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CN102074703B - Negative pole lead paste for lead-carbon super storage battery and preparation method thereof - Google Patents

Negative pole lead paste for lead-carbon super storage battery and preparation method thereof Download PDF

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Publication number
CN102074703B
CN102074703B CN2010106093726A CN201010609372A CN102074703B CN 102074703 B CN102074703 B CN 102074703B CN 2010106093726 A CN2010106093726 A CN 2010106093726A CN 201010609372 A CN201010609372 A CN 201010609372A CN 102074703 B CN102074703 B CN 102074703B
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lead
plumbous
negative pole
carbon
carbon composite
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CN102074703A (en
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石光
李正明
张德晶
陈红雨
王辉
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South China Normal University
Zhuzhou Smelter Group Co Ltd
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South China Normal University
Zhuzhou Smelter Group Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention relates to negative pole lead paste for a lead-carbon super storage battery. The lead paste is prepared by mixing solid raw materials consisting of 1 to 93 percent of lead powder and 2 to 95 percent of lead-carbon composite material by using a paste mixing machine via a dry-mixing method and a wet-mixing method. The lead-carbon composite material of the negative pole lead paste for the lead-carbon super storage battery is prepared by the electro-deposition method and contains 25 to 55 weight parts of lead. The negative pole lead paste can increase the porosity and the utilization rate of negative pole active substances, improve the contraction state of a negative polar plate and enhance the bonding force between the lead paste and the polar plate as well as between the lead powder and the active carbon with high specific area, functions like a negative pole lead paste super capacitor under the condition of high carbon-added quantity, and improves the comprehensive performance of the storage battery.

