt%-3wt% Graphene; High surface activity carbon is not less than 9: 1 with the ratio of tenor; Modification high-ratio surface functionalization absorbent charcoal material slurry solid content is 15wt%-30wt%, particle diameter 10-30um, specific area 1500-1800m 2/ g, pore-size distribution is 3-8nm, and 0.1-0.5cm is melted in hole 3/ g; Proportion 0.75-0.9g/cm 3; Conductive agent is one or more in electrically conductive graphite, acetylene black, conductive carbon fibre, carbon nano-tube, Graphene.
In above-mentioned positive electrode material, accumulation energy type Pb/C ultracapacitor battery positive pole will will form electric double layer and chemistry two kinds of energy storage mechnism after modification high-ratio surface functionalization absorbent charcoal material slurry and other component Homogeneous phase mixing in same monomer, this just makes pole plate obviously be better than the pole plate of single energy storage mechnism to the absorbability of electric charge, modification high-ratio surface functionalization absorbent charcoal material has very flourishing pore structure, impel the electrolyte in storage battery fully can contact with active material, to charged particle, electric charge is in pole piece, internal migration has great facilitation, charged particle is evenly distributed on modification high-ratio surface functionalization absorbent charcoal material surface, improve the energy storage density in unit are, effectively can suppress the sulphation phenomenon of pole piece in thermal energy storage process, the compound of modification high-ratio surface functionalization absorbent charcoal material area load can effectively suppress Barium sulfate crystals refinement, improve active material hydrogen-evolution overpotential point in the electrolytic solution.
The positive pole of power-type Pb/C ultracapacitor battery modification high-ratio surface functionalization absorbent charcoal material is evenly coated in lead acid battery positive electrode sheet surface, this kind of preparation method does not still realize electric double layer, chemical energy storage in same monomer, and electric double layer energy storage is had an effect the earliest in thermal energy storage process; The modification high-ratio surface functionalization absorbent charcoal material of pore structure prosperity can adsorb charged particle, transmission charge fast, and this interaction energy is accelerated pole piece and stored and release electric energy, improves the power density in unit are; Modification high-ratio surface functionalization absorbent charcoal material can adsorb a large amount of electrolyte to material surface in addition, and electrolyte can not be reduced or the electro-ionic migration of inhibition zone because of electrolyte solidification under compared with low ambient temperature condition.
The present invention has following beneficial effect compared to prior art:
Use the present invention to adopt and active carbon is carried out surface chemical modification process, change the surface acid of active carbon, alkalescence, introduce at carbon surface or remove some functional group, active carbon can be made to have certain special absorption property and catalysis characteristics, make opposed polarity material, metal ion, anode prepared by the modification high-ratio surface functionalization absorbent charcoal material that the pollutants such as metal simple-substance have efficient deep purifying, storage battery large current density power is strengthened, active material utilization improves, the energy density of storage battery, power density obviously promotes, it is 1.5-2 times of conventional accumulators, cycle life is used obviously to promote in addition, accumulator low temperature performance is given prominence to,-30 DEG C of efficiency for charge-discharges are greater than 60%,
The present invention adopts the modification high-ratio surface functionalization absorbent charcoal material with flourishing micropore and great specific area as a part for positive electrode, due to it, to have specific area large, ratio capacitance is large, pore-size distribution is narrow, good conductivity, chemical stability advantages of higher, pole piece electrodialysis effect can be strengthened, enhance the infiltration of electrolyte to pole piece, improve electrode conductivity, increase pole plate porosity, the microcrystalline carbon materials of this modification high-ratio surface functionalization absorbent charcoal material can give full play to electric double layer, the power density of asymmetric capacitor is high, capacitance is large, leakage current is little, the features such as charge and discharge process is fast and have extended cycle life.
