CN104993154B - A kind of lead accumulator grid metal containing graphene and preparation method thereof - Google Patents
A kind of lead accumulator grid metal containing graphene and preparation method thereof Download PDFInfo
- Publication number
- CN104993154B CN104993154B CN201510266049.6A CN201510266049A CN104993154B CN 104993154 B CN104993154 B CN 104993154B CN 201510266049 A CN201510266049 A CN 201510266049A CN 104993154 B CN104993154 B CN 104993154B
- Authority
- CN
- China
- Prior art keywords
- lead
- graphene
- calcium
- added
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 116
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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
- 239000007788 liquid Substances 0.000 claims abstract description 40
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004411 aluminium Substances 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
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000005587 bubbling Effects 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 9
- 239000000155 melt Substances 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000013019 agitation Methods 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 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
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- WWGNOEDOFJKLST-UHFFFAOYSA-N [Cd].[Sb] Chemical compound [Cd].[Sb] WWGNOEDOFJKLST-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 230000008859 change Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method 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
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 230000035800 maturation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 kind of lead accumulator grid metal containing graphene, it includes 0.015 ~ 0.15% graphene, 1.0 ~ 1.5% tin, 0.02 ~ 0.04% aluminium, 0.05 ~ 0.1% calcium and 98.21 ~ 98.915% lead.Its preparation method is：2/3 lead is inserted in market pot, is heated to 680 °C to lead fusing；Graphene is added in lead liquid under agitation；After 20 minutes, pure tin bar and fine aluminium bar are successively added, is stirred more than half an hour；The calcium that addition has been encapsulated with sheet lead, calcium is pressed into lead liquid bottom by the bell jar for having small opening with bottom, when lead liquid no longer bubbling, after mixing slowly mixing half an hour, the lead of surplus is added in market pot, treats that lead melts completely, continues to stir, ingot casting after one hour.The preparation method of the present invention is simple and reliable, and the device structure used is simple, and cost is low；Grid creep resistant and corrosion resistant performance are strong made of the metal made of this method, disclosure satisfy that the requirement of deeper cavity and high current charge-discharge.
Description
Technical field
The invention belongs to Lead-acid Battery Technology field, is related to a kind of lead accumulator grid metal containing graphene
And preparation method thereof.
Background technology
In recent years, with the deterioration of environment, green energy resource is just increasingly causing the concern of society, electric automobile and micro- mixed vapour
Car is exactly to solve one of effective way of this problem.Cost is cheap, the reliable lead-acid accumulator of technology maturation is 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 of pole plate, determine the service life of battery, dehydration, large current discharging capability etc..Lead
The battery of antimony cadmium positive grid alloy manufacture has the characteristics of resistance to deeper cavity charging and discharging capabilities, is accepted extensively by market, but due to
Cadmium element harm to the human body in lead-antimony alloy is very big, is forbidden producing and is used by China；At present, lead acid accumulator plate grid is most
The alloy generally used is lead-calcium alloy, due to easily forming showing for stomata during the grid generally existing cast panel of lead-calcium alloy
As grid creep-resistant property and corrosion resistant performance are poor, and easy the shortcomings of forming barrier layer, can not meet deeper cavity after battery deep discharge
It is short with the requirement of high current charge-discharge, service life.