Description

A kind of plumbous charcoal super accumulator is with cathode lead plaster and preparation method thereof
Technical field
The present invention relates to a kind of lead-acid battery electrode material and preparation method, especially for electronic and energy storage with super accumulator cathode lead plaster and preparation method thereof, genus battery technology field.
Background technology
Because the stable performance of lead acid accumulator, cost is lower, is still one of alternative battery of PHEV and pure power vehicle in the new forms of energy industry at present.As far back as 1996, the report of PHEV (HEV) with analysing valve control type lead-acid accumulator battery just arranged, after 2000, under the promotion of United States advanced lead-acid battery federation (ALABC), carried out a large amount of research and extensions and used.But for electrokinetic cell; Charge acceptance is an important indicator of storage battery; Its reflection be storage battery to charging into the acceptance level of electric weight, the capacity that it directly influences storage battery and life-span etc., and lead acid accumulator performance in this respect still remains raising at present.In addition, the failure mode of sealed type valve-regulated lead-acid battery when (HRPSoC) when operation is with conventional the use under high magnification partial charging state is different, and wherein most typical failure mode is the serious sulfation of negative pole.
Along with global economy and fast development of society; The petrochemical industry resource and the energy is shortage day by day; Biological environment goes from bad to worse, and environmental protection pressure increases severely, and the mankind will depend on regenerative resources such as solar energy, wind energy, biological energy source and Hydrogen Energy more; But the energy of generations such as solar energy, wind energy, biological energy source and Hydrogen Energy can not directly be incorporated into the power networks, and needs energy storage device to store the energy earlier.Because energy storage device need adapt to high low temperature rugged environment influence, and often is under the floating charge state, common lead acid accumulator is difficult to reach requirement.
To these problems, the expert considers that in battery terminal negative, adding charcoal improves the application of lead acid accumulator as electrokinetic cell and energy-storage battery both at home and abroad, and proposes the notion of superbattery gradually, manufactures and designs the storage battery with ultracapacitor function.Though strengthen carbon content in the negative pole; Having prolonged useful life and its performance of lead acid accumulator when HRPSoC moves greatly, the performance with Ni-MH battery is close; But in dark cyclic process and as the easy expansion drop of charcoal in the energy-storage battery time spent negative pole; Adhesion is relatively poor, and the cycle performance in the high and low temperature environment is relatively poor, and serious sulfation problem occurs.
Summary of the invention
The objective of the invention is to overcome above-mentioned prior art defective; Provide a kind of plumbous charcoal super accumulator to use cathode lead plaster, this cathode lead plaster can improve negative electrode active material porosity and utilance, improve the contraction state of negative plate, strengthen the adhesion between lead plaster and pole plate and lead powder and the additive; In improving lead plaster under the situation of charcoal addition; Can improve the combination property of storage battery, the function of performance ultracapacitor is to adapt to the requirement as electrical source of power and accumulation power supply.
In addition, the present invention also provides the preparation method of above-mentioned plumbous charcoal super accumulator with cathode lead plaster.
The object of the invention is realized by following technical scheme:
A kind of plumbous charcoal super accumulator is used cathode lead plaster, and its solid material is made up of following substances, and the mass percent of each component is respectively:
Lead powder: 1 ~ 93%;
Plumbous carbon composite: 2 ~ 95%;
Carbon black: 0.1 ~ 0.8%;
Barium sulfate: 0.3 ~ 2.8%;
Sodium lignin sulfonate: 0.05 ~ 1.35%;
Polyester fiber: 0.05 ~ 0.07%;
Humic acid: 0.8 ~ 2%.
Further, plumbous carbon composite is to make through electro-deposition method.
Further, the preparation process of plumbous carbon composite is following:
Active carbon, carbon black, Kynoar and n-formyl sarcolysine base pyrrolidones are pressed (60 ~ 80): (5 ~ 10): (5 ~ 10): the mass ratio of (20 ~ 30) mixes; Compound evenly is coated on the titanium plate; Be put in the vacuum drying chamber, drying is 4 ~ 8 hours under 50 ~ 60 ℃ of conditions; Again above-mentioned titanium plate being immersed into concentration as negative pole is in 0.4 ~ 1.0mol/L lead fluoborate solution, soaks into after 10 ~ 30 minutes, is anodal with the stereotype, is 50 ~ 200 mA/cm in current density 2Electro-deposition is 10 ~ 30 seconds under the condition, and the titanium plate after the electro-deposition is taken out, and is put in the vacuum drying chamber, and drying is 5 ~ 8 hours under 70 ~ 80 ℃ of conditions, and desciccate is scraped from the titanium plate, promptly obtains plumbous carbon composite.
Further, plumbous shared mass ratio is 25 ~ 55 % in the plumbous carbon composite.
A kind of plumbous charcoal super accumulator may further comprise the steps with the preparation method of cathode lead plaster:
(1) batching: take by weighing each solid material by the said solid material proportioning of claim 1;
(2) dried mixing: above-mentioned solid material is put into paste mixing machine did mixed 10 ~ 30 minutes;
(3) wet mixing: the deionized water and stirring of adding solid material total weight 10 ~ 13% 20 ~ 80 minutes;
