CN104022287A - Additive for negative electrode plate of lead storage battery, and preparation method thereof - Google Patents
Additive for negative electrode plate of lead storage battery, and preparation method thereof Download PDFInfo
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- CN104022287A CN104022287A CN201410217182.8A CN201410217182A CN104022287A CN 104022287 A CN104022287 A CN 104022287A CN 201410217182 A CN201410217182 A CN 201410217182A CN 104022287 A CN104022287 A CN 104022287A
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- lead
- carbon
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- lead accumulator
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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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
Abstract
The invention provides an additive for a negative electrode plate of a lead storage battery, and a preparation method thereof. The additive is a layered carbon/lead oxide composite material. The layer number of the layered carbon is 1-50; lead oxide particles are uniformly adhered on the layered carbon; the size of the lead oxide particles is 5-200 nm; and a mass ratio of the layered carbon to lead oxide is 1:1-200. The additive for the negative electrode plate of the lead storage battery can effectively increase energy density, power density and cycle life of the lead storage battery.
Description
Technical field
The present invention relates to a kind of battery cathode additive and preparation method thereof, specifically relate to a kind of lead acid accumulator composite negative pole additive and preparation method.
Background technology
Along with developing rapidly of electric automobiles such as pure electric vehicle and hybrid electric vehicle HEV, lead accumulator because its raw material resources are abundant, cheap, technical maturity and the feature such as fail safe is good, in electric motor car, there is good application prospect, but due to the shortcoming such as specific power useful life lower and high power discharge of lead accumulator is short, restricted its development.And cause the problems referred to above main cause, be due to negative pole, under high-density current discharge scenario, a large amount of lead ions that negative pole produces enter electrolyte, the situation of answering is in contrast sulfate ion diffusion limited in electrolyte, cause lead ion supersaturation, thereby the lead sulfate beds of precipitation that form one deck densification in negative terminal surface, cause negative terminal surface passivation.Due to lead sulfate poorly conductive, solubility is little, so can cause the inner plumbous reactivity of negative pole to reduce, increases reaction overpotential, and while causing charging, liberation of hydrogen is comparatively serious, and charge efficiency declines, and forms vicious circle.If continue high-power discharging and recharging, above situation can further worsen, and lead sulfate deposit seed increases, and such increase process is irreversible again, finally causes negative pole to lose reactivity, battery failure.
Active carbon is directly added in the prior art that promotes battery impulse power in negative plate of lead storage battery just like 200810136333.1,200880009193.X and No. 200910098917.9 Chinese patents all have and directly add lead-acid battery electrode plate to improve the record of device performance active carbon.Yet active carbon, carbon nano-tube and Graphene significantly improve as the cost of additive battery, and carbonaceous material can accelerate the liberation of hydrogen effect of battery.
Summary of the invention
The lead-acid battery negative pole plate additive and preparation method thereof that the object of this invention is to provide a kind of energy density, power density and service life cycle of effective raising lead accumulator.
Concrete scheme of the present invention is: a kind of lead-acid battery negative pole plate additive, described additive is stratiform carbon/lead oxide composite material, the number of plies of layered carbon is 1-50 layer, particles of lead oxide is attached on stratiform carbon uniformly, the particle size of described lead oxide is 5-200nm, the mass ratio of layered carbon and lead oxide is 1: 1-200, wherein, the addition of described additive is the 0.05-0.5% of lead accumulator negative electrode lead opaque amount.
The preparation method of negative plate of lead storage battery additive of the present invention, concrete steps comprise:
(1) stratiform carbon is prepared in vapour deposition: catalyst substrate material is put into reactor, at 700-1200 ℃, in described reactor, pass into carbon source reaction 0.5-2.0 hour, in substrate surface deposition stratiform carbon-coating.
(2) stratiform carbon and lead oxide is compound: it is the lead nitrate solution of 0.05～0.20mol/L that the stratiform carbon of step (1) gained is added to concentration together with base material, in solution plumbi nitras quality be catalyst substrate quality of materials 2-5 doubly, product heat treatment 0.5-2.0 hour at 300～450 ℃ of normal temperature, the lower reaction of stirring 0.5-2.0 hour, suction filtration, obtains negative plate of lead storage battery additive.