Graphene is a kind of new material for the individual layer laminated structure being made up of carbon atom.It is a kind of miscellaneous with sp2 by carbon atom
Change the flat film that track composition hexangle type is in honeycomb lattice, the two-dimensional material of only one carbon atom thickness.Graphene goes out
Present scientific circles have evoked huge great waves, it has been found that, graphene has excellent electric conductivity, beyond steel decades of times
Intensity and fabulous translucency, strong support is provided to improve metal and lead plaster performance.Say in theory, by graphene
Mix in battery metal, the big electricity of pole plate can be increased substantially using the excellent electric conductivity of graphene and strength character
The creep resistant and decay resistance of charge-discharge performance and grid are flowed, but how to be compared the graphene dispersion of nano material to it
It is the key factor for perplexing lead carbon battery development always in the larger metal of heavy phase difference.At present, though there is some to be related to graphene
The preparation method of metal, have plenty of and directly mix graphene with other metal oxides, then carry out redox, generate
Graphene foundry alloy；Have plenty of by by graphite and strong acid or other Strong oxdiative materials by carried out after oxidation ultrasonic disperse or
HTHP moment voltage drop method is prepared into graphene oxide, then is gone back again after graphene oxide is mixed with the oxide of other metals
Originally it was graphene foundry alloy；Made of finally graphene foundry alloy being placed in the lead liquid of melting.These preparation methods exist with
Lower problem：1st, it is related to a large amount of and professional smeltings, combination reaction equipment and raw material, and sealing to equipment, bearing capacity, workshop
The requirements such as environment are very strict, and general metal factory can not realize.2nd, the reduction reaction time is very long, and it is small to generally require dozens of
When even more long, it is necessary to which HTHP, oxygen-free environment, technical difficulty is bigger, it is difficult to popularize production.
The content of the invention
The purpose of the present invention is exactly to solve problems of the prior art, there is provided a kind of lead accumulator containing graphene
Grid metal and preparation method thereof, grid creep resistant and corrosion resistant performance are strong made of the metal, disclosure satisfy that deeper cavity
With the requirement of high current charge-discharge, high mechanical strength, service life length；The preparation method is simple and reliable, the device structure used
Simply, cost is low.
To achieve the above object, the technical scheme is that：A kind of lead accumulator grid containing graphene is closed with lead
Gold, count by weight percentage, it includes 0.015 ~ 0.15% graphene, 1.0 ~ 1.5% tin, 0.02 ~ 0.04% aluminium,
0.05 ~ 0.1% calcium and 98.21 ~ 98.915% lead.
Graphene described above is one in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip
Kind is a variety of.Described graphene can be produced using physical method, can also be produced using chemical method.
The preparation method of lead accumulator grid metal described above containing graphene, it comprises the following steps：
(1) 2/3 lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to lead；(2) it is then turned on
Centrifugal blender, by the graphene of the amount, slowly continuous addition or interruption addition in batches add in the case of moderate-speed mixer
Into lead liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, centrifugal blender continues to be stirred half
More than hour；(4) centrifugal blender is closed, adds the calcium encapsulated with sheet lead of the amount, the calcium bottom that sheet lead has been encapsulated
There is the bell jar press-in lead liquid bottom of small opening in portion, when lead liquid no longer bubbling, starts centrifugal blender and mixes slowly mixing；(5) half
After hour, centrifugal blender is closed, the lead of surplus is added in market pot, treats that lead melts completely, opens centrifugal blender, after
It is continuous to mix slowly, ingot casting after one hour.
A kind of lead accumulator grid containing graphene of the present invention is with the characteristics of metal and preparation method thereof：
1st, after graphene uniform is blended in lead-calcium alloy, graphene exists with close grid configuration in the alloy,
Favourable conductive mesh is formed, after grid is fabricated to, the conductive network that graphene is formed spreads all over inside whole grid and surface, table
The graphene in face directly contacts with active material, can suitably reduce grid surface corrosion condition, the conductive network that graphene is formed
Closely it is connected with active material with alloy grid, thoroughly solves PCL-1, PCL-2, PCL-3.In addition, graphene is in grid Intranet
Lattice distribution, plus its distinctive mechanical strength, grid mechanical strength can be strengthened as the skeletal support of grid.In a word, using this
It the battery grid that the graphene metal that method makes makes, can effectively strengthen the conductance of grid, improve plate
The mechanical strength of grid, grid is unlikely to deform during battery high current charge-discharge in the future, and lead plaster is difficult for drop-off.Graphene
Addition can suitably alleviate the phenomenon of grid surface oxide etch during battery use, and can thoroughly solve to make plate because of corrosion layer
The shortcomings that grid electric conductivity declines, and then enhance battery charging and discharging performance and cycle life.