(4) drench acid: the density with spray shape adding solid material total weight 7 ~ 11% is 1.3 ~ 1.4g/cm while stirring 3Sulfuric acid solution, continue to stir 0.5 ~ 2.5 hour, control and cream temperature are 50 ~ 60 ℃, after temperature is reduced to below 45 ℃, go out cream, obtain plumbous charcoal super accumulator and use cathode lead plaster.
The plumbous carbon composite that is added in the above-mentioned cathode lead plaster prescription plays crucial effects; Lead in the plumbous carbon composite has good interface to combine with charcoal; When mixing with lead powder, the lead that carbon surface combined becomes the transition region that charcoal combines with lead powder under the effect of aqueous sulfuric acid; Improve the mixed and dispersed effect between raw material of wood-charcoal material and the lead powder, and increased the interface bond strength of charcoal and lead powder.Compare with the method for direct adding absorbent charcoal material; Form with plumbous carbon composite can add more substantial raw material of wood-charcoal material uniformly in cathode lead plaster; Make cathode lead plaster have bigger specific area; Improve the contact area and the amount of contact with electrolyte, help the raising of negative electrode active material utilance and the enhancing of charge acceptance.The adding of plumbous carbon composite has strengthened the interface bond strength between raw material of wood-charcoal material and lead powder, can better suppress the volume contraction of negative electrode active material in charge and discharge process, the cycle life of significant prolongation battery.Active carbon with high specific surface area in the cathode lead plaster has good electric double layer capacitance characteristic in sulfuric acid electrolyte; The adding of plumbous carbon composite organically combines the super capacitor characteristic of active carbon and the battery performance of lead acid accumulator; Under the high current charge-discharge situation; The super capacitor function can play the effect of buffer, and accumulator negative electrode active substance is had good protective action.The storage battery of using this cathode lead plaster manufacturing has the superbattery characteristic, has long especially useful life, and good big electric current fast charging and discharging ability is specially adapted to the application aspect electrokinetic cell, is suitable for the power set as PHEV.
Embodiment
The present invention is according to the requirement of power super accumulator and energy storage super accumulator, selected cathode formula, and provide each components contents in the prescription, and the desired value of contained material in the plumbous carbon composite of important composition thing.Core technology of the present invention is plumbous carbon composite, controls the adding proportion of charcoal and content carbon black and other each component in the plumbous carbon composite, and the cathode lead plaster that obtains has excellent performance.Find that according to experiment contrast plumbous charcoal adhesion relatively poorly comes off easily when directly adding charcoal in the cathode lead plaster, electric conductivity is relatively poor, and the amount that adds is less; Generally≤2%, cause the loss of charcoal easily, reduce the specific area of active material; Changed the negative pole pattern; Cause efficiency for charge-discharge to reduce, make battery capacity descend end-of-life.
Have when adopting the present invention's prescription also to demonstrate with cream better manufacturability can, avoid or reduce because of controlling the improper early stage capacitance loss phenomenon of battery that makes.
Provide embodiment below so that the present invention is carried out concrete description; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection range of the present invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the technical staff in this field according to the present invention.
Embodiment 1
Take by weighing lead powder 62.84kg, plumbous shared mass percent and be 25% plumbous carbon composite 35kg, sodium lignin sulfonate 0.5kg, barium sulfate 0.3kg, carbon black 0.5kg, long for the 8mm diameter be that polyester fiber 0.06kg, the lead acid accumulator of 12 μ m used humic acid 0.8kg; Above-mentioned material is put into paste mixing machine to be stirred 25 minutes; Add the 10.7kg deionized water then fast; Mixed 50 minutes, drenching density is 1.35g/cm 3The sulfuric acid solution 8.7kg of (25 ℃) mixed 1.5 hours, and the lotion temperature is 50 ~ 60 ℃ in control and the cream process, and discharging when temperature is reduced to 45 ℃ obtains plumbous charcoal super accumulator and uses cathode lead plaster, can coat negative plate.Pole plate after coating can be handled according to the curing and the drying process of common polar plate of lead acid storage battery, goes forward side by side into the assembling of super battery and is internalized into operation, and all the other technologies can adopt the present production technology of sending out valve controlled sealed lead-acid accumulator to carry out fully.
The preparation process of the plumbous carbon composite that present embodiment is used is following: with specific area is 1060m 2/ g active carbon, carbon black, Kynoar and n-formyl sarcolysine base pyrrolidones mix by the mass ratio of 80:10:10:30, and compound evenly is coated on the titanium plate, are put in the vacuum drying chamber, and drying is 4 hours under 60 ℃ of conditions; Again above-mentioned titanium plate being immersed into concentration as negative pole is in the 0.40mol/L lead fluoborate solution, soaks into after 26 minutes, is anodal with the stereotype, is 50 mA/cm in current density 2Electro-deposition 10s under the condition takes out the titanium plate after the electro-deposition, is put in the vacuum drying chamber, and drying is 5 hours under 80 ℃ of conditions, and desciccate is scraped from the titanium plate, and promptly obtaining lead tolerance is the plumbous carbon composite of 25wt%.
