CN103035895A - Method for preparing carbon coated lead powder composite material for lead carbon battery - Google Patents
Method for preparing carbon coated lead powder composite material for lead carbon battery Download PDFInfo
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- CN103035895A CN103035895A CN201210556404XA CN201210556404A CN103035895A CN 103035895 A CN103035895 A CN 103035895A CN 201210556404X A CN201210556404X A CN 201210556404XA CN 201210556404 A CN201210556404 A CN 201210556404A CN 103035895 A CN103035895 A CN 103035895A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the field of chemical power sources, in particular to a preparation method suitable for producing a carbon coated lead powder composite material for a lead carbon battery on a large scale. By the method, the problems that the stability of negative electrode lead carbon mixed material paste and the strength of a negative plate are difficult to guarantee due to non-uniform mixing of a carbon material and lead powder in the prior art are solved. The method comprises the following steps: weighing an organic carbon source and lead powder; placing the organic carbon source and the lead powder into a ball-milling jar; mechanically mixing the organic carbon source and the lead powder by a ball-milling method to prepare a uniformly mixed pasted mixture; performing carbonization treatment on the pasted mixture by using a tube furnace, wherein protective gas is adopted in the carbonization process, so that the carbon is coated on the surfaces of the lead powder particles; alternately washing the coated material by using an organic solvent and deionized water; and performing vacuum drying to obtain the carbon coated lead powder composite material. The carbon coated lead powder composite material effectively improves the large current charge/discharge cycle life of a lead-acid storage battery, increases mass specific power and provides an idea for large-scale production.
Description
Technical field
The present invention relates to field of chemical power source, particularly a kind of large-scale production lead carbon battery that is suitable for coats lead powder composite manufacture method with carbon.
Background technology
The scale process of the New Energy Industries such as photovoltaic, wind-powered electricity generation is proposed to carry forward vigorously along with National Energy Board " 12 " planning; base oneself upon simultaneously the automobile industries such as new forms of energy; the target that realization is made the country prosperous from automobile superpower to automobile and changed; in the large-scale application and electric automobile fast development process of regenerative resource, battery technology is the key technology that solves new forms of energy energy storage, motive use bottleneck.Lead-acid battery is widely used owing to advantages such as its capacity are high, low, the stable performance of price, the serviceability temperature wide ranges as the most ancient secondary cell, also makes it become a strong competitor in future competition.Although there has been huge advance made in the existing analysing valve control type lead-acid accumulator battery past, but still there are energy density, deficiency that power density is lower, in the traditional market of lead acid accumulator and new forms of energy energy storage, power market, all face the strong challenge of ferric phosphate lithium cell.Therefore, to improve the performance of lead-acid battery imperative for sophistication (such as plumbous charcoal negative pole technology).
Plumbous charcoal negative pole technology is to add a certain amount of material with carbon element with Fabrication of High Specific Capacitance character in the plumbous negative pole of tradition, thereby makes plumbous charcoal negative pole have the character of ultracapacitor, and when moment stored or discharge electric charge, the anticathode plate played good buffer current effect.Therefore, adopt the plumbous charcoal storage battery of plumbous charcoal negative pole Technical form to have excellent high rate during charging-discharging.Simultaneously, the material with carbon element in the negative pole can effectively suppress sulfation, prolongs the cycle life of battery under high magnification partial state of charge (HRPSOC) condition.
At present, what plumbous charcoal negative pole mainly adopted is the DIC material, joins in the negative plate by the mode with itself and lead powder mechanical mixture.When using the method to prepare, material with carbon element mixes even not with lead powder, and is difficult to guarantee that negative electrode lead charcoal compound is coated with the intensity of steadiness and the negative plate of cream.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of lead carbon battery to coat lead powder composite manufacture method with carbon, the material with carbon element that exists in the solution prior art mixes even not with lead powder, and is difficult to guarantee that negative electrode lead charcoal compound is coated with the problems such as intensity of steadiness and the negative plate of cream.
To achieve these goals, the present invention adopts following technical scheme:
A kind of lead carbon battery coats lead powder composite manufacture method with carbon; take by weighing organic carbon source and lead powder places ball grinder; this organic carbon source and lead powder are carried out mechanical mixture by ball-milling method; make the paste mixture that mixes; adopt tube furnace that this paste mixture is carried out carbonization treatment; carbonisation adopts protective gas simultaneously; so that carbon is coated on the lead powder particle surface; replace the material that washs after coating with organic solvent and deionized water again, vacuumize obtains carbon and coats the lead powder composite material.