2nd, the preparation method of a kind of lead accumulator grid metal containing graphene of the present invention, does not recycle oxygen
The mode for changing reduction makes graphene foundry alloy, but graphene finished product is added during lead-calcium alloy is allocated, and is subject to machine
Tool stirs, and graphene is formed eutectic with metal, and it can not only be well dispersed in graphene in lead-calcium alloy, and entirely
Preparation process only needs 3 to 4 hours to complete, and 5 can be saved by making graphene alloy compared to other redox modes
~15 hours；
3rd, whole preparation process only needs market pot and some simple mechanical stirring devices to can be achieved, compared to other one
A little redox modes make a large amount of professional smelting equipments needed in the preparation process of graphene alloy and combination reaction is set
For standby, equipment and technical conditions required for the present invention are simply and readily realized, smelt the conventional production of factory in metal
Equipment can be completed, and relative cost reduces a lot.
Embodiment
With reference to embodiment and experiment detection, the present invention is described further：
A kind of embodiment 1, lead accumulator grid metal containing graphene, is calculated by weight, and it includes 0.015%
Graphene, 1.0% tin, 0.02% aluminium, 0.05% sponge calcium and 98.915% lead.Its preparation method includes following step
Suddenly：(1) 2/3 electrolytic lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to electrolytic lead；(2) and then open
Centrifugal blender is opened, slow continuous addition or interruption addition in batches add in the case of moderate-speed mixer by the graphene of the amount
Enter into lead liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, centrifugal blender continues to be stirred
It is more than half an hour；(4) centrifugal blender is closed, the sponge calcium encapsulated with sheet lead of the amount is added, sheet lead has been encapsulated
The bell jar press-in lead liquid bottom of small opening is arranged at sponge calcium bottom, is encapsulated when adding sponge calcium with sheet lead, then have leakage with bottom
The bell jar press-in lead liquid bottom in hole, allows sponge calcium slowly to be melted in lead liquid bottom, because calcium is very active metal, in high temperature
Lower easy firing loss, is encapsulated with sheet lead, to reduce the loss of sponge calcium before addition for this.When lead liquid no longer bubbling,
Start centrifugal blender and mix slowly mixing；(5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed
Melt completely, continue to stir, ingot casting after one hour.Graphene described above is single-layer graphene, bilayer graphene, few layer stone
One or more in black alkene or graphene microchip.Graphene can be produced using physical method, can also use chemical method system
Take.
Embodiment 2, a kind of lead accumulator grid metal containing graphene, count by weight percentage, it is included
0.03% graphene, 1.2% tin, 0.04% aluminium, 0.08% sponge calcium and 98.65% lead.Its preparation method includes following
Step：(1) 2/3 electrolytic lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to electrolytic lead；(2) then
Centrifugal blender is opened, the graphene of the amount is slowly continuously added in the case of moderate-speed mixer or interruption is added in batches
It is added in lead liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, it is mixed that centrifugal blender continues stirring
Close more than half an hour；(4) centrifugal blender is closed, the sponge calcium encapsulated with sheet lead of the amount is added, sheet lead is encapsulated
Sponge calcium bottom have the bell jar press-in lead liquid bottom of small opening, encapsulated when adding sponge calcium with sheet lead, then have with bottom
The bell jar press-in lead liquid bottom of small opening, allows sponge calcium slowly to be melted in lead liquid bottom, because calcium is very active metal, in height
The lower easy firing loss of temperature, is encapsulated with sheet lead, to reduce the loss of sponge calcium before addition for this.When the no longer bubbling of lead liquid
When, start centrifugal blender and mix slowly mixing；(5) after half an hour, the electrolytic lead of surplus is added in market pot, it is to be electrolysed
Lead melts completely, continues to stir, ingot casting after one hour.Graphene described above is single-layer graphene, bilayer graphene, few layer
One or more in graphene or graphene microchip.Graphene can be produced using physical method, can also use chemical method
Produce.