Embodiment 2
Take by weighing lead powder 93kg, plumbous shared mass percent and be 38% plumbous carbon composite 2kg, sodium lignin sulfonate 1.35kg, barium sulfate 0.78kg, carbon black 0.8kg, long for the 8mm diameter be that polyester fiber 0.07kg, the lead acid accumulator of 12 μ m used humic acid 2kg; Above-mentioned material is put into paste mixing machine to be stirred 10 minutes; Add the 13kg deionized water then fast; Mixed 80 minutes, drenching density is 1.4g/cm 3The sulfuric acid solution 11kg of (25 ℃) mixed 0.5 hour, and the lotion temperature is 50 ~ 60 ℃ in control and the cream process, and discharging when temperature is reduced to 45 ℃ obtains plumbous charcoal super accumulator and uses cathode lead plaster.
The preparation process of the plumbous carbon composite that present embodiment is used is following: with specific area is 1530m 2/ g active carbon, carbon black, Kynoar and n-formyl sarcolysine base pyrrolidones mix by the mass ratio of 60:8:8:24, and compound evenly is coated on the titanium plate, are put in the vacuum drying chamber, and drying is 8 hours under 50 ℃ of conditions; Again above-mentioned titanium plate being immersed into concentration as negative pole is in the 0.60mol/L lead fluoborate solution, soaks into after 10 minutes, is anodal with the stereotype, is 125 mA/cm in current density 2Electro-deposition 16s under the condition takes out the titanium plate after the electro-deposition, is put in the vacuum drying chamber, and drying is 8 hours under 70 ℃ of conditions, and desciccate is scraped from the titanium plate, and promptly obtaining lead tolerance is the plumbous carbon composite of 38wt%.
Embodiment 3
Take by weighing lead powder 1kg, plumbous shared mass percent and be 55% plumbous carbon composite 95kg, sodium lignin sulfonate 0.05kg, barium sulfate 2.8kg, carbon black 0.1kg, long for the 8mm diameter be that polyester fiber 0.05kg, the lead acid accumulator of 12 μ m used humic acid 1kg; Above-mentioned material is put into paste mixing machine to be stirred 30 minutes; Add the 10kg deionized water then fast; Mixed 20 minutes, drenching density is 1.3g/cm 3The sulfuric acid solution 7kg of (25 ℃) mixed 2.5 hours, and the lotion temperature is 50 ~ 60 ℃ in control and the cream process, and discharging when temperature is reduced to 45 ℃ obtains plumbous charcoal super accumulator and uses cathode lead plaster.
The preparation process of the plumbous carbon composite that present embodiment is used is following: with specific area is 2030m 2/ g active carbon, carbon black, Kynoar and n-formyl sarcolysine base pyrrolidones mix by the mass ratio of 70:5:5:20, and compound evenly is coated on the titanium plate, are put in the vacuum drying chamber, and drying is 6 hours under 55 ℃ of conditions; Again above-mentioned titanium plate being immersed into concentration as negative pole is in the 1.0mol/L lead fluoborate solution, soaks into after 30 minutes, is anodal with the stereotype, is 200 mA/cm in current density 2Electro-deposition 30s under the condition takes out the titanium plate after the electro-deposition, is put in the vacuum drying chamber, and drying is 6 hours under 75 ℃ of conditions, and desciccate is scraped from the titanium plate, and promptly obtaining lead tolerance is the plumbous carbon composite of 55wt%.
Embodiment 4
Take by weighing lead powder 76.3kg, plumbous shared mass percent and be 45% plumbous carbon composite 20kg, sodium lignin sulfonate 0.15kg, barium sulfate 0.45kg, carbon black 0.34kg, long for the 8mm diameter be that polyester fiber 0.06kg, the lead acid accumulator of 12 μ m used humic acid 1.7kg; Above-mentioned material is put into paste mixing machine to be stirred 18 minutes; Add the 11.6kg deionized water then fast; Mixed 70 minutes, drenching density is 1.32g/cm 3The sulfuric acid solution 9.7kg of (25 ℃) mixed 2 hours, and the lotion temperature is 50 ~ 60 ℃ in control and the cream process, and discharging when temperature is reduced to 45 ℃ obtains plumbous charcoal super accumulator and uses cathode lead plaster.
The preparation process of the plumbous carbon composite that present embodiment is used is following: with specific area is 1610m 2/ g active carbon, carbon black, Kynoar and n-formyl sarcolysine base pyrrolidones mix by the mass ratio of 75:5:15:28, and compound evenly is coated on the titanium plate, are put in the vacuum drying chamber, and drying is 4 hours under 60 ℃ of conditions; Again above-mentioned titanium plate being immersed into concentration as negative pole is in the 0.80mol/L lead fluoborate solution, soaks into after 21 minutes, is anodal with the stereotype, is 175 mA/cm in current density 2Electro-deposition 20s under the condition takes out the titanium plate after the electro-deposition, is put in the vacuum drying chamber, and drying is 6 hours under 80 ℃ of conditions, and desciccate is scraped from the titanium plate, and promptly obtaining lead tolerance is the plumbous carbon composite of 45wt%.
Use the valve controlled sealed lead-acid accumulator that cathode lead plaster of the present invention is assembled into and carry out performance test, compare with the battery that absorbent charcoal material assembled that adds equal consumption, the power supply discharge power doubles, and the life-span doubles; 25%DOD cycle-index>4000 time;-10 ℃ of 30hr100%DOD>400 time; The 100mA charging, cell can reach voltage 2.40V; Floating charge cycle-index>6000 time; Charge acceptance >=98%.The result shows, adopts the valve controlled sealed lead-acid accumulator of negative electrode active substance formulation preparation of the present invention can be applied to electrokinetic cell fully and the field such as recycles.