Described lead carbon battery coats lead powder composite manufacture method with carbon, and ball-milling method carries out in the mechanical mixture process, and adding can make organic carbon source and lead powder be mixed into the solvent of paste, and this solvent is water or ethanol.
Described lead carbon battery coats lead powder composite manufacture method with carbon, and organic carbon source is one or more mixing in glucose, sucrose, maltose, starch or the citric acid.
Described lead carbon battery coats lead powder composite manufacture method with carbon, the mass ratio of organic carbon source and lead powder be 1:50-1:4(preferably, the mass ratio of organic carbon source and lead powder is 1:30-1:5).
Described lead carbon battery coats lead powder composite manufacture method with carbon, and lead powder is the technical grade lead powder for the production of lead acid accumulator.
Described lead carbon battery coats lead powder composite manufacture method with carbon, ball-milling method mixing condition: ball material mass ratio is 5:1-30:1, rotational speed of ball-mill is 200-800r/min, Ball-milling Time be 4h-20h(preferably, ball material mass ratio is 10:1-20:1, rotational speed of ball-mill is 300-600r/min, and Ball-milling Time is 8h-12h).
Described lead carbon battery coats lead powder composite manufacture method with carbon, and the carbonization treatment condition: carburizing temperature is 200-1000 ℃, carbonization time be 2-12h(preferably, carburizing temperature is 300-800 ℃, carbonization time is 4-10h).
Described lead carbon battery coats lead powder composite manufacture method with carbon, and protective gas is N
2, Ar or airborne a kind of.
Described lead carbon battery coats lead powder composite manufacture method with carbon, and organic solvent is one or more in absolute ethyl alcohol, acetone, butanols or the carbon tetrachloride.
Described lead carbon battery coats lead powder composite manufacture method with carbon, and the drying condition of composite material is: 40-70 ℃ of vacuumize 6-10h, vacuum degree be 0-100kPa(preferably, vacuum degree is 50kPa-90kPa).
Use above-mentioned carbon to coat the lead powder composite material and make lead carbon battery, concrete grammar is as follows: count by weight, ultra-fine barium sulfate (325 order), 0.3-0.5 part sodium lignin sulfonate, 0.05-0.2 part acetylene black, 0.1-0.3 part polyester fiber and 0.5-2 part carboxymethyl cellulose (CMC) that 100 parts carbon coats lead powder composite material, 0.2-0.4 part mix, and then add 8-12%, the 1.32g/cm that accounts for above-mentioned material gross mass
3Sulfuric acid and the deionized water of 8-12%, under 50-55 ℃, stir into lead plaster.Lead plaster is coated on the negative electrode grid, and carries out polar plate solidification and change into, make the negative plate of lead carbon battery.
Advantage of the present invention and beneficial effect are:
1, the present invention adopts the method for carbon coating lead powder to prepare plumbous carbon composite, carbon source mainly adopts organic carbon source, add partial solvent, make it become solution or colloidal sol, in ball milling and carbonisation, carbon is coated on the lead powder particle surface uniformly, so that this material has high power performance and high capacity characteristics simultaneously.
2, the pole plate that adopts composite material of the present invention to make has extraordinary mechanical strength, adopt simultaneously above-mentioned carbon to coat the lead carbon battery that the lead powder composite material is made, after tested, the battery quality specific power obviously increases, and fast charging and discharging performance and cycle life significantly improve.
Embodiment
Embodiment 1
Take by weighing citric acid 2kg, lead powder 10kg, place ball grinder, add as required and can make organic carbon source and lead powder be mixed into the water of paste, make paste mixture, take ball material mass ratio as 10:1 under the rotating speed of 400r/min after the ball milling 4h, at N
2Carry out carbonization treatment in the atmosphere; The Carbonization Conditions that adopts is: carburizing temperature is 400 ℃, and carbonization time is 4h; After the product cooling, alternately wash this product four times with absolute ethyl alcohol and deionized water, 60 ℃ of vacuumize 6h, vacuum degree is 90kPa, obtains carbon and coats the lead powder composite material.
Use above-mentioned carbon to coat the lead powder composite material and make lead carbon battery, concrete grammar is as follows: count by weight, 100 parts carbon coats lead powder composite material, 0.3 part ultra-fine barium sulfate (325 order), 0.4 part of sodium lignin sulfonate, 0.1 part of acetylene black, 0.2 part of polyester fiber and 1 part of carboxymethyl cellulose (CMC) to be mixed, then add account for above-mentioned material gross mass 10%, 1.32g/cm
3Sulfuric acid and 10% deionized water, under 50-55 ℃, stir into lead plaster.Lead plaster is coated on the negative electrode grid, and carries out polar plate solidification and change into, make the negative plate of lead carbon battery.
