CN105321730B - The preparation method of Pb/C ultracapacitor battery cathode - Google Patents
The preparation method of Pb/C ultracapacitor battery cathode Download PDFInfo
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Abstract
A kind of preparation method of Pb/C ultracapacitors battery cathode proposed by the present invention, it is high to be intended to provide a kind of active material utilization, power characteristic is good, leakage current is small, has extended cycle life, the ultracapacitor battery cathode preparation method that pole piece stores and release electric energy is had excellent performance.The technical scheme is that：High-ratio surface functionalization absorbent charcoal material slurry is modified by 5%~15% to add in agitator tank, stir 10~15min first；The negative electrode active material lead powder (oxidizability 75%) of 50wt%~65wt%, 1wt%~5wt% conductive agents and 1wt%~3wt% auxiliary agents are added in agitator tank again, stir 5~10min；Then 10wt% deionized waters are added in, stir 25~30min；It is eventually adding 10wt%H2SO4(6mol/L) stirs 20min, accumulation energy type or power type super capacitor battery negative material lotion is made.Wherein, in advance through HNO3、H3PO4After being cleaned with 90~100 DEG C of temperature urea liquids, and loading section metallic compound.
Description
Technical field
The present invention relates to a kind of collection physical storage charges and chemistry to store charge in integrated energy storage device~super capacitor
Device battery cathode preparation method.
Background technology
Existing lead-acid battery cathode active material utilization is low, and pole piece is poor to electrolyte wettability, dehydration is serious, and
Power density, energy density, service life, charge storage are all mutually far short of what is expected compared with super capacitance cell.Super capacitance cell
It is a kind of new type of energy storage device for having both high-energy density and high power density, it mainly passes through electric double layer capacitance and fake capacitance two
The advantages of kind mode carries out " difunctional " energy storage, combines both lead-acid accumulator and double layer capacitor, becomes and grinds in recent years
One of hot spot studied carefully.The research of ultracapacitor is concentrated mainly in the preparation to high performance electrode material at present.Because it influences
In all factors of chemical cell performance, the performance of electrode material plays most important effect.Pb/C super capacitance cell electrodes
Typically using the carbon material with high surface activity (AC) with difunctional energy storage characteristic, Delanium (AG) and lead oxide powder as original
Material, the brown lead oxide/activated carbon composite positive pole and Delanium/activated carbon Compound Negative prepared using the method for physical mixed
Pole material preparation.Specific surface area and pore size distribution are to influence the important parameter of adsorbent gas storage performance.High-specific surface area stone at present
Most of oil coke matrix activated carbon, pore-size distribution concentrate below 2nm.Due to petroleum coke compact structure, crystallinity is high, and activation is tired
Difficulty lacks the required just hole of activation, mass production need to be used of high cost, and seriously polluted highly basic activates pore-forming.Therefore optimize
Activating process reduces the key that the dosage of alkali develops as High-specific Area Activated Carbon.
Invention content
Power density, energy density of the present invention to improve existing lead-acid accumulator, improve service life, charge storage energy
Power, solving that existing lead-acid battery cathode active material utilization is low, and pole piece is poor to electrolyte wettability, dehydration is serious etc. lacks
Point provides a kind of active material utilization height, and good conductivity, chemical stability are high, power characteristic is good, leakage current is small, accumulator
Energy density, power density are big, and cryogenic property protrudes, and low temperature (~30 DEG C) efficiency for charge-discharge is more than 60%, can accelerate pole piece and deposit
Storage and release electric energy, have high specific capacity and the Pb/C ultracapacitor activated carbon battery cathode preparation methods of high-specific-power.