Large, the micro-pore distribution concentration of specific area of modification high-ratio surface functionalization active carbon that the present invention adopts and good adsorption performance, performance index are far away higher than normal activated carbon, and specific area is at 1800 ~ 2500m 2/ g.Through pernitric acid and urea cleaning, the surface-functionalized absorbent charcoal material surface of height after high-temperature process can forming section containing oxygen, nitrogen functional group.Or pass through H 2sO 4, HNO 3, H 2o 2, (NH 4) oxidizing solution such as 2S208 increases the quantity of the functional group such as carboxyl, carbonyl, phenolic hydroxyl group on porous carbon material surface at load Bi 2o 3, PbTiO 4, in the metallic compound process such as ZnO, metal complex can be formed with metal ions such as Bi, Pb, Zn, Ba containing oxygen, nitrogen functional group, what make that the compound of load more can be stable is adsorbed on carbon material with high surface activity surface; In addition, this hydrophily that can improve high surface carbon surface containing oxygen, nitrogen functional group, is conducive to the absorption of electrolyte ion, increases the ability forming electric double layer, the C/PbO formed in Pb/C battery system 2, C/C ultracapacitor principle can improve positive electrode active material utilization greatly, generally can improve 15-18%, charge transport ability improves 20%, and charge and discharge circulation life brings up to more than 2000 times.
The Pb/C ultracapacitor battery adopting the corresponding right negative pole of Pb/C ultracapacitor battery positive pole of the present invention to be formed can apply and electrical vehicular power power supply, start power supply, also can be used as wind-force, photovoltaic energy storage equipment, various stand-by power supply, energy storage of avoiding the peak hour, the fields such as communication, electric power.
Embodiment
The present invention is further illustrated below by embodiment and comparative example.Pb/C ultracapacitor battery positive pole disclosed by the invention comprises into accumulation energy type, power-type two kinds, is to the addition of modification high-ratio surface functionalization absorbent charcoal material slurry 5-35%, active material 70-90%, conductive agent 1-20%, bonding agent 1-10%, other additive 0.5-10% and form the anode preparation method of accumulation energy type, power-type two kinds of Pb/C ultracapacitor batteries by different adding proportion on plus plate current-collecting body (foamy graphite, charcoal collector, calcium alloy stereotype).
In the following Examples and Comparative Examples, described ultracapacitor battery cell positive material also comprises bonding agent and other additive, and the bonding agent content wherein in accumulation energy type ultracapacitor battery positive electrode material is 1wt%-10wt%, other additive 0.5wt%-10wt%.
Accumulation energy type Pb/C ultracapacitor battery positive pole comprises modification high-ratio surface functionalization absorbent charcoal material slurry 5wt%-15wt%, positive active material 70wt%-90wt%, conductive agent 1wt%-20wt%, bonding agent 1wt%-10wt%, other additive 0.5wt%-10wt%; The modification high-ratio surface functionalization absorbent charcoal material solid content related in the present invention is at 15wt%-35wt%, and preferred solid content is 20%, viscosity 3000-5000mps.The modification high-ratio surface functionalization absorbent charcoal material composition related in the present invention comprises carbon material with high surface activity, Bi 2o 3, PbTiO 4, its ratio is: 5: 3: 2 or 5: 2.5: 2.5; The particle diameter of modification high-ratio surface functionalization absorbent charcoal material is 10-30um, and specific area is 1200-1800m 2/ g, pore-size distribution is: 3-10nm, Kong Rong: 0.1-0.5cm 3/ g; Proportion is 0.75-0.9g/cm 3; Wherein material with carbon element is not less than 8: 1 with the ratio of tenor;
Comprise 0.5-3wt% Graphene in modification high-ratio surface functionalization absorbent charcoal material slurry, the Graphene number of plies is 5-10 layer, and specific surface is at 500-750m 2/ g; Electrically conductive graphite content is not less than 25wt%;
Carbon Materials in modification high-ratio surface functionalization absorbent charcoal material slurry need through HNO 3, H 3pO 4cleaning, 90-100 DEG C of high temperature urea liquid.
Active material in accumulation energy type Pb/C ultracapacitor battery positive electrode material is lead powder, and density is 1.39 ± 0.005g/cm 3;
Bonding agent in accumulation energy type Pb/C ultracapacitor active carbon anode material comprises: HPMC, polyacrylic acid, polyvinyl alcohol, ethylene-vinyl acetate copolymer EVA are also known as one or more in EVA resin, LA132/133 etc., and additive package contains: red lead, sulfuric acid, deionized water, short fiber etc.
Conductive agent in accumulation energy type Pb/C ultracapacitor battery positive electrode material comprises: one or more in electrically conductive graphite, acetylene black, conductive carbon fibre, carbon nano-tube, Graphene etc.;
Conductive agent in power-type Pb/C ultracapacitor battery positive electrode material comprises: electrically conductive graphite, carbon nanometer, other additive comprises: red lead, sulfuric acid, deionized water, short fiber etc.