Embodiment 2
Take by weighing glucose 2kg, lead powder 10kg, place ball grinder, add as required and can make organic carbon source and lead powder be mixed into the water of paste, make paste mixture, take ball material mass ratio as 10:1 under the rotating speed of 200r/min after the ball milling 4h, at N
2Carry out carbonization treatment in the atmosphere; The Carbonization Conditions that adopts is: carburizing temperature is 600 ℃, and carbonization time is 4h; After the product cooling, alternately wash this product four times with absolute ethyl alcohol and deionized water, 60 ℃ of vacuumize 6h, vacuum degree is 90kPa, obtains carbon and coats the lead powder composite material.
Use above-mentioned carbon to coat the lead powder composite material and make lead carbon battery, manufacture method is with embodiment 1.
Embodiment 3
Take by weighing sucrose 2kg, lead powder 10kg, place ball grinder, add as required and can make organic carbon source and lead powder be mixed into the water of paste, make paste mixture, take ball material mass ratio as 10:1 under the rotating speed of 300r/min after the ball milling 4h, at N
2Carry out carbonization treatment in the atmosphere; The Carbonization Conditions that adopts is: carburizing temperature is 650 ℃, and carbonization time is 4h; After the product cooling, alternately wash this product four times with absolute ethyl alcohol and deionized water, 60 ℃ of vacuumize 6h, vacuum degree is 90kPa, obtains carbon and coats the lead powder composite material.
Use above-mentioned carbon to coat the lead powder composite material and make lead carbon battery, manufacture method is with embodiment 1.
Embodiment 4
Take by weighing starch 2kg, lead powder 20kg, place ball grinder, adding can make organic carbon source and lead powder be mixed into the water of paste as required, makes paste mixture, under the rotating speed of 400r/min, after the ball milling 6h, in Ar atmosphere, carry out carbonization treatment take ball material mass ratio as 15:1; The Carbonization Conditions that adopts is: carburizing temperature is 600 ℃, and carbonization time is 6h; After the product cooling, alternately wash this product four times with acetone and deionized water, 60 ℃ of vacuumize 10h, vacuum degree is 95kPa, obtains carbon and coats the lead powder composite material.
Use above-mentioned carbon to coat the lead powder composite material and make lead carbon battery, manufacture method is with embodiment 1.
Embodiment 5
Take by weighing maltose 2kg, lead powder 40kg, place ball grinder, adding can make organic carbon source and lead powder be mixed into the water of paste as required, makes paste mixture, under the rotating speed of 400r/min, after the ball milling 6h, in Ar atmosphere, carry out carbonization treatment take ball material mass ratio as 20:1; The Carbonization Conditions that adopts is: carburizing temperature is 800 ℃, and carbonization time is 4h; After the product cooling, alternately wash this product four times with butanols and deionized water, 50 ℃ of vacuumize 6h, vacuum degree is 90kPa, obtains carbon and coats the lead powder composite material.
Use above-mentioned carbon to coat the lead powder composite material and make lead carbon battery, manufacture method is with embodiment 1.
After tested, use the lead carbon battery quality of carbon coating lead powder composite material preparation than the obvious raising of power in above-described embodiment, under the high power charging-discharging multiplying power, cycle life also is greatly improved.Concrete technical indicator is as follows: the quality of above-mentioned lead carbon battery has improved 8-15% than the existing lead-acid battery of power ratio, and cycle life is 1.5-2.2 times of existing lead-acid battery.
Embodiment result shows, the present invention carries out mechanical mixture by ball-milling method with organic carbon source and lead powder according to a certain percentage, make the paste mixture that mixes, then carry out carbonization treatment in tube furnace the inside, carbonisation adopts protective gas, so that carbon is coated on the lead powder particle surface; Alternately wash material after this coating with organic solvent and deionized water, vacuumize obtains carbon and coats the lead powder composite material.This material can effectively improve lead acid accumulator high current charge-discharge cycle life, improves quality than power, and provides thinking for large-scale production.
Claims (10)
1. a lead carbon battery coats lead powder composite manufacture method with carbon; it is characterized in that: take by weighing organic carbon source and lead powder places ball grinder; this organic carbon source and lead powder are carried out mechanical mixture by ball-milling method; make the paste mixture that mixes; adopt tube furnace that this paste mixture is carried out carbonization treatment; carbonisation adopts protective gas simultaneously; so that carbon is coated on the lead powder particle surface; replace the material that washs after coating with organic solvent and deionized water again, vacuumize obtains carbon and coats the lead powder composite material.
2. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: ball-milling method carries out in the mechanical mixture process, and adding can make organic carbon source and lead powder be mixed into the solvent of paste, and this solvent is water or ethanol.
3. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: organic carbon source is one or more mixing in glucose, sucrose, maltose, starch or the citric acid.
4. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: the mass ratio of organic carbon source and lead powder is 1:50-1:4.
5. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, it is characterized in that: lead powder is the technical grade lead powder for the production of lead acid accumulator.
6. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: ball-milling method mixing condition: ball material mass ratio is 5:1-30:1, and rotational speed of ball-mill is 200-800r/min, and Ball-milling Time is 4h-20h.
7. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: the carbonization treatment condition: carburizing temperature is 200-1000 ℃, and carbonization time is 2-12h.
8. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: protective gas is N
2, Ar or airborne a kind of.
9. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: organic solvent is one or more in absolute ethyl alcohol, acetone, butanols or the carbon tetrachloride.
10. lead carbon battery according to claim 1 coats lead powder composite manufacture method with carbon, and it is characterized in that: the drying condition of composite material is: 40-70 ℃ of vacuumize 6-10h, vacuum degree is 0-100kPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210556404XA CN103035895A (en) | 2012-12-18 | 2012-12-18 | Method for preparing carbon coated lead powder composite material for lead carbon battery |
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| CN201210556404XA CN103035895A (en) | 2012-12-18 | 2012-12-18 | Method for preparing carbon coated lead powder composite material for lead carbon battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103943859A (en) * | 2014-03-13 | 2014-07-23 | 天能电池集团有限公司 | Lead-carbon composite material, and preparation method and application thereof |
| CN105990578A (en) * | 2016-04-27 | 2016-10-05 | 厦门百美特生物材料科技有限公司 | Lead carbon compound material as well as preparation method and application thereof |
| CN106486645A (en) * | 2015-08-24 | 2017-03-08 | 中国科学院金属研究所 | A kind of lead carbon battery negative plate containing network-like material with carbon element and preparation method thereof |
| CN108899492A (en) * | 2018-06-21 | 2018-11-27 | 华中科技大学 | A kind of lead carbon composite, preparation method and application |
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| CN102522531A (en) * | 2011-12-14 | 2012-06-27 | 深圳市雄韬电源科技股份有限公司 | Carbonaceous lead powder, its preparation method, battery lead paste and its application |
| CN102610801A (en) * | 2011-12-30 | 2012-07-25 | 华南师范大学 | Hydrothermal preparation method of carbon coated lead powder composite materials for lead carbon super batteries |
| CN102637858A (en) * | 2012-03-16 | 2012-08-15 | 天能电池集团有限公司 | Microwave preparation method for carbon-coated lead powder composite for lead-carbon super batteries |
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2012
- 2012-12-18 CN CN201210556404XA patent/CN103035895A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522531A (en) * | 2011-12-14 | 2012-06-27 | 深圳市雄韬电源科技股份有限公司 | Carbonaceous lead powder, its preparation method, battery lead paste and its application |
| CN102610801A (en) * | 2011-12-30 | 2012-07-25 | 华南师范大学 | Hydrothermal preparation method of carbon coated lead powder composite materials for lead carbon super batteries |
| CN102637858A (en) * | 2012-03-16 | 2012-08-15 | 天能电池集团有限公司 | Microwave preparation method for carbon-coated lead powder composite for lead-carbon super batteries |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103943859A (en) * | 2014-03-13 | 2014-07-23 | 天能电池集团有限公司 | Lead-carbon composite material, and preparation method and application thereof |
| CN103943859B (en) * | 2014-03-13 | 2017-01-18 | 天能电池集团有限公司 | Lead-carbon composite material, and preparation method and application thereof |
| CN106486645A (en) * | 2015-08-24 | 2017-03-08 | 中国科学院金属研究所 | A kind of lead carbon battery negative plate containing network-like material with carbon element and preparation method thereof |
| CN105990578A (en) * | 2016-04-27 | 2016-10-05 | 厦门百美特生物材料科技有限公司 | Lead carbon compound material as well as preparation method and application thereof |
| CN108899492A (en) * | 2018-06-21 | 2018-11-27 | 华中科技大学 | A kind of lead carbon composite, preparation method and application |
| CN108899492B (en) * | 2018-06-21 | 2020-05-19 | 华中科技大学 | Lead-carbon composite material, and preparation method and application thereof |
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Application publication date: 20130410 |