The above-mentioned purpose of the present invention can be reached by following measures, a kind of system of Pb/C ultracapacitors battery cathode
Preparation Method, it is characterised in that include the following steps：
It is 20wt%~30wt%, 10~30um of grain size, 1200~1800m of specific surface area first by solid content2/ g, aperture
3~10nm is distributed as, 0.3~1cm is melted in hole3/ g, proportion are 0.75~0.9g/cm3Modification high-ratio surface functionalization activity raw material of wood-charcoal
Slurry material, through HNO3、H3PO4After being cleaned with 90~100 DEG C of temperature urea liquids, loading section metallic compound, metallic compound
For zinc oxide ZnO, barium sulfate BaSO4, lead titanates PbSO4, wherein, the ratio between high surface activity carbon and metallic compound content be not low
In 8: 1；High surface activity carbon, ZnO, BaSO4、PbSO4Ratio is：6: 1: 1: 2 or 6: 2: 1: 1；Then by weight percentage,
5%~15% above-mentioned modified high-ratio surface functionalization activated carbon slurry is added in agitator tank, stirs 10~15min；Again will
Negative electrode active material lead powder Pb/C and 1wt%~5wt% conductive agent, bonding agent and the other additives of 50wt%~65wt% adds
Enter in agitator tank, stir 5~10min；10wt% deionized waters are added, stir 20min；It is eventually adding the 6mol/L of 10%wt
H2SO4, 20min is stirred, accumulation energy type or power type super capacitor activated carbon battery cathode substance lotion, above-mentioned conduction is made
Agent is one or more of electrically conductive graphite, acetylene black, conductive carbon fibre, conductive black, graphene.
In above-mentioned negative material, accumulation energy type Pb/C ultracapacitor battery cathode are that modified high-ratio surface functionalization is lived
Property Carbon Materials slurry uniformly mixed with other components after electric double layer and chemical two kinds of energy storage mechnisms will be formed in same monomer,
This allows for the pole plate that pole plate is substantially better than the absorbability of charge single energy storage mechnism, modified high-ratio surface functionalization activity
Carbon Materials have very flourishing pore structure, and the electrolysis liquid energy in accumulator is promoted to be come into full contact with active material, to electrification
Particle, charge greatly facilitate effect in pole piece, internal migration, and charged particle is evenly distributed on modified high-ratio surface work(
Absorbent charcoal material surface can be changed, improve the energy storage density in unit area, can effectively inhibit negative plate in thermal energy storage process
Sulphation phenomenon, the compound of modified high-ratio surface functionalization absorbent charcoal material area load can effectively inhibit Barium sulfate crystals thin
Change, improve the hydrogen-evolution overpotential point of active material in the electrolytic solution.
The cathode of power-type Pb/C ultracapacitor batteries is uniformly to apply modified high-ratio surface functionalization absorbent charcoal material
Acid accumulator negative pole lead piece surface is overlayed on, this kind of preparation method does not realize electric double layer, chemical energy storage still in same monomer, and
And electric double layer energy storage is had an effect earliest in thermal energy storage process；The modification high-ratio surface functionalization activity raw material of wood-charcoal of pore structure prosperity
Material can quickly adsorb charged particle, transmit charge, and this effect can accelerate pole piece storage and release electric energy, improve unit plane
Power density in product；In addition a large amount of electrolyte can be adsorbed to material surface by being modified high-ratio surface functionalization absorbent charcoal material,
So that electrolyte will not reduce or inhibit the migration of charged ion due to electrolyte cures under relatively low ambient temperature conditions.
The present invention has the advantages that compared with the prior art：
Surface chemical modification processing is carried out using by activated carbon using the present invention, changes the surface alkalinity of activated carbon,
Carbon surface introduces or removes certain functional groups, and activated carbon can be made to have certain special absorption property and catalysis characteristics, made pair
The modification high-ratio surface functionalization that the pollutants such as opposed polarity substance, metal ion, metal simple-substance have efficient deep purifying is lived
Property Carbon Materials prepare battery cathode so that accumulator high current charge-discharge ability is strengthened, active material utilization improve,
Energy density, the power density of accumulator are obviously improved, and are 1.5~2 times of conventional accumulators, in addition apparent using cycle life
It is promoted, accumulator low temperature performance protrudes, and~30 DEG C of efficiency for charge-discharges reach 60%；
The present invention is using the modification high-ratio surface functionalization absorbent charcoal material with flourishing micropore and great specific surface area
As a part for negative material, due to it with large specific surface area, specific capacitance is big, pore-size distribution is narrow, good conductivity, chemistry are steady
The advantages that qualitative high, can enhance pole piece electrodialysis effect, enhance infiltration of the electrolyte to pole piece, improve electrode conductivity, increase
Add pole plate porosity, the microcrystalline carbon materials of this modified high-ratio surface functionalization absorbent charcoal material can give full play to double electricity
Layer, the spies such as the power density of asymmetric capacitor is high, capacitance is big, leakage current is small, charge and discharge process is fast and has extended cycle life
Point.