Embodiment 3, a kind of lead accumulator grid metal containing graphene, count by weight percentage, it is included
0.06% graphene, 1.2% tin, 0.04% aluminium, 0.1% sponge calcium and 98.6% lead.Its preparation method includes following step
Suddenly：(1) 2/3 electrolytic lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to electrolytic lead；(2) and then open
Centrifugal blender is opened, slow continuous addition or interruption addition in batches add in the case of moderate-speed mixer by the graphene of the amount
Enter into lead liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, centrifugal blender continues to be stirred
It is more than half an hour；(4) centrifugal blender is closed, the sponge calcium encapsulated with sheet lead of the amount is added, sheet lead has been encapsulated
The bell jar press-in lead liquid bottom of small opening is arranged at sponge calcium bottom, is encapsulated when adding sponge calcium with sheet lead, then have leakage with bottom
The bell jar press-in lead liquid bottom in hole, allows sponge calcium slowly to be melted in lead liquid bottom, because calcium is very active metal, in high temperature
Lower easy firing loss, is encapsulated with sheet lead, to reduce the loss of sponge calcium before addition for this.When lead liquid no longer bubbling,
Start centrifugal blender and mix slowly mixing；(5) after half an hour, the electrolytic lead of surplus is added in market pot, lead to be electrolysed
Melt completely, continue to stir, ingot casting after one hour.Graphene described above is single-layer graphene, bilayer graphene, few layer stone
One or more in black alkene or graphene microchip.Graphene can be produced using physical method, can also use chemical method system
Take.
Embodiment 4, a kind of lead accumulator grid metal containing graphene, count by weight percentage, it is included
0.09% graphene, 1.1% tin, 0.025% aluminium, 0.07% sponge calcium and 98.715% lead.Its preparation method include with
Lower step：(1) 2/3 electrolytic lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to electrolytic lead；(2) so
After open centrifugal blender, the slowly continuous addition or interruption adds in batches in the case of moderate-speed mixer by the graphene of the amount
It is added in lead liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, centrifugal blender continues to stir
Mixing is more than half an hour；(4) centrifugal blender is closed, the sponge calcium encapsulated with sheet lead of the amount is added, sheet lead is encapsulated
The bell jar press-in lead liquid bottom of small opening is arranged at good sponge calcium bottom, is encapsulated when adding sponge calcium with sheet lead, then use bottom
There is the bell jar press-in lead liquid bottom of small opening, allow sponge calcium slowly to be melted in lead liquid bottom, because calcium is very active metal,
Easy firing is lost under high temperature, is encapsulated before addition with sheet lead for this, to reduce the loss of sponge calcium.When the no longer bubbling of lead liquid
When, start centrifugal blender and mix slowly mixing；(5) after half an hour, the electrolytic lead of surplus is added in market pot, it is to be electrolysed
Lead melts completely, continues to stir, ingot casting after one hour.Graphene described above is single-layer graphene, bilayer graphene, few layer
One or more in graphene or graphene microchip.Graphene can be produced using physical method, can also use chemical method
Produce.
Embodiment 5, a kind of lead accumulator grid metal containing graphene, count by weight percentage, it is included
0.12% graphene, 1.2% tin, 0.035% aluminium, 0.09% sponge calcium and 98.555% lead.Its preparation method include with
Lower step：(1) 2/3 electrolytic lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to electrolytic lead；(2) so
After open centrifugal blender, the slowly continuous addition or interruption adds in batches in the case of moderate-speed mixer by the graphene of the amount
It is added in lead liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, centrifugal blender continues to stir
Mixing is more than half an hour；(4) centrifugal blender is closed, the sponge calcium encapsulated with sheet lead of the amount is added, sheet lead is encapsulated
The bell jar press-in lead liquid bottom of small opening is arranged at good sponge calcium bottom, is encapsulated when adding sponge calcium with sheet lead, then use bottom
There is the bell jar press-in lead liquid bottom of small opening, allow sponge calcium slowly to be melted in lead liquid bottom, because calcium is very active metal,
Easy firing is lost under high temperature, is encapsulated before addition with sheet lead for this, to reduce the loss of sponge calcium.When the no longer bubbling of lead liquid
When, start centrifugal blender and mix slowly mixing；(5) after half an hour, the electrolytic lead of surplus is added in market pot, it is to be electrolysed
Lead melts completely, continues to stir, ingot casting after one hour.Graphene described above is single-layer graphene, bilayer graphene, few layer
One or more in graphene or graphene microchip.Graphene can be produced using physical method, can also use chemical method
Produce.
