CN104993154A - Graphene-containing lead alloy for lead storage battery grids, and preparation method thereof - Google Patents
Graphene-containing lead alloy for lead storage battery grids, and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 229910000978 Pb alloy Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000003860 storage Methods 0.000 title abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 51
- 239000011575 calcium Substances 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005266 casting Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 37
- 239000004411 aluminium Substances 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 12
- 230000005587 bubbling Effects 0.000 claims description 8
- 238000005304 joining Methods 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004382 potting Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000000053 physical method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002142 lead-calcium alloy Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 241000168254 Siro Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WWGNOEDOFJKLST-UHFFFAOYSA-N [Cd].[Sb] Chemical compound [Cd].[Sb] WWGNOEDOFJKLST-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000000763 evoking effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001999 grid alloy Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
- H01M4/685—Lead alloys
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
- H01M4/84—Multi-step processes for manufacturing carriers for lead-acid accumulators involving casting
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a graphene-containing lead alloy for lead storage battery grids. The graphene-containing lead alloy includes 0.015-0.15% of graphene, 1.0-1.5% of tin, 0.02-0.04% of aluminum, 0.05-0.1% of calcium and 98.21-98.915% of lead. A preparation method of the graphene-containing lead alloy comprises the following steps: putting 2/3 of lead in a lead melting pot, and heating to 680DEG C in order to melt lead; adding graphene to molten lead; adding pure tin strips and pure aluminum strips 20min later, and stirring and mixing for above 0.5h; adding lead sheath packaged calcium, pressing calcium into the bottom of the molten lead by using a bell jar with the bottom provided with leakage holes, slowly stirring and mixing for above 0.5h when the molten lead does not bubble, adding the residual lead into the lead melting pot, continuously stirring after the lead is completely molten, and carrying out ingot casting 1h later. The preparation method has the advantages of simplicity, reliability, simple structure of a used device, and low cost; and the grids made by using the lead alloy prepared through the method have strong creep and corrosion resistance, and can meet deep cycle and heavy current charge and discharge requirements.
Description
Technical field
The invention belongs to Lead-acid Battery Technology field, relate to a kind of lead accumulator grid lead alloy containing Graphene and preparation method thereof.
Background technology
In recent years, along with the deterioration of environment, green energy resource just more and more causes the concern of society, one of effective way that electric automobile and micro-mixed automobile address this problem just.The reliable lead acid accumulator of with low cost, technology maturation as traditional electrical source of power also anxious pending technological improvement to adapt to the development need of electric automobile.The performance of lead acid accumulator depends primarily on pole plate, and grid is then the important component part of pole plate, determines the useful life, dehydration, large current discharging capability etc. of battery.The battery of plumbous antimony cadmium positive grid alloy manufacture has the feature of resistance to deeper cavity charging and discharging capabilities, is accepted extensively by market, but due to the cadmium element in lead-antimony alloy very large to harm, forbidden producing and using by China; At present, the alloy that lead acid accumulator plate grid the most generally uses is lead-calcium alloy, owing to easily forming the phenomenon of pore in the grid ubiquity cast panel process of lead-calcium alloy, grid creep-resistant property and corrosion resistant performance poor, easily the shortcomings such as barrier layer are formed after battery deep discharge, cannot meet the requirement of deeper cavity and high current charge-discharge, useful life is short.
