CN107287470A - A kind of lead accumulator grid alloy comprising nanometer tungsten carbide material and preparation method - Google Patents
A kind of lead accumulator grid alloy comprising nanometer tungsten carbide material and preparation method Download PDFInfo
- Publication number
- CN107287470A CN107287470A CN201710380920.4A CN201710380920A CN107287470A CN 107287470 A CN107287470 A CN 107287470A CN 201710380920 A CN201710380920 A CN 201710380920A CN 107287470 A CN107287470 A CN 107287470A
- Authority
- CN
- China
- Prior art keywords
- lead
- alloy
- tungsten carbide
- nanometer tungsten
- preparation
- 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.)
- Granted
Links
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000001999 grid alloy Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 50
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000011858 nanopowder Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000003818 cinder Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 22
- 239000002184 metal Substances 0.000 abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052791 calcium Inorganic materials 0.000 abstract description 9
- 239000011575 calcium Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000002308 calcification Effects 0.000 abstract description 3
- 238000007499 fusion processing Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 5
- 229910018725 Sn—Al Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
-
- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a kind of lead accumulator grid alloy comprising nanometer tungsten carbide material and preparation method, belong to lead accumulator preparing technical field.The grid alloy, by weight percentage, consisting of:Tin 0.1~0.8%, nanometer tungsten carbide 0.05~0.5%, lead are surplus.The present invention substitutes used calcium metal, substantially reduces the grid alloy intercrystalline corrosion as caused by calcification lead by adding nanometer tungsten carbide material;Improve combination and the institutional framework of metal crystal grain boundary, significantly improve hardness, creep-resistant property, decay resistance of metal etc..The present invention prepares the foundry alloy containing tungsten carbide composite by cold melt process, recycles foundry alloy to prepare tungsten carbide composite alloy, it is ensured that nanometer tungsten carbide material is dispersed in metal, to improve metal performance.Other whole preparation process temperature control significantly saves the lead skim produced in the energy, and fusion process less below 500 DEG C.
Description
Technical field
The present invention relates to lead accumulator preparing technical field, and in particular to a kind of lead electric power storage for including nanometer tungsten carbide material
Pond grid alloy and preparation method.
Background technology
Metal is battery plate grid material, and its decay resistance directly affects the cycle life of battery.At present, mainly
Using Pb-Ca-Sn-Al alloy as grid material, the hardness of the material is higher, it is ensured that industrialized production.Due to element calcium master
To be present in the form of calcification lead between crystal boundary, therefore its decay resistance is poor.It is early that Pb-Ca-Sn-Al alloy easily causes battery
Phase capacitance loss, so, from new added material, while ensureing alloy rigidity, its decay resistance is improved, is lead electric power storage
The emphasis of pond research.
Deepened continuously because the corrosion of metal is main since crystal boundary, ultimately result in intercrystalline combination and come off, so,
The decay resistance for improving material in crystal boundary performance or raising crystal boundary is to improve the key of metal decay resistance.
Such as A of patent document CN 105322179 disclose a kind of green alloy of the anticorrosive positive grid of lead-acid accumulator, including
Following components in percentage by weight:Tin 0.8~1.5%, calcium 0.08~0.15%, aluminium 0.01~0.04%, cerium 0.02~
0.2%th, lanthanum 0.02~0.2%, neodymium 0.02~0.2%, silver 0.001~0.05%, remaining is lead.By scientific and reasonable examination
Test, by adding Ce, La, Nd, Ag of formula ratio, retain the operability and high hydrogen-evolution overpotential in original alloy, original Pb-
Ca-Sn-Al is brilliant to have essential change as structure, finds its decay resistance than original Pb-Ca-Sn- by corrosion-resistant experiment
Al alloys lift 3-4 times, and the green alloy of the anticorrosive positive grid of the invention lead-acid accumulator reaches positive grid during 800 100%DOD
Do not corrode.
As the A of patent document CN 106058267 disclose a kind of preparation side of lead-acid battery graphene lead and neodymium isotopes
Method, is decomposed to form carbon source from metal carbides or solid carbon-contg organic compound and enters under the high temperature conditions under the high temperature conditions
Enter in lead solution, and lead forms the combination of atomic level, and the graphene formed after being cooled can be uniformly dispersed in metal
In;The reaction carried out in atmospheric conditions also largely saves cost;The graphene grid alloy prepared using the method
The mechanical performance of grid alloy is improved, strengthens its creep resisting ability.
Wherein metal carbides are tungsten carbide, and tungsten carbide is a kind of compound being made up of tungsten and carbon, are that production hard is closed
The primary raw material of gold, is black hexagonal, there is metallic luster, hardness is close with diamond, is electricity, the good conductor of heat.Carbon
The chemical property for changing tungsten is stable, and more than 500 DEG C start active oxidation in air, and oxidation resistance is weak.
In addition, traditional Pb-Ca-Sn-Al alloy is because addition calcium metal more than 650 DEG C, it is necessary to carry out melting, in melting
During easily produce lead skim, be unfavorable for energy-conservation.
The content of the invention
It is an object of the invention to provide a kind of lead accumulator grid alloy comprising nanometer tungsten carbide material, using nanometer
Calcium metal in the traditional metal of tungsten carbide substitution, to reduce alloy grain size, significantly improves lead accumulator grid creep resistant
Performance in terms of property, corrosion resistance.