Preferably, catalyst substrate of the present invention is the mixture of any one or two kinds in potash, sodium carbonate, and base material used is Powdered.
Another is preferred, and carbon source of the present invention is a kind of or its combination in any in methane, carbon monoxide, acetylene.
One is preferred again, and the flow of described carbon source is 5-200sccm; 20-100sccm more preferably.
One is preferred again, and the reaction time of described vapor deposition reaction is 30-120 minute; 30-60 minute more preferably.
One is preferred again, described stratiform carbon, and long and wide is 0.5-200 μ m.
Adopt technique scheme, technique effect of the present invention has:
Thereby the stratiform carbon of this additive provides larger specific area to be conducive to the dispersed of particles of lead oxide and the express passway of electric transmission is provided, and has improved the electron conduction of negative pole.Particles of lead oxide is evenly distributed on stratiform carbon, has suppressed the liberation of hydrogen of stratiform carbon, also makes the binding ability of composite material and lead plaster strong.Stratiform carbon and lead oxide composite additives have larger compacted density, are easy to evenly mix with lead plaster; The combination of the stratiform carbon of high conductivity and the excellent structure of the evengranular distribution of Nanometer sized lead oxide, the sulfation producing when anticathode is discharged plays inhibitory action.In preparation process, select the lead nitrate solution of 0.05～0.20mol/L, too dense meeting causes lead oxide cannot be deposited in uniformly on stratiform carbon, and too rare meeting makes that the deposition of lead oxide is too low cannot obtain good effect.The preparation process price of composite material is low, easy and simple to handle, easily industrialization.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.
Embodiment 1
The crucible that fills 10g potash is put into Muffle furnace, Muffle furnace is warming up to 700 ℃, then to the acetylene and the methane mass ratio mist of 1: 1 that pass into 50sccm in stove, react and after 60 minutes, powdered product is joined in 500mL, 0.2mol/L lead nitrate solution and reacted 0.8 hour, at washing, dry latter 400 ℃, heat treatment obtains negative plate of lead storage battery additive for 1 hour.In gained additive, the mass ratio of charcoal and lead oxide is 1: 200 after testing, and with ESEM, recording stratiform charcoal length and width is respectively 2.50 μ m and 1.50 μ m, and the average number of plies is 10 layers, and lead oxide particulate average-size is 100nm, at stratiform carbon surface, is uniformly distributed.
0.2% the ratio according to its quality in negative pole lead powder adds gained additive, and prepare 12V12Ah specification battery according to conventional method, battery 10 hour rates that obtain and 2 hour rate specific discharge capacities (based on negative pole quality) are respectively 150.3mAh/g and 122.7mAh/g, than the specific capacity of common 12V12Ah battery discharge, improved respectively 18.3% and 30.3%, shown significant performance and improve.After 100 circulations of battery of 2 hour rates, battery capacity conservation rate is 92%, higher than 71% of common 12V12Ah battery.Battery 10C electric discharge duration is greater than 180 seconds, has excellent power discharge performance, and in contrast, under the large electric current of common 12V12Ah lead-acid battery 10C, electric discharge can only be discharged 6 seconds.Except being otherwise noted, common lead-acid battery of the present invention is for being added with the lead-acid battery of the carbon black of lead powder quality 0.3% in its negative plates.
Embodiment 2
By tile corundum crucible bottom of the mixture of 5g potash and 5g sodium carbonate, crucible is put into Muffle furnace, Muffle furnace is warmed up to 700 ℃, then to the acetylene and the methane mass ratio mist of 1: 3 that pass into 100sccm in stove, react and after 60 minutes, powdered product is joined in 500mL, 0.15mol/L lead nitrate solution and reacted 1.1 hours, after product is washed, is dried, in air, 400 ℃ of heat treatments obtain additive product after 1 hour.In additive, charcoal and lead oxide mass ratio are 1: 20 after tested, by scanning electron microscope observation, learn that stratiform charcoal length and width are respectively 150 μ m and 50 μ m, and the average number of plies is 10 layers, and lead oxide particulate average-size is 120nm, at stratiform carbon surface, is uniformly distributed.