Embodiment 6, a kind of lead accumulator grid metal containing graphene, count by weight percentage, it is included
0.15% graphene, 1.5% tin, 0.04% aluminium, 0.1% sponge calcium and 98.21% lead.Its preparation method includes following
Step：(1) 2/3 electrolytic lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to electrolytic lead；(2) then
Centrifugal blender is opened, the graphene of the amount is slowly continuously added in the case of moderate-speed mixer or interruption is added in batches
It is added in lead liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, it is mixed that centrifugal blender continues stirring
Close more than half an hour；(4) centrifugal blender is closed, the sponge calcium encapsulated with sheet lead of the amount is added, sheet lead is encapsulated
Sponge calcium bottom have the bell jar press-in lead liquid bottom of small opening, encapsulated when adding sponge calcium with sheet lead, then have with bottom
The bell jar press-in lead liquid bottom of small opening, allows sponge calcium slowly to be melted in lead liquid bottom, because calcium is very active metal, in height
The lower easy firing loss of temperature, is encapsulated with sheet lead, to reduce the loss of sponge calcium before addition for this.When the no longer bubbling of lead liquid
When, start centrifugal blender and mix slowly mixing；(5) after half an hour, the electrolytic lead of surplus is added in market pot, it is to be electrolysed
Lead melts completely, continues to stir, ingot casting after one hour.Graphene described above is single-layer graphene, bilayer graphene, few layer
One or more in graphene or graphene microchip.Graphene can be produced using physical method, can also use chemical method
Produce.
Hardness, tensile strength and the resistivity of obtained graphene metal in embodiment 1~6 are detected respectively,
And draw data below：
It will be made after graphene metal makes 6-DZM-20 resultant battery, be tested, battery in embodiment 1~6
Initial capacity is 22.6Ah, by 150 times it is shallow fill deep discharge after, residual capacity be respectively 21.1Ah, 21.3Ah, 21.5Ah,
21.7Ah, 21.8Ah, 21.8Ah, barrier layer phenomenon is not found, is continued cycling through, it is remaining after 350 100% DOD are circulated
Capacity is respectively 20.2Ah, 20.1Ah, 20.4Ah, 20.5Ah, 20.6Ah, 20.5Ah.Dissection and analysis, it is found that grid is a small amount of
Corrosion and active material ruckbildung.But it is small on battery performance influence, absolutely prove that graphene can slow down grid corrosion situation,
And can thoroughly solve because of grid corrosion and caused by series of negative influence.
Can be seen that graphene addition is more, and grid hardness is higher by above experimental data, tensile strength is better,
Resistivity is lower, it is sufficient to which grid mechanical strength can be improved by illustrating the addition of graphene, reduce grid deflection, and enhancing grid is conductive
Property.We have concluded that as long as the hardness of grid reaches the requirement that 22N/mm2 applies cream with regard to that can meet in conventional production, by experiment I
Draw graphene content at 0.015%, grid passes through short-term timeliness, and its hardness can reach the requirement of conventional coated plate, and anti-
Tensile strength and resistivity also surmount in Standard.Graphene content is higher, and grid performance is better, but when graphene content is high
When 0.15%, alloy grid performance is far more than Standard, and also more without help big again, addition to battery performance
Graphene also simply waste, so the desired contents of graphene should be controlled in the range of 0.015~0.15%.