Graphene is a kind of new material of the individual layer laminated structure be made up of carbon atom.Be a kind ofly form with sp2 hybridized orbit the flat film that hexangle type is honeycomb lattice by carbon atom, only have the two-dimensional material of a carbon atom thickness.The scientific circles that appear at of Graphene have evoked huge great waves, it is found that, Graphene has excellent electric conductivity, exceeds the intensity of iron and steel decades of times and fabulous light transmission, for improving lead alloy and lead plaster performance provides strong support.Say in theory, Graphene is mixed in storage battery lead alloy, utilize the electric conductivity of Graphene excellence and strength character can increase substantially the high rate during charging-discharging of pole plate and the creep resistant of grid and decay resistance, but be how perplex the key factor that lead carbon battery develops by the graphene dispersion of nano material to differing with its proportion in larger lead alloy always.At present, though there are some to relate to the preparation method of Graphene lead alloy, have plenty of and directly Graphene is mixed with other metal oxide, then carry out redox, generate Graphene foundry alloy; Have plenty of by by graphite and strong acid or other Strong oxdiative material by carry out after be oxidized ultrasonic disperse or HTHP instantaneously voltage drop method be prepared into graphene oxide, then to restore after graphene oxide is mixed with the oxide of other metal as Graphene foundry alloy; The plumbous liquid finally Graphene foundry alloy being placed in melting is made.There is following problem in these preparation methods: 1, relates to a large amount of and the smelting of specialty, combination reaction equipment and raw material, and to the sealing of equipment, bearing capacity, workshop condition etc. require very strict, and general lead alloy factory cannot realize.2, reduction reaction is chronic, and often need dozens of hour even more of a specified duration, need HTHP, oxygen-free environment, technical difficulty is larger, is difficult to universal production.
Summary of the invention
Object of the present invention solves problems of the prior art exactly, a kind of lead accumulator grid lead alloy containing Graphene and preparation method thereof is provided, the grid creep resistant that this lead alloy is made and corrosion resistant performance strong, the requirement of deeper cavity and high current charge-discharge can be met, mechanical strength is high, long service life; This preparation method is simple and reliable, and the device structure of use is simple, and cost is low.
For achieving the above object, technical scheme of the present invention is: a kind of lead accumulator grid lead alloy containing Graphene, counts by weight percentage, it comprises the Graphene of 0.015 ~ 0.15%, the tin of 1.0 ~ 1.5%, the aluminium of 0.02 ~ 0.04%, the calcium of 0.05 ~ 0.1% and the lead of 98.21 ~ 98.915%.
Graphene described above is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.Described Graphene can adopt physical method to produce, and chemical method also can be adopted to produce.
The preparation method of the lead accumulator grid lead alloy containing Graphene described above, it comprises the following steps:
(1) lead of 2/3 of described amount is inserted in market pot, be heated to 680 ° of C and melt completely to lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) close centrifugal blender, add the calcium encapsulated with sheet lead of described amount, the calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid, when plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, close centrifugal blender, the lead of surplus is added in market pot, treats that lead melts completely, open centrifugal blender, continue low rate mixing, ingot casting after a hour.
The feature of a kind of lead accumulator grid lead alloy containing Graphene of the present invention and preparation method thereof is:
1, by after graphene uniform blending is in lead-calcium alloy, Graphene is in the alloy with grid configuration existence closely, form favourable conductive mesh, after being made into grid, it is inner and surperficial that the conductive network that Graphene is formed spreads all over whole grid, and the Graphene on surface directly contacts with active material, can suitably reduce grid surface corrosion condition, the conductive network that Graphene is formed and active material and alloy grid compact siro spinning technology, thoroughly solve PCL-1, PCL-2, PCL-3.In addition, Graphene, at grid Intranet lattice distribution, adds its distinctive mechanical strength, can be used as the skeletal support of grid, strengthens grid mechanical strength.In a word, the battery grid that the Graphene lead alloy that adopts manufacture method of the present invention to make makes, effectively can strengthen the conductance of grid, improves the mechanical strength of grid, and in the process of battery high current charge-discharge in the future, grid is not yielding, lead plaster difficult drop-off.Graphene add the phenomenon suitably alleviating grid surface oxide etch in battery use procedure, and thoroughly can solve shortcoming grid electric conductivity being declined because of corrosion layer, and then enhance battery charging and discharging serviceability and cycle life.
2, the preparation method of a kind of lead accumulator grid lead alloy containing Graphene of the present invention, do not recycle redox mode and make Graphene foundry alloy, but Graphene finished product is added in the process of allotment lead-calcium alloy, mechanical agitation in addition, Graphene and metal is made to form eutectic, it not only can be dispersed in Graphene in lead-calcium alloy well, and whole preparation process only needs to complete for 3 to 4 hours, compare other redox mode and make Graphene alloy and can save 5 ~ 15 hours;
3, whole preparation process only needs market pot and some simple mechanical stirring devices to realize, compare some other redox mode and make in the preparation process of Graphene alloy a large amount of professional smelting equipment and combination reaction equipment that need, the equipment wanted required for the present invention and technical conditions are simply and easily realize, the conventional production equipment smelting factory at lead alloy can complete, and relative cost reduces a lot.