0.5% the ratio according to its quality in negative pole lead powder adds gained additive, and prepare 12V20Ah battery according to conventional method, battery 10 hour rates that obtain, 2 hour rate specific discharge capacities (based on negative pole quality) are respectively 157.8mAh/g and 137.1mAh/g, capacity than common 12V20Ah respective rate electric discharge has improved respectively 24.5% and 45.8%, shows significant performance and improves.After 2 hour rate 100 times circulations, battery capacity conservation rate is 93%, far above 71% of common 12V20Ah battery.In addition, battery 10C electric discharge duration is greater than 200 seconds, has excellent power discharge performance, and in contrast, under the large electric current of common 12V20Ah lead-acid battery 10C, electric discharge can only be discharged 6 seconds.
Embodiment 3
By tile corundum crucible bottom of the mixture of 3g potash and 5g sodium carbonate, crucible is put into Muffle furnace, Muffle furnace is warmed up to 1100 ℃, then to the carbon monoxide and the methane mass ratio mist of 1: 1 that pass into 80sccm in stove, react and after 120 minutes, product is taken out, product powder is joined in 600mL, 0.20mol/L lead nitrate solution and reacted 2.0 hours, and after product is washed, is dried, in air, 400 ℃ of heat treatments obtain additive product after 1 hour.In additive, charcoal and lead oxide mass ratio are 1.5: 10 after tested, by scanning electron microscope observation, learn that stratiform charcoal length and width are respectively 200 μ m and 70 μ m, and the average number of plies is 20 layers, and lead oxide particulate average-size is 100nm, at stratiform carbon surface, is uniformly distributed.
0.4% the ratio according to its quality in negative pole lead powder adds gained additive, and prepare 12V20Ah battery according to conventional method, battery 10 hour rates that obtain, 2 hour rate specific discharge capacities (based on negative pole quality) are respectively 169.8mAh/g and 148.1mAh/g, capacity than common 12V20Ah respective rate electric discharge has improved respectively 34.0% and 91.4%, shows significant performance and improves.After 2 hour rate 100 times circulations, battery capacity conservation rate is 95%, far above 71% of common 12V20Ah battery.In addition, battery 10C electric discharge duration is greater than 210 seconds, has excellent power discharge performance, and in contrast, under the large electric current of common 12V20Ah lead-acid battery 10C, electric discharge can only be discharged 6 seconds.
Embodiment 4
By tile corundum crucible bottom of the mixture of 5g potash and 1g sodium carbonate, crucible is put into Muffle furnace, Muffle furnace is warmed up to 820 ℃, then to the acetylene and the carbon monoxide mass ratio mist of 1: 1 that pass into 10sccm in stove, react and after 30 minutes, product is taken out, product powder is joined in 750mL, 0.05mol/L lead nitrate solution and reacted 0.5 hour, and after product is washed, is dried, in air, 400 ℃ of heat treatments obtain additive product after 1 hour.In additive, charcoal and lead oxide mass ratio are 1: 20 after tested, by scanning electron microscope observation, learn that stratiform charcoal length and width are respectively 120 μ m and 40 μ m, and the average number of plies is 3 layers, and lead oxide particulate average-size is 90nm, at stratiform carbon surface, is uniformly distributed.
0.05% the ratio according to its quality in negative pole lead powder adds gained additive, and prepare 12V20Ah battery according to conventional method, battery 10 hour rates that obtain, 2 hour rate specific discharge capacities (based on negative pole quality) are respectively 130.2mAh/g and 101.1mAh/g, capacity than common 12V20Ah respective rate electric discharge has improved respectively 3.0% and 7.6%, shows performance and improves.After 2 hour rate 100 times circulations, battery capacity conservation rate is 81%, higher than 71% of common 12V20Ah battery.In addition, battery 10C electric discharge duration is greater than 50 seconds, has excellent power discharge performance, and in contrast, under the large electric current of common 12V20Ah lead-acid battery 10C, electric discharge can only be discharged 6 seconds.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit, although the present invention is had been described in detail with reference to above-described embodiment, those of ordinary skill in the field are to be understood that: still can modify or be equal to replacement the specific embodiment of the present invention, and do not depart from any modification of spirit and scope of the invention or be equal to replacement, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. a lead accumulator cathode additive agent, it is characterized in that, described additive is stratiform carbon and lead oxide composite material, described lead oxide is evenly attached on the outermost layer of stratiform carbon that the number of plies is 1-50 layer, the mass ratio of layered carbon and lead oxide is 1: 1-200, the particle size of described lead oxide is 5-200nm.