Claims (3)

1. a plumbous charcoal super accumulator is used cathode lead plaster, it is characterized in that its solid material is made up of following substances, and the mass percent of each component is respectively:
Lead powder: 1 ~ 93%;
Plumbous carbon composite: 2 ~ 95%;
Carbon black: 0.1 ~ 0.8%;
Barium sulfate: 0.3 ~ 2.8%;
Sodium lignin sulfonate: 0.05 ~ 1.35%;
Polyester fiber: 0.05 ~ 0.07%;
Humic acid: 0.8 ~ 2%;
Said plumbous carbon composite is to make through electro-deposition method, and it is following specifically to prepare process:
Active carbon, carbon black, Kynoar and n-formyl sarcolysine base pyrrolidones are pressed (60 ~ 80): (5 ~ 10): (5 ~ 10): the mass ratio of (20 ~ 30) mixes; Compound evenly is coated on the titanium plate; Be put in the vacuum drying chamber, drying is 4 ~ 8 hours under 50 ~ 60 ℃ of conditions; Again above-mentioned titanium plate being immersed into concentration as negative pole is in 0.4 ~ 1.0mol/L lead fluoborate solution, soaks into after 10 ~ 30 minutes, is anodal with the stereotype, is 50 ~ 200 mA/cm in current density 2Electro-deposition is 10 ~ 30 seconds under the condition, and the titanium plate after the electro-deposition is taken out, and is put in the vacuum drying chamber, and drying is 5 ~ 8 hours under 70 ~ 80 ℃ of conditions, and desciccate is scraped from the titanium plate, promptly obtains plumbous carbon composite.
2. plumbous charcoal super accumulator according to claim 1 is used cathode lead plaster, it is characterized in that plumbous shared mass ratio is 25 ~ 55 % in the plumbous carbon composite.
3. a plumbous charcoal super accumulator is characterized in that may further comprise the steps with the preparation method of cathode lead plaster:
(1) batching: take by weighing each solid material by the said solid material proportioning of claim 1;
(2) dried mixing: above-mentioned solid material is put into paste mixing machine did mixed 10 ~ 30 minutes;
(3) wet mixing: the deionized water and stirring of adding solid material total weight 10 ~ 13% 20 ~ 80 minutes;
(4) drench acid: the density with spray shape adding solid material total weight 7 ~ 11% is 1.3 ~ 1.4g/cm while stirring 3Sulfuric acid solution, continue to stir 0.5 ~ 2.5 hour, control and cream temperature are 50 ~ 60 ℃, after temperature is reduced to below 45 ℃, go out cream, obtain plumbous charcoal super accumulator and use cathode lead plaster.
CN2010106093726A 2010-12-28 2010-12-28 Negative pole lead paste for lead-carbon super storage battery and preparation method thereof Active CN102074703B (en)

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Publication number Priority date Publication date Assignee Title
CN102610801B (en) * 2011-12-30 2014-06-18 华南师范大学 Hydrothermal preparation method of carbon coated lead powder composite materials for lead carbon super batteries
CN102637858B (en) * 2012-03-16 2015-01-14 天能电池集团有限公司 Microwave preparation method for carbon-coated lead powder composite for lead-carbon super batteries
CN102709526B (en) * 2012-06-18 2015-06-10 奇瑞汽车股份有限公司 Negative lead plaster of lead-carbon battery and preparation method thereof, negative polar plate and lead-carbon battery
CN103022429A (en) * 2012-11-28 2013-04-03 上海锦众信息科技有限公司 Method for preparing negative pole of carbon-based lead-acid storage battery
CN103413919B (en) * 2012-12-11 2015-06-10 骆驼集团襄阳蓄电池有限公司 Superbattery negative plate and manufacturing method thereof
CN104518202A (en) * 2014-10-20 2015-04-15 江苏欧力特能源科技有限公司 Method for preparing coated type lead carbon negative plate
CN105080418A (en) * 2015-08-03 2015-11-25 安徽新能电源科技有限公司 Lead-acid storage battery negative electrode plate negative pressure paste mixing technology
CN106531972B (en) * 2016-08-17 2022-07-26 重庆大学 Preparation method of lead-graphene composite material for lead-carbon battery

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CN101330140A (en) * 2008-08-04 2008-12-24 风帆股份有限公司 High-temperature lead-acid accumulator cathode diachylon and preparation method
CN101847718A (en) * 2010-05-31 2010-09-29 张天任 Negative pole lead plaster for enhancing charging receptivity of lead-acid battery and preparation method thereof
CN101916861A (en) * 2010-07-30 2010-12-15 风帆股份有限公司 Cathode lead plaster capable of prolonging fast charge-discharge circulating life of battery and preparation method thereof

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CN101847718A (en) * 2010-05-31 2010-09-29 张天任 Negative pole lead plaster for enhancing charging receptivity of lead-acid battery and preparation method thereof
CN101916861A (en) * 2010-07-30 2010-12-15 风帆股份有限公司 Cathode lead plaster capable of prolonging fast charge-discharge circulating life of battery and preparation method thereof

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