Embodiment
Below in conjunction with embodiment and experiment detect the present invention is described further:
Embodiment 1, a kind of lead accumulator grid lead alloy containing Graphene, calculate by weight, it comprises the Graphene of 0.015%, the tin of 1.0%, the aluminium of 0.02%, the sponge calcium of 0.05% and the lead of 98.915%.Its preparation method comprises the following steps: the electrolytic lead of 2/3 of described amount is inserted in market pot by (1), is heated to 680 ° of C and melts completely to electrolytic lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) centrifugal blender is closed; add the sponge calcium encapsulated with sheet lead of described amount; the sponge calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid; encapsulate with sheet lead when adding sponge calcium, then have the bell jar of small opening to be pressed into bottom plumbous liquid with bottom, allow sponge calcium slowly melt bottom plumbous liquid; because calcium is very active metal; at high temperature easy firing loss, encapsulates with sheet lead for this reason before addition, to reduce the loss of sponge calcium.When plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed melts completely, continues to stir, ingot casting after a hour.Graphene described above is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.Graphene can adopt physical method to produce, and chemical method also can be adopted to produce.
Embodiment 2, a kind of lead accumulator grid lead alloy containing Graphene, count by weight percentage, it comprises the Graphene of 0.03%, the tin of 1.2%, the aluminium of 0.04%, the sponge calcium of 0.08% and the lead of 98.65%.Its preparation method comprises the following steps: the electrolytic lead of 2/3 of described amount is inserted in market pot by (1), is heated to 680 ° of C and melts completely to electrolytic lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) centrifugal blender is closed; add the sponge calcium encapsulated with sheet lead of described amount; the sponge calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid; encapsulate with sheet lead when adding sponge calcium, then have the bell jar of small opening to be pressed into bottom plumbous liquid with bottom, allow sponge calcium slowly melt bottom plumbous liquid; because calcium is very active metal; at high temperature easy firing loss, encapsulates with sheet lead for this reason before addition, to reduce the loss of sponge calcium.When plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed melts completely, continues to stir, ingot casting after a hour.Graphene described above is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.Graphene can adopt physical method to produce, and chemical method also can be adopted to produce.
Embodiment 3, a kind of lead accumulator grid lead alloy containing Graphene, count by weight percentage, it comprises the Graphene of 0.06%, the tin of 1.2%, the aluminium of 0.04%, the sponge calcium of 0.1% and the lead of 98.6%.Its preparation method comprises the following steps: the electrolytic lead of 2/3 of described amount is inserted in market pot by (1), is heated to 680 ° of C and melts completely to electrolytic lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) centrifugal blender is closed; add the sponge calcium encapsulated with sheet lead of described amount; the sponge calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid; encapsulate with sheet lead when adding sponge calcium, then have the bell jar of small opening to be pressed into bottom plumbous liquid with bottom, allow sponge calcium slowly melt bottom plumbous liquid; because calcium is very active metal; at high temperature easy firing loss, encapsulates with sheet lead for this reason before addition, to reduce the loss of sponge calcium.When plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed melts completely, continues to stir, ingot casting after a hour.Graphene described above is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.Graphene can adopt physical method to produce, and chemical method also can be adopted to produce.