2. lead accumulator cathode additive agent as claimed in claim 1, is characterized in that, the addition of described additive is the 0.05-0.5% of lead accumulator negative electrode lead opaque amount.
3. lead accumulator cathode additive agent as claimed in claim 1, is characterized in that, the mass ratio of layered carbon and lead oxide is 1: 1-20, described lead oxide is that granularity is the particle of 90-120nm.
4. the preparation method of lead accumulator cathode additive agent as claimed in claim 1, its step comprises:
(1) stratiform carbon is prepared in vapour deposition: catalyst substrate material is put into the reactor of 700-1200 ℃, in described reactor, passed into carbon source reaction 0.5-2 hour, at the surface deposition stratiform carbon-coating of base material.
(2) stratiform carbon and lead oxide is compound: it is the lead nitrate solution of 0.05～0.20mol/L that the stratiform carbon of step (1) gained is added to concentration together with base material, in solution plumbi nitras quality be catalyst substrate quality 2-5 doubly, under stirring at normal temperature, reaction 0.5-2.0 hour, after suction filtration at 300～450 ℃ heat treatment 0.5-2.0 hour, obtain negative plate of lead storage battery additive.
5. the preparation method of lead accumulator cathode additive agent as claimed in claim 4, is characterized in that, described catalyst substrate material is the mixture of any one or two kinds in potash, sodium carbonate.
6. the preparation method of lead accumulator cathode additive agent as claimed in claim 4, is characterized in that, described carbon source is a kind of or its combination in any in methane, carbon monoxide, acetylene.
7. the preparation method of lead accumulator cathode additive agent as claimed in claim 4, is characterized in that, the flow of described carbon source is 5-200sccm.
8. the preparation method of lead accumulator cathode additive agent as claimed in claim 7, is characterized in that, the flow of described carbon source is 20-100sccm.
9. the preparation method of lead accumulator cathode additive agent as claimed in claim 4, is characterized in that, it is characterized in that, the reaction time of described vapor deposition reaction is 30-120 minute.
10. the preparation method of lead accumulator cathode additive agent as claimed in claim 9, is characterized in that, the reaction time of described vapor deposition reaction is 30-60 minute.
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| CN201410217182.8A CN104022287B (en) | 2014-05-22 | 2014-05-22 | A kind of Additives in negative electrode of lead-acid battery and preparation method thereof |
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| CN201410217182.8A CN104022287B (en) | 2014-05-22 | 2014-05-22 | A kind of Additives in negative electrode of lead-acid battery and preparation method thereof |
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| CN104022287A true CN104022287A (en) | 2014-09-03 |
| CN104022287B CN104022287B (en) | 2016-08-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953192A (en) * | 2015-06-12 | 2015-09-30 | 河北师范大学 | Preparation method of Pb-containing lead-acid battery negative electrode additive |
Citations (2)
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|---|---|---|---|---|
| CN102064319A (en) * | 2010-12-14 | 2011-05-18 | 哈尔滨工业大学 | Negative plate of lead acid super battery, production method and lead acid super battery assembled by negative plate |
| CN103137955A (en) * | 2013-03-12 | 2013-06-05 | 深圳市雄韬电源科技股份有限公司 | Lead/carbon composite for storage battery and preparation method of lead/carbon composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102064319A (en) * | 2010-12-14 | 2011-05-18 | 哈尔滨工业大学 | Negative plate of lead acid super battery, production method and lead acid super battery assembled by negative plate |
| CN103137955A (en) * | 2013-03-12 | 2013-06-05 | 深圳市雄韬电源科技股份有限公司 | Lead/carbon composite for storage battery and preparation method of lead/carbon composite material |
Non-Patent Citations (1)
| Title |
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| YONGHENG ZHANG，ET AL.: "Synthesis of Carbon Nanofibers and Foam by Catalytic Chemical Vapor Deposition Using a Water-Soluble Alkali Salt Catalyst", 《ADVANCED MATERIALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953192A (en) * | 2015-06-12 | 2015-09-30 | 河北师范大学 | Preparation method of Pb-containing lead-acid battery negative electrode additive |
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