Power-type Pb/C ultracapacitor battery positive electrode material comprises modification high-ratio surface functionalization absorbent charcoal material slurry 10wt%-15wt%, active material 70wt%-85wt%, conductive agent 1wt%-15wt%), bonding agent 1wt%-10wt%, other additive 0.5wt%-10wt%.Modification high-ratio surface functionalization absorbent charcoal material solid content is at 15-35wt%, and preferred solid content is 30wt%, viscosity 3000-5000mps;
Its composition of modification high-ratio surface functionalization absorbent charcoal material comprises high surface activity carbon, ZnO, Bi2O3, and its ratio is: 7: 1.5: 1.5 or 6: 1: 3; Wherein the particle diameter of modification high-ratio surface functionalization absorbent charcoal material is 10-30um, and specific area is 1500-1800m 2/ g, pore-size distribution is: 3-8nm, Kong Rong: 0.1-0.5cm 3/ g; Proportion is 0.75-0.9g/cm 3; Wherein the ratio of material with carbon element metallizing thing content is not less than 9: 1;
Comprise 0.5wt%-3wt% Graphene in modification high-ratio surface functionalization absorbent charcoal material slurry, the Graphene number of plies is 5-10 layer, and specific surface is at 500-750m 2/ g; In the surface-functionalized absorbent charcoal material slurry of high-modification-ratio, electrically conductive graphite content is not less than 25wt%;
Carbon Materials in modification high-ratio surface functionalization absorbent charcoal material slurry need through HNO 3, H 3pO 4cleaning, 90-100 DEG C of temperature urea liquid cleaning;
Active material in power-type Pb/C ultracapacitor battery positive electrode material is lead powder, density is 1.39g/cm3, and the bonding agent in power-type Pb/C ultracapacitor battery positive electrode material comprises: one or more in LA132/133, polyvinyl alcohol, SBR, butadiene-styrene rubber, HPMC etc.
Conductive agent in power-type Pb/C ultracapacitor battery positive electrode material comprises: electrically conductive graphite, carbon nanometer, and other additive in power-type Pb/C ultracapacitor battery positive electrode material comprises: red lead, sulfuric acid, deionized water, short fiber etc.;
Preparation method:
Mixing method: accumulation energy type ultracapacitor battery positive active material active material, additive are joined in proportion in mixer, stirs 5-10min; Proportionally add high-ratio surface modified activated carbon material paste, stir 10-15min; Add 15wt% deionized water, stir 15-20min; Add 10wt%H 2sO 4(6mol/L), stir 20min and namely obtain accumulation energy type ultracapacitor battery positive electrode paste, then by lotion even application on anode collection screen, dry, solidification can obtain accumulation energy type ultracapacitor battery positive pole; Wherein the oxidizability of lead powder is 65-85%.
Brushing method: according to lead-acid battery positive plate preparation method, the lead-acid battery positive plate prepared by conventional program is invaded and is steeped 30min in deionized water, take out air-dry 12h, at positive plate surface xxx formula spray gun or craft, high-ratio surface modified activated carbon material paste is uniformly sprayed in pole piece, namely often spray once that drying is once, baking temperature 85 DEG C, time 15min, repeatedly brush 3-5 time, make coating layer thickness reach 0.75-0.85mm thick, dry solidification can obtain power type super capacitor battery positive pole.
Embodiment 1
In accumulation energy type Pb/C ultracapacitor battery anode formula: at normal temperatures and pressures, respectively by each component of specifying in table 1, by modification high-ratio surface functionalization absorbent charcoal material slurry: 76.5kg, lead powder: the 500kg of oxidizability 75 ± 2%, deionized water: 48kg, short fiber: 2.3kg, 1.3g/cm 3sulfuric acid 52kg mixture enters and stirs in vertical paddle agitator.Adopt dry and legal system for positive electrode paste: in vertical blade stirring-type paste mixing machine, to add lead powder and short fiber stirs 10min, add high-ratio surface modified activated carbon material paste again and stir 15min, then slowly join in paste mixing machine at 15-20min inland river sulfuric acid, add deionized water subsequently, time controling, in 15min, then stirs 20min and can obtain accumulation energy type Pb/C ultracapacitor active carbon anode lotion (half sand mold lead plaster); Adopt domestic coating machine by positive electrode paste even application on lead-calcium alloy plate (Carbon foam screen), drying process adopts first temperature 40 DEG C, solidifies 24h under relative humidity 90% condition; Temperature 60 C again, solidifies 48h under relative humidity 60% condition; Can obtain accumulation energy type Pb/C super capacitor (device) anode, dried substrate thickness is between 4.25-4.3mm.