Embodiment 4, a kind of lead accumulator grid lead alloy containing Graphene, count by weight percentage, it comprises the Graphene of 0.09%, the tin of 1.1%, the aluminium of 0.025%, the sponge calcium of 0.07% and the lead of 98.715%.Its preparation method comprises the following steps: the electrolytic lead of 2/3 of described amount is inserted in market pot by (1), is heated to 680 ° of C and melts completely to electrolytic lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) centrifugal blender is closed; add the sponge calcium encapsulated with sheet lead of described amount; the sponge calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid; encapsulate with sheet lead when adding sponge calcium, then have the bell jar of small opening to be pressed into bottom plumbous liquid with bottom, allow sponge calcium slowly melt bottom plumbous liquid; because calcium is very active metal; at high temperature easy firing loss, encapsulates with sheet lead for this reason before addition, to reduce the loss of sponge calcium.When plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed melts completely, continues to stir, ingot casting after a hour.Graphene described above is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.Graphene can adopt physical method to produce, and chemical method also can be adopted to produce.
Embodiment 5, a kind of lead accumulator grid lead alloy containing Graphene, count by weight percentage, it comprises the Graphene of 0.12%, the tin of 1.2%, the aluminium of 0.035%, the sponge calcium of 0.09% and the lead of 98.555%.Its preparation method comprises the following steps: the electrolytic lead of 2/3 of described amount is inserted in market pot by (1), is heated to 680 ° of C and melts completely to electrolytic lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) centrifugal blender is closed; add the sponge calcium encapsulated with sheet lead of described amount; the sponge calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid; encapsulate with sheet lead when adding sponge calcium, then have the bell jar of small opening to be pressed into bottom plumbous liquid with bottom, allow sponge calcium slowly melt bottom plumbous liquid; because calcium is very active metal; at high temperature easy firing loss, encapsulates with sheet lead for this reason before addition, to reduce the loss of sponge calcium.When plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed melts completely, continues to stir, ingot casting after a hour.Graphene described above is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.Graphene can adopt physical method to produce, and chemical method also can be adopted to produce.
Embodiment 6, a kind of lead accumulator grid lead alloy containing Graphene, count by weight percentage, it comprises the Graphene of 0.15%, the tin of 1.5%, the aluminium of 0.04%, the sponge calcium of 0.1% and the lead of 98.21%.Its preparation method comprises the following steps: the electrolytic lead of 2/3 of described amount is inserted in market pot by (1), is heated to 680 ° of C and melts completely to electrolytic lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) centrifugal blender is closed; add the sponge calcium encapsulated with sheet lead of described amount; the sponge calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid; encapsulate with sheet lead when adding sponge calcium, then have the bell jar of small opening to be pressed into bottom plumbous liquid with bottom, allow sponge calcium slowly melt bottom plumbous liquid; because calcium is very active metal; at high temperature easy firing loss, encapsulates with sheet lead for this reason before addition, to reduce the loss of sponge calcium.When plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed melts completely, continues to stir, ingot casting after a hour.Graphene described above is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.Graphene can adopt physical method to produce, and chemical method also can be adopted to produce.
Respectively the hardness of Graphene lead alloy obtained in embodiment 1 ~ 6, tensile strength and resistivity are detected, and draw following data:
After Graphene lead alloy obtained in embodiment 1 ~ 6 is made the resultant battery of 6-DZM-20, test, battery initial capacity is 22.6Ah, through 150 times shallow fill deep discharge after, residual capacity is respectively 21.1Ah, 21.3Ah, 21.5Ah, 21.7Ah, 21.8Ah, 21.8Ah, does not find barrier layer phenomenon, continues circulation, after 350 100% DOD circulations, residual capacity is respectively 20.2Ah, 20.1Ah, 20.4Ah, 20.5Ah, 20.6Ah, 20.5Ah.Dissection and analysis, finds the existing a small amount of corrosion of grid and active material ruckbildung.But small on battery performance impact, absolutely prove that Graphene can slow down grid corrosion situation, and thoroughly can solve the series of negative impact produced because of grid corrosion.
Can be found out by above experimental data, Graphene addition is more, and grid hardness is higher, and tensile strength is better, and resistivity is lower, is enough to illustrate can improve grid mechanical strength adding of Graphene, reduces grid deflection, strengthens grid conductivity.As long as the hardness that in producing conventional, we sum up grid reaches the requirement that 22N/mm2 just can meet painting cream, we show that Graphene content is 0.015% time by experiment, grid is through short-term timeliness, its hardness just can reach the requirement of conventional coated plate, and tensile strength and resistivity also all surmount in Standard.The higher grid performance of Graphene content is better, but when Graphene content higher than 0.15% time, alloy grid performance is far more than Standard, and large help is not had yet again to battery performance, add the also just waste of more Graphene, so the desired contents of Graphene should control in 0.015 ~ 0.15% scope.