Large specific surface area, micro- pore distribution concentration and the adsorptivity of modification high-ratio surface functionalization activated carbon that the present invention uses
Can be excellent, performance indicator is significantly larger than normal activated carbon, and specific surface area is in 1800~2500m2/g.It is clear through pernitric acid and urea
It washes, the surface-functionalized absorbent charcoal material surface of height after high-temperature process can form that part is oxygen-containing, nitrogen functional group.Or pass through
H2SO4、HNO3、H2O2、(NH4) oxidizing solutions such as 2S208 increase the carboxyl on porous carbon material surface, carbonyl, phenolic hydroxyl group etc.
The quantity of functional group is in load BaSO4、PbSO4, during the metallic compounds such as ZnO, oxygen-containing, nitrogen functional group can be with Pb, Zn, Ba
Metal ions is waited to form metal complex, make the absorption that the compound of load can more be stablized on carbon material with high surface activity surface；
In addition, this oxygen-containing, nitrogen functional group can improve the hydrophily of high surface carbon surface, be conducive to the suction of electrolyte ion
It is attached, increase the ability for forming electric double layer, the C/PbO formed in Pb/C battery systems2, C/C ultracapacitor principles can be significantly
Positive electrode active material utilization is improved, can generally improve 15~18%, charge transport ability improves 20%, charge and discharge cycles
Service life is increased to 2000 times or more.
Pb/C ultracapacitors battery anode using the present invention correspondingly to cathode formed Pb/C super capacitors
Device battery can apply with electrical vehicular power power supply, startup power supply, also can be used as wind-force, photovoltaic energy storage equipment, various standby electricities
The fields such as source, energy storage of avoiding the peak hour, communication, electric power.
Specific embodiment
It is further illustrated the present invention below by embodiment and comparative example.Pb/C ultracapacitors battery disclosed by the invention
Cathode is included into two kinds of accumulation energy type, power-type, is pressed on negative current collector (foamy graphite, charcoal collector, calcium alloy stereotype)
Different adding proportions are added to modified high-ratio surface functionalization absorbent charcoal material slurry 5~15%, active material 50~65%, lead
Electric agent 1~5%, bonding agent 0.5~1.5%, other additives 0.5~1% and to form two kinds of accumulation energy type, power-type Pb/C super
The cathode preparation method of capacitor battery.
In the following Examples and Comparative Examples, the ultracapacitor battery cell negative electrode material further include bonding agent and
Bonding agent content in other additives, wherein accumulation energy type ultracapacitor battery negative material is 1wt%~1.5wt%, it
Its additive 0.5wt%~1wt%.
Accumulation energy type Pb/C ultracapacitor batteries cathode includes modified high-ratio surface functionalization absorbent charcoal material slurry 5wt%
~15wt%, negative electrode active material 50wt%~65wt%, conductive agent 1wt%~5wt%, bonding agent 1wt%~1.5wt%,
Other additive 0.5wt%~1wt%；Modification high-ratio surface functionalization absorbent charcoal material solid content involved in the present invention exists
20wt%~30wt%, preferably solid content are 25%, 3000~5000mps of viscosity.Modification Gao Bibiao involved in the present invention
Face functionalization absorbent charcoal material ingredient includes carbon material with high surface activity, ZnO, BaSO4、PbSO4, its ratio be：6: 1: 1: 2 or
Person 6: 2: 1: 1；The grain size of modified high-ratio surface functionalization absorbent charcoal material is 10~30um, specific surface area for 1200~
1800m2/ g, pore-size distribution are：3~10nm, Kong Rong：0.3~1.0cm3/g；Proportion is 0.75~0.9g/cm3；Wherein carbon material
It is not less than 8: 1 with the ratio between tenor；
Comprising 0.5~3wt% graphenes in modified high-ratio surface functionalization absorbent charcoal material slurry, the graphene number of plies is 5
~10 layers, specific surface is in 500~750m2/g；Electrically conductive graphite content is not less than 25wt%；
Carbon Materials in modified high-ratio surface functionalization absorbent charcoal material slurry need to pass through HNO3、H3PO4Cleaning, 90~100
DEG C high temperature urea liquid.
Active material in accumulation energy type Pb/C ultracapacitor battery negative materials is lead powder, density for 1.39 ±
0.005g/cm3；
Bonding agent in accumulation energy type Pb/C ultracapacitor activated carbon battery cathode substances includes：HPMC, polyacrylic acid, gather
Vinyl alcohol, ethylene~vinyl acetate copolymer eva are also known as one or more in EVA resin, LA132/133 etc., additive packet
Contain：Humic acid, sodium lignosulfonate, barium stearate, sulfuric acid, deionized water, staple fiber etc..