Claims (2)
- A kind of 1. lead accumulator grid metal containing graphene, it is characterised in that：Count by weight percentage, it is included 0.015 ~ 0.15% graphene, 1.0 ~ 1.5% tin, 0.02 ~ 0.04% aluminium, 0.05 ~ 0.1% calcium and 98.21 ~ 98.915% Lead；It is made up of following preparation method,(1) 2/3 lead of the amount is inserted in market pot, is heated to 680 °C and is completely melt to lead；(2) it is then turned on centrifuging Mixer, the graphene of the amount is slowly continuously added in the case of moderate-speed mixer or interruption is added to lead in batches In liquid；After (3) 20 minutes, the pure tin bar and fine aluminium bar of the amount are successively added, centrifugal blender continues to be stirred half an hour More than；(4) centrifugal blender is closed, adds the calcium encapsulated with sheet lead of the amount, the calcium that sheet lead has been encapsulated has with bottom The bell jar press-in lead liquid bottom of small opening, when lead liquid no longer bubbling, starts centrifugal blender and mixes slowly mixing；(5) half an hour Afterwards, centrifugal blender is closed, the lead of surplus is added in market pot, treats that lead melts completely, opens centrifugal blender, is continued slow Speed stirring, ingot casting after one hour.
- 2. the lead accumulator grid metal according to claim 1 containing graphene, it is characterised in that：Described stone Black alkene is the one or more in single-layer graphene, bilayer graphene, few layer graphene or graphene microchip.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510266049.6A CN104993154B (en) | 2015-05-23 | 2015-05-23 | A kind of lead accumulator grid metal containing graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510266049.6A CN104993154B (en) | 2015-05-23 | 2015-05-23 | A kind of lead accumulator grid metal containing graphene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104993154A CN104993154A (en) | 2015-10-21 |
| CN104993154B true CN104993154B (en) | 2018-02-16 |
Family
ID=54304932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510266049.6A Active CN104993154B (en) | 2015-05-23 | 2015-05-23 | A kind of lead accumulator grid metal containing graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104993154B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106312045B (en) * | 2016-08-21 | 2018-10-26 | 超威电源有限公司 | A kind of graphene-lead and neodymium isotopes master batch and preparation method thereof |
| CN111864174B (en) * | 2018-02-01 | 2022-05-24 | 超威电源集团有限公司 | Processing method of high-conductivity bus bar for lead-acid storage battery |
| 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 |
| CN110224141B (en) * | 2019-05-16 | 2022-01-04 | 旭派电源有限公司 | Preparation method of negative grid alloy of all-lead-carbon battery |
| 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 |
| 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 |
| CN112522536B (en) * | 2020-12-08 | 2021-10-15 | 英德奥克莱电源有限公司 | Lead-calcium alloy for positive grid and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096727A (en) * | 2006-06-30 | 2008-01-02 | 上海飞轮有色冶炼厂 | Production method of calcium lead alloy |
| CN103943865A (en) * | 2014-05-07 | 2014-07-23 | 厦门华天高科电池科技有限公司 | Graphene-lead alloy as well as preparation method and application thereof |
| CN103985879A (en) * | 2014-05-16 | 2014-08-13 | 浙江天能电池(江苏)有限公司 | Lead-calcium-tin-aluminum positive grid alloy and preparation method thereof |
| CN104232990A (en) * | 2014-08-08 | 2014-12-24 | 超威电源有限公司 | Grid alloy for single-walled carbon nano-tube storage battery and preparation method thereof |
-
2015
- 2015-05-23 CN CN201510266049.6A patent/CN104993154B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096727A (en) * | 2006-06-30 | 2008-01-02 | 上海飞轮有色冶炼厂 | Production method of calcium lead alloy |
| CN103943865A (en) * | 2014-05-07 | 2014-07-23 | 厦门华天高科电池科技有限公司 | Graphene-lead alloy as well as preparation method and application thereof |
| CN103985879A (en) * | 2014-05-16 | 2014-08-13 | 浙江天能电池(江苏)有限公司 | Lead-calcium-tin-aluminum positive grid alloy and preparation method thereof |