Claims (3)
1. the lead accumulator grid lead alloy containing Graphene, it is characterized in that: count by weight percentage, it comprises the Graphene of 0.015 ~ 0.15%, the tin of 1.0 ~ 1.5%, the aluminium of 0.02 ~ 0.04%, the calcium of 0.05 ~ 0.1% and the lead of 98.21 ~ 98.915%.
2. the lead accumulator grid lead alloy containing Graphene according to claim 1, is characterized in that: described Graphene is one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.
3. a method processed for the lead accumulator grid lead alloy containing Graphene described in claim 1 or 2, is characterized in that: it comprises the following steps:
(1) lead of 2/3 of described amount is inserted in market pot, be heated to 680 ° of C and melt completely to lead; (2) then open centrifugal blender, slowly add the Graphene of described amount continuously or be interrupted interpolation in batches joining in plumbous liquid when moderate-speed mixer; After (3) 20 minutes, successively add pure tin bar and the fine aluminium bar of described amount, centrifugal blender continues to be uniformly mixed half an hour more than; (4) close centrifugal blender, add the calcium encapsulated with sheet lead of described amount, the calcium bottom of being encapsulated by sheet lead has the bell jar of small opening to be pressed into bottom plumbous liquid, when plumbous liquid no longer bubbling time, start centrifugal blender low rate mixing mixing; (5) after half an hour, close centrifugal blender, the lead of surplus is added in market pot, treats that lead melts completely, open centrifugal blender, continue low rate mixing, ingot casting after a hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510266049.6A CN104993154B (en) | 2015-05-23 | 2015-05-23 | A kind of lead accumulator grid metal containing graphene and preparation method thereof |
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| CN201510266049.6A CN104993154B (en) | 2015-05-23 | 2015-05-23 | A kind of lead accumulator grid metal containing graphene and preparation method thereof |
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| CN104993154A true CN104993154A (en) | 2015-10-21 |
| CN104993154B CN104993154B (en) | 2018-02-16 |
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| CN106784858A (en) * | 2015-11-25 | 2017-05-31 | 衡阳瑞达电源有限公司 | Lead accumulator grid additive, preparation method, grid and high connductivity lead accumulator |
| CN108390005A (en) * | 2018-02-01 | 2018-08-10 | 超威电源有限公司 | A kind of highly conductive bus structures of lead-acid accumulator |
| CN109778000A (en) * | 2018-12-19 | 2019-05-21 | 安徽理士电源技术有限公司 | A kind of graphene-based corrosion resisting alloy grid of battery and preparation method thereof |
| CN110224143A (en) * | 2019-07-01 | 2019-09-10 | 清华大学深圳研究生院 | Lead-acid battery collector, preparation method, pole plate and lead-acid battery |
| CN110224141A (en) * | 2019-05-16 | 2019-09-10 | 旭派电源有限公司 | A kind of preparation method of full lead carbon battery negative plate grid alloy |
| CN111816846A (en) * | 2020-07-03 | 2020-10-23 | 肇庆理士电源技术有限公司 | Graphene doping-based lead-carbon battery negative grid and preparation method thereof |
| CN112522536A (en) * | 2020-12-08 | 2021-03-19 | 英德奥克莱电源有限公司 | Lead-calcium alloy for positive grid and preparation method thereof |
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| CN111816846A (en) * | 2020-07-03 | 2020-10-23 | 肇庆理士电源技术有限公司 | Graphene doping-based lead-carbon battery negative grid and preparation method thereof |
| CN112522536A (en) * | 2020-12-08 | 2021-03-19 | 英德奥克莱电源有限公司 | Lead-calcium alloy for positive grid and preparation method thereof |
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