Conductive agent in accumulation energy type Pb/C ultracapacitor battery negative materials includes：Electrically conductive graphite, acetylene black, conductive carbon
It is one or more in fiber, carbon nanotube, graphene etc.；
Conductive agent in power-type Pb/C ultracapacitor battery negative materials includes：Electrically conductive graphite, carbon nanometer, Qi Tatian
Agent is added to include：Humic acid, sodium lignosulfonate, barium stearate, sulfuric acid, deionized water, staple fiber etc..
Power-type Pb/C ultracapacitor batteries negative material includes modified high-ratio surface functionalization absorbent charcoal material slurry
10wt%~15wt%, active material 60wt%~65wt%, conductive agent 3wt%~5wt%), bonding agent 1wt%~
1.5wt%, other additive 0.5wt%~1wt%.Modified high-ratio surface functionalization absorbent charcoal material solid content 20~
30wt%, preferably solid content are 30wt%, 3000~5000mps of viscosity；
Its ingredient of modified high-ratio surface functionalization absorbent charcoal material includes high surface activity carbon, ZnO, BaSO4、PbSO4,
Ratio is 6: 1: 1: 2 or 6: 2: 1: 1；The grain size of wherein modified high-ratio surface functionalization absorbent charcoal material is 10~30um, than
Surface area is 1200~1800m2/ g, pore-size distribution are：3~8nm, Kong Rong：0.3~1.0cm3/g；Proportion is 0.75~0.9g/
cm3；Wherein the ratio between carbon material and metallic compound content are not less than 8: 1；
0.5wt%~3wt% graphenes, the graphene number of plies are included in modified high-ratio surface functionalization absorbent charcoal material slurry
It it is 5~10 layers, specific surface is in 500~750m2/g；Electrically conductive graphite content in the surface-functionalized absorbent charcoal material slurry of high-modification-ratio
Not less than 25wt%；
Carbon Materials in modified high-ratio surface functionalization absorbent charcoal material slurry need to pass through HNO3、H3PO4Cleaning, 90~100
The cleaning of DEG C temperature urea liquid；
Active material in power-type Pb/C ultracapacitor battery negative materials is lead powder, density 1.39g/cm3, work(
Bonding agent in rate type Pb/C ultracapacitor battery negative materials includes：LA132/133, polyvinyl alcohol, SBR, butadiene-styrene rubber,
One or more of HPMC etc..
Conductive agent in power-type Pb/C ultracapacitor battery negative materials includes：Electrically conductive graphite, carbon nanometer, power-type
Other additives in Pb/C ultracapacitor battery negative materials include：Red lead, sulfuric acid, deionized water, staple fiber etc.；
Preparation method：
Mixing method：Accumulation energy type ultracapacitor battery negative electrode active material active material, additive are proportionally added into
In blender, 5~10min is stirred；High-ratio surface modified activated carbon material paste is proportionally added in, stirs 10~15min；
10wt% deionized waters are added in, stir 15~20min；Add in 10wt%H2SO4(6mol/L), stirring 20min surpass up to accumulation energy type
Grade capacitor battery positive electrode paste, then by lotion even application on negative pole currect collecting screen, dry, curing can obtain accumulation energy type
Ultracapacitor battery cathode；Wherein the oxidizability of lead powder is 75%.
Brushing method：According to lead-acid battery cathode piece production method, by the lead-acid battery positive plate prepared invade bubble go from
30min in sub- water takes out and air-dries 12h, uniformly sprayed the high surface charcoal slurry of modification with xxx formulas spray gun on positive plate surface
Pole piece, often spraying is primary i.e. dry primary, and 85 DEG C, time 15min of drying temperature is brushed 3~5 times, makes painting thickness repeatedly
Degree reaches 0.75~0.85mm thickness, and dry solidification can obtain accumulation energy type super capacitor (device) battery cathode, dry solidification temperature
For：80~90 DEG C, the time is 2~4h.