Embodiment 2
By the method repeating EXPERIMENTAL EXAMPLE 1 with each combined content of specifying in following table 1, list test result in Table 1.
In power-type Pb/C super capacitor (device) anode formula: the lead powder of oxidizability 75 ± 2%: 500kg, deionized water: 51kg, short fiber: 2.7kg, 1.25g/cm 3sulfuric acid 45kg, acetylene black: 3kg, electrically conductive graphite: 2kg.Do with legal system for positive electrode paste.In vertical blade stirring-type paste mixing machine, add lead powder, acetylene black, electrically conductive graphite and short fiber stir 10min, then in 10min, sulfuric acid is slowly joined in paste mixing machine, add deionized water subsequently, time controling, in 15min, then stirs 15min and can obtain power-type Pb/C super capacitor (device) anode lotion (half sand mold lead plaster).Adopt domestic coating machine by positive electrode paste even application on lead-calcium alloy plate, drying process adopts first temperature 40 DEG C, solidifies 24h under relative humidity 90% condition; Temperature 60 C again, solidifies 48h under relative humidity 60% condition; Dried substrate thickness is between 3.75-3.8mm.Dried pole piece adopts manually or high-ratio surface modified activated carbon material paste is brushed in pole piece by paint formula flush coater uniformly, 80 DEG C of dry 2h in air dry oven again, take out, above operation 3 times repeatedly, last drying time is 8h, make external coating layer thickness at 0.15mm, power-type Pb/C ultracapacitor active carbon anode can be obtained.
The formula component property index of table 1 embodiment 1 ~ 8
Each constituent content (weight portion) wt% Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8
Lead powder 76 73.5 72 65.5 75.5 75.5 71.5 75
High-ratio surface functionalization active carbon 5 5 8 8 10 10 12.5 15
HPMC 3.5 1 2 1
Polyacrylic acid 1 1 2 0.5
Polyvinyl alcohol 1 1 1
EVA copolymer 1 0.5
LA132/133 2.5 1 1 1 1
Electrically conductive graphite 2 2 2 1 0.5
Acetylene black 2 2 2 2 1 1 1
Conductive carbon fibre 1 2 3 2 1 1
Carbon nano-tube 1 0.5
Graphene 1 2 0.5
Red lead 1 1 1 1 0.5 0.5 0.5 0.5
Short fiber 2.5 3 1 4 0.5 0.5 0.5 0.5
Humic acid 2 1 0.5 0.5 0.5 0.5 0.5
Baking temperature (DEG C) 60 60 60 60 80 80 80 80
Hydrogen-evolution overpotential point 2.56 2.62 2.53 2.65 2.62 2.64 2.65 2.66
Low temperature efficiency for charge-discharge/% (-15 DEG C) 85 82 80 87 75 82 80 80
Low temperature efficiency for charge-discharge/% (-30 DEG C) 61.3 60.5 60.7 62.1 65.5 63.7 64.8 64.6
Circulate 1500 capacity attenuation rate/% 10 8 9 7 15 10 13 9
Embodiment 1-4 is accumulation energy type Pb/C ultracapacitor battery, and main method adopts modification high-ratio surface functionalization absorbent charcoal material slurry Homogeneous phase mixing together with other material; Embodiment 5-8 is power-type Pb/C ultracapacitor battery, and main method adopts spraying process to be coated in pole piece in modification high-ratio surface functionalization absorbent charcoal material slurry.

Claims (10)

1. a preparation method for Pb/C ultracapacitor battery positive pole, is characterized in that comprising the steps:
By weight percentage, first 5%-15% modification high-ratio surface functionalization active carbon slurry is added in agitator tank, stir 10-15min; Again the positive active material lead powder of 70wt%-90wt% and 1wt%-20wt% conductive agent, bonding agent are added in agitator tank, stir 5-10min; Then add 15wt% deionized water, stir 15-20min; Finally add the 6mol/LH of 10%d 2sO 4, stir 20min, obtained accumulation energy type or power type super capacitor battery positive electrode material lotion, wherein, in advance through HNO 3, H 3pO 4after 90-100 DEG C of temperature urea liquid cleaning, and the modification high-ratio surface functionalization absorbent charcoal material slurry solid content of loading section metallic compound is 15wt%-35wt%, particle diameter 10-30um, specific area 1200-1800m 2/ g, pore-size distribution is 3-10nm, and 0.1-0.5cm is melted in hole 3/ g; Proportion 0.75-0.9g/cm 3, high surface activity carbon, bismuth oxide Bi 2o 3, lead titanates PbTiO 4ratio is: 5: 3: 2 or 5: 2.5: 2.5; High surface activity carbon is not less than 8: 1 with the ratio of tenor; Conductive agent is one or more in electrically conductive graphite, acetylene black, conductive carbon fibre, carbon nano-tube, Graphene.
2. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 1, it is characterized in that: described ultracapacitor battery positive electrode also comprises bonding agent and other additive, and the bonding agent content wherein in accumulation energy type ultracapacitor battery positive electrode material is 1wt%-10wt%, other additive is 0.5wt%-10wt%.
3. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 2, is characterized in that: the bonding agent in accumulation energy type Pb/C ultracapacitor active carbon anode material comprises: one or more in Hydroxypropyl methylcellulose HPMC, polyacrylic acid, polyvinyl alcohol, ethylene-vinyl acetate copolymer EVA copolymer, aqueous binder LA132/133.
4. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 2, is characterized in that: the additive package in accumulation energy type or power-type Pb/C ultracapacitor battery positive electrode material contains: red lead, sulfuric acid, deionized water and short fiber.
5. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 1, is characterized in that: described Pb/C ultracapacitor battery positive electrode material, comprises and being made up of following steps, by active carbon with high specific surface area in advance through HNO 3, H 3pO 4after 90-100 DEG C of temperature urea liquid (or other weak oxidant solution) cleaning, and the modification high-ratio surface functionalization absorbent charcoal material of loading section metal (Zn, Pb, Ba etc.) compound, by weight percentage, the modification high-ratio surface functionalization active carbon slurry of 10wt%-15wt% is added in agitator tank, stirs 10-15min; Again the positive active material lead powder of 70wt%-85wt% and 1wt%-20wt% conductive agent are added in agitator tank, stir 5-10min; Then add 15wt% deionized water, stir 15-20min; Finally add the 6mol/LH of 10% 2sO 4, stir 20min, obtained power type super capacitor battery positive electrode material lotion, wherein, it is 1800-2200m that modification high-ratio surface functionalization absorbent charcoal material composition comprises specific surface 2the high surface activity carbon of/g, ratio are ZnO, Bi2O3 of 7: 1.5: 1.5 or 6: 1: 3,0.5wt%-3wt% Graphene; High surface activity carbon is greater than 9: 1 with the ratio of tenor; High-ratio surface modified activated carbon solid content is 15wt%-30wt%, particle diameter 10-30um, specific area 1500-1800m 2/ g, pore-size distribution is 3-8nm, and 0.1-0.5cm is melted in hole 3/ g; Proportion 0.75-0.9g/cm 3; Conductive agent is one or more in electrically conductive graphite, acetylene black, conductive carbon fibre, carbon nano-tube, Graphene.
6. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 1, is characterized in that: the conductive agent in power-type Pb/C ultracapacitor active carbon anode material is 1wt%-15wt%, bonding agent 1wt%-10wt%, other additive 0.5wt%-10wt%.
7. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 1, is characterized in that: the bonding agent in power-type Pb/C ultracapacitor battery positive electrode material comprises: one or more in aqueous adhesive LA132/133/135, polyvinyl alcohol, styrene butadiene rubber sbr, Hydroxypropyl methylcellulose HPMC.
8. the preparation method of Pb/C ultracapacitor battery positive electrode as claimed in claim 1, it is characterized in that: in modification high-ratio surface functionalization absorbent charcoal material slurry, comprise 0.5wt%-3wt% Graphene, the Graphene number of plies is 5-10 layer, and specific surface is at 500-750m 2/ g.
9. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 1, is characterized in that: in modification high-ratio surface functionalization absorbent charcoal material slurry, electrically conductive graphite content is greater than 15wt%.
10. the preparation method of Pb/C ultracapacitor battery positive pole as claimed in claim 1, is characterized in that: the oxidizability of lead powder is 75-85%.
CN201410331915.0A 2014-07-14 2014-07-14 Preparation method of anode of Pb/C super-capacitor battery Pending CN105280398A (en)

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Application publication date: 20160127