| CN104232990A (en) * | 2014-08-08 | 2014-12-24 | 超威电源有限公司 | Grid alloy for single-walled carbon nano-tube storage battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104993154A (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104993154B (en) | A kind of lead accumulator grid metal containing graphene and preparation method thereof | |
| CN103943865B (en) | A kind of Graphene metal, preparation method and its usage | |
| TWI628291B (en) | Lead-based alloy and related processes and products | |
| CN104835965B (en) | A kind of motorcycle lead carbon battery and preparation method thereof | |
| CN106898738A (en) | A kind of negative electrode of lithium ionic secondary battery and preparation method, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery | |
| CN105518913B (en) | Vulcanize lithium-iron-carbon complex | |
| CN103208615B (en) | Silicon-carbon composite material, and preparation method and application thereof | |
| CN106129375B (en) | A kind of method of compound lithium salts modified electrode material | |
| CN105406143A (en) | Method for preparing lead storage battery electrode plate from lead-bearing compound in waste lead storage battery as raw material | |
| CN106450336A (en) | Lithium ion battery negative electrode slurry and preparation method thereof | |
| CN107516740A (en) | A kind of carbon ink, graphene powder combined conductive agent and preparation method thereof, application | |
| CN105932224A (en) | Modified silicon-based negative electrode material, preparation method and application thereof | |
| Zhao et al. | Advanced structures in electrodeposited tin base anodes for lithium ion batteries | |
| CN105024083B (en) | A kind of preparation method of Lead-acid Storage Battery carbon anode plate grid | |
| CN101950806B (en) | Anode material capable of being used for lithium-iodine cell and preparation method thereof | |
| CN101593826A (en) | Lithium ion battery SnSb alloy/graphite nanosheet composite material negative pole and preparation method thereof | |
| CN104112852A (en) | A preparing method of a lithium ion battery cathode material | |
| CN100347900C (en) | Solid-state battery for electric vehicle | |
| CN105140474A (en) | Anode lead paste for power lead-acid storage battery and preparation method of anode lead paste | |
| CN104332626B (en) | Preparation method of negative electrode material Mn2CoO4/poly(3,4-ethylenedioxythiophene) | |
| CN105244563A (en) | Preparation method of lead storage battery negative plate by using lead-containing compound in waste lead storage battery as raw material | |
| CN103762388B (en) | A kind of internal formation process of electric motor car valve-regulated lead-acid battery | |
| CN105226343A (en) | With the lead-containing compounds in waste lead accumulator for the method for positive plate of lead storage battery prepared by raw material | |
| CN102157269A (en) | Method for preparing manganese dioxide serving as cathode material of super capacitor and secondary battery | |
| CN105047939B (en) | A kind of lead-acid battery is with modified short fine preparation method and includes the short fine negative plate of the modification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200330 Address after: Room 8017, 2599 Xiangyang North Street, Baoding City, Hebei Province Patentee after: BAODING ZHONGCHUANG YANYUAN SEMICONDUCTOR TECHNOLOGY Co.,Ltd. Address before: 071051 No. 2599 Xiangyang North Street, Hebei, Baoding Patentee before: BAODING GOLDEN SUNLIGHT POWER EQUIPMENT TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200527 Address after: Room 8017, 2599 Xiangyang North Street, Baoding City, Hebei Province Patentee after: BAODING ZHONGCHUANG YANYUAN SEMICONDUCTOR TECHNOLOGY Co.,Ltd. Address before: 071051 No. 2599 Xiangyang North Street, Hebei, Baoding Patentee before: BAODING GOLDEN SUNLIGHT POWER EQUIPMENT TECHNOLOGY Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A lead alloy containing graphene for lead-acid battery grid and its preparation method Granted publication date: 20180216 Pledgee: Bank of China Limited Baoding Branch Pledgor: BAODING ZHONGCHUANG YANYUAN SEMICONDUCTOR TECHNOLOGY Co.,Ltd. Registration number: Y2024980001413 |