Embodiment 1
In accumulation energy type Pb/C ultracapacitor battery cathode formulas：At normal temperatures and pressures, respectively by each group specified in table 1
Point, by modified high-ratio surface functionalization absorbent charcoal material slurry：96.7kg lead powder：The 500kg of oxidizability 75 ± 2%, deionization
Water：55kg, sodium lignosulfonate：2kg, carbon black：1.5kg, barium stearate：1.0kg, staple fiber：1.5kg, 1.25g/cm3Sulfuric acid
52kg mixtures enter to be stirred in vertical paddle agitator.Cathode lotion is prepared using dry and method：In vertical blade stirring-type
Lead powder and staple fiber stirring 10min are added in paste mixing machine, adds the stirring of high-ratio surface modified activated carbon material paste
Then sulfuric acid is slowly added into paste mixing machine by 15min in 15~20min, then add in deionized water, and time control exists
In 15min, it is followed by stirring for 20min and can obtain accumulation energy type Pb/C ultracapacitor activated carbon battery cathode lotion (half sand mold lead
Cream)；Using domestic coating machine by cathode lotion even application on lead-calcium alloy plate (Carbon foam screen), drying process using first
Cure for 24 hours under the conditions of 40 DEG C of temperature, relative humidity 90%；Temperature 60 C again cures 48h under the conditions of relative humidity 60%；I.e.
Accumulation energy type Pb/C super capacitors (device) battery cathode is can obtain, dried substrate thickness is between 3.7~3.8mm.
Embodiment 2
The method that EXPERIMENTAL EXAMPLE 1 is repeated by each combined content specified in following table 1 lists test knot in table 1
Fruit.
In power-type Pb/C super capacitors (device) battery cathode formula：The lead powder of oxidizability 75 ± 2%：500kg, deionization
Water：65kg, staple fiber：1.5kg, sodium lignosulfonate：1.5kg, carbon black：1.75kg barium stearate：1.0kg, staple fiber：
1.5kg, 1.25g/cm3Sulfuric acid 65kg, acetylene black：3kg, electrically conductive graphite：2kg.Cathode lotion is prepared using dry and method：Vertical
Lead powder, acetylene black, electrically conductive graphite and staple fiber stirring 10min are added in blade stirring formula paste mixing machine, it then will in 10min
Sulfuric acid is slowly added into paste mixing machine, then adds in deionized water, and in 15min, being followed by stirring for 15min can obtain time control
To power-type Pb/C super capacitor (device) battery cathode lotion (half sand mold lead plaster).It is using domestic coating machine that cathode lotion is uniform
Coated on lead-calcium alloy plate, drying process is cured for 24 hours using first under the conditions of 40 DEG C of temperature, relative humidity 90%；Again in temperature
60 DEG C are spent, cures 48h under the conditions of relative humidity 60%；Dried substrate thickness is between 3.5~3.6mm.Dried pole
Piece is uniformly brushed high-ratio surface modified activated carbon material paste in pole piece using artificial or paint formula flush coater, then
80 DEG C of dry 2h in air dry oven take out, and repeatedly above to operate 5 times, last time drying time is 8h, makes external coating
Layer thickness is in 0.5mm, you can obtains power-type Pb/C ultracapacitor activated carbon battery cathode.
The formula composition performance indicator of 1 Examples 1 to 8 of table
Examples 1 to 4 is accumulation energy type Pb/C ultracapacitor batteries, and main method use will be modified high-ratio surface functionalization
Absorbent charcoal material slurry uniformly mixes together with other materials；Embodiment 5~8 is power-type Pb/C ultracapacitor batteries, main
It is that modified high-ratio surface functionalization absorbent charcoal material slurry is coated in pole piece using spray coating method to want method.
Claims (10)
1. a kind of preparation method of Pb/C ultracapacitors battery cathode, it is characterised in that include the following steps：
It is 20wt%~30wt%, 10~30um of grain size, 1200~1800m of specific surface area first by solid content2/ g, pore-size distribution
For 3~10nm, hole holds 0.3~1cm3/ g, proportion are 0.75~0.9g/cm3Modification high-ratio surface functionalization absorbent charcoal material slurry
Material, through HNO3、H3PO4After being cleaned with 90~100 DEG C of temperature urea liquids, loading section metallic compound, metallic compound is oxygen
Change zinc ZnO, barium sulfate BaSO4, lead titanates PbTiSO4, wherein, the height in modified high-ratio surface functionalization absorbent charcoal material slurry
The ratio between surface activity carbon and metallic compound content are not more than 8: 1；High surface activity carbon, ZnO, BaSO4、PbTiSO4Ratio is：6
: 1: 1: 2 or 6: 2: 1: 1；Then by weight percentage, by 5%~15% above-mentioned modified high-ratio surface functionalization activated carbon
Material paste is added in agitator tank, stirs 10~15min；Again by the negative electrode active material lead powder Pb/C of 50wt%~65wt% and
1wt%~5wt% conductive agents, bonding agent and other additives are added in agitator tank, stir 5~10min；10wt% is added to go
Ionized water stirs 20min；It is eventually adding the H of the 6mol/L of 10%wt2SO4, 20min is stirred, accumulation energy type is made or power-type surpasses
Grade capacitor activated carbon battery cathode substance lotion, above-mentioned conductive agent are electrically conductive graphite, acetylene black, conductive carbon fibre, conductive charcoal
One or more of black, graphene.
2. the preparation method of Pb/C ultracapacitors battery cathode as described in claim 1, it is characterised in that：Accumulation energy type is super
Bonding agent content in capacitor battery negative material lotion is 0.5wt%~1.5wt%, other additives be 0.5wt%~
1wt%.
3. the preparation method of Pb/C ultracapacitors battery cathode as claimed in claim 2, it is characterised in that：The bonding agent
Including：It is hydroxypropyl methylcellulose HPMC, polyacrylic acid, polyvinyl alcohol, ethylene~vinyl acetate copolymer eva copolymer, aqueous viscous
It is one or more in mixture LA132/133.
4. the preparation method of Pb/C ultracapacitors battery cathode as claimed in claim 2, it is characterised in that：The additive
Comprising：Humic acid, barium stearate, marasperse BS, deionized water and staple fiber.
5. the preparation method of Pb/C ultracapacitors battery cathode as described in claim 1, it is characterised in that：Power type super
Conductive agent content in capacitor activated carbon battery cathode substance lotion for 10wt%~15wt%, bonding agent 0.5wt%~
1.5wt%, other additive 0.5wt%~1wt%.
6. the preparation method of Pb/C ultracapacitors battery cathode as described in claim 1, it is characterised in that：Power-type Pb/C
Bonding agent in ultracapacitor activated carbon battery cathode substance lotion includes：Aqueous adhesive LA132/133, polyvinyl alcohol,
One or more of styrene butadiene rubber sbr, sodium cellulose glycolate CMC.
7. the preparation method of Pb/C ultracapacitors battery cathode as described in claim 1, it is characterised in that：Modified Gao Bibiao
The graphene of 0.5wt%~3wt% is contained in the functionalization absorbent charcoal material slurry of face, the graphene number of plies is 5~10 layers, compares table
Face is 500~750m2/g。
8. the preparation method of Pb/C ultracapacitors battery cathode as described in claim 1, it is characterised in that：Modified Gao Bibiao
Electrically conductive graphite content is 10wt% in the functionalization absorbent charcoal material slurry of face.
9. the preparation method of Pb/C ultracapacitors battery cathode as described in claim 1, it is characterised in that：The oxidation of lead powder
Spend is 75%.
10. the preparation method of Pb/C ultracapacitors battery cathode as described in claim 1, it is characterised in that：Using dry and
Method prepares cathode lotion：Lead powder and staple fiber stirring 10min are added in vertical blade stirring-type paste mixing machine, adds modification
High-ratio surface functionalization absorbent charcoal material slurry agitation 15min, is then slowly added into paste mixing machine in 15~20min by sulfuric acid
In, deionized water is then added in, time control is followed by stirring for 20min and can obtain accumulation energy type Pb/C super capacitors in 15min
Device activated carbon battery cathode substance lotion.
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| CN102881867A (en) * | 2012-09-29 | 2013-01-16 | 浙江南都电源动力股份有限公司 | Lead carbon mixed negative lead paste and preparation method thereof |
| CN103531791A (en) * | 2013-10-29 | 2014-01-22 | 上饶市云龙实业有限公司 | Super-capacitor lead carbon battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102881867A (en) * | 2012-09-29 | 2013-01-16 | 浙江南都电源动力股份有限公司 | Lead carbon mixed negative lead paste and preparation method thereof |
| CN103531791A (en) * | 2013-10-29 | 2014-01-22 | 上饶市云龙实业有限公司 | Super-capacitor lead carbon battery and preparation method thereof |
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