To achieve the above object, the present invention is adopted the following technical scheme that:
A kind of lead accumulator grid alloy comprising nanometer tungsten carbide material, by weight percentage, consisting of:Tin
0.1~0.8%, nanometer tungsten carbide 0.05~0.5%, lead are surplus.
In the present invention, the addition of nanometer tungsten carbide can not only significantly improve the hardness of metal, can also significantly improve
Crystal grain, the grain boundary features of alloy, crystallite dimension are substantially reduced, grain boundary area increase, under same current density, can substantially reduce corruption
Erosion amount, so as to extend the cycle life of battery.
The effect that the present invention adds tin in lead accumulator grid formula is the mobility and ductility for improving alloy.
Preferably, by weight percentage, the composition of alloy is:Tin 0.2~0.5%, nanometer tungsten carbide 0.2~
0.5%th, lead is surplus.
When preparing grid alloy, it is desirable to the nano powder of tungsten carbide of addition, particle diameter be 10~100nm, its purity >=
99.9%, carbon content >=5.0%, single metals content impurity≤0.01%.
Because the particle diameter of nano powder of tungsten carbide is nanoscale, make its dispersed by being stirred in lead liquid.
Present invention also offers a kind of side for preparing the described lead accumulator grid alloy comprising nanometer tungsten carbide material
Method, including:
(1) foundry alloy is prepared
A) metallic tin is added in the lead liquid of fusing, heating is melted and stirred, and obtains aluminium alloy;
B) the sheet lead bag for being enclosed with nano powder of tungsten carbide is pressed into aluminium alloy, stirring makes by temperature control to 350~400 DEG C
Nano powder of tungsten carbide is dispersed in aluminium alloy, is cast into master alloy ingot;
(2) grid alloy is prepared
I) lead pig for accounting for lead gross mass 70~80% is added in intermediate frequency furnace, heating fusing;
II) control temperature is in 380~450 DEG C of master alloy ingots that into melt prepared by addition step (1), and stirring makes foundry alloy
It is completely melt and is well mixed;
III) add remaining lead pig, fusing, stirring, cast alloys ingot after scarfing cinder.
The present invention prepares the foundry alloy containing tungsten carbide composite by cold melt process, recycles foundry alloy to prepare carbon
Change tungsten composite alloy, it is ensured that nanometer tungsten carbide material is dispersed in metal, to improve metal performance.It is whole in addition
Preparation process temperature control significantly saves the lead skim produced in the energy, and fusion process less below 500 DEG C.
Preferably, in step a), lead pig being added in intermediate frequency furnace be heated to 480~520 DEG C first, it is fully melted
Change, then add metallic tin, stir 5~60min, be completely melt metallic tin.
Preferably, in step b), 1~3h is stirred after press-in sheet lead bag.
Preferably, step I) in, being heated to 320~350 DEG C melts lead pig.
Preferably, step II) in, add and 5~60min is stirred after master alloy ingot.
In above-mentioned whipping process, the speed of stirring can have an impact for the slag yield of alloy, and stir speed (S.S.) is unsuitable too fast.If
Metal Theil indices are not enough in foundry alloy, can be in step II) when add the desired amount of metallic tin.
The beneficial effect that the present invention possesses:
(1) by adding nanometer tungsten carbide material, used calcium metal is substituted, the grid as caused by calcification lead is substantially reduced
Alloy intercrystalline corrosion;Crystal grain, the grain boundary features of alloy can be significantly improved, crystallite dimension is substantially reduced, grain boundary area increase;Change
The combination of kind metal crystal grain boundary and institutional framework, make hardness, creep-resistant property, decay resistance of metal etc. significantly carry
It is high.
(2) present invention uses low smelting heat technique, significantly saves lead skim in the energy, and fusion process less.
Embodiment
With reference to embodiment, the invention will be further described.But following embodiments are only being preferable to carry out for the present invention
Example, and it is not all.Based on the embodiment in embodiment, those skilled in the art are not on the premise of creative work is made
Obtained other embodiments, belong to protection scope of the present invention.
Embodiment 1
1st, foundry alloy is prepared
Foundry alloy formula is as follows:Tin:5.0%th, nanometer tungsten carbide 3.0%, lead are surplus, and aforementioned proportion is weight percent
Than.
(1) according to said ratio, metallic tin, nanometer tungsten carbide, lead are weighed;
(2) 2/3 amount of raw material lead is added in mid-frequency melting furnace and is heated to 500 DEG C, lead button is fully melted;
(3) metallic tin is added to melt, stirring at low speed (magnetic force or mechanical agitation) 30min makes metallic tin be completely melt simultaneously
It is well mixed;
(4) 380 DEG C are cooled to, the nano powder of tungsten carbide of quality, is pressed into lead liquid needed for wrapping up proportioning with sheet lead,
Moderate-speed mixer 3h, makes tungsten-carbide powder be dispersed in lead liquid;
(5) foundry alloy composition is measured, cast alloys ingot after setting proportioning is reached.
In above-mentioned preparation method, the nano powder of tungsten carbide particle diameter of addition is 10~100nm, its purity >=99.9%, carbon
Content >=5.0%, single metals content impurity≤0.01%.
2nd, the preparation of lead accumulator grid alloy
By weight percentage, constitute and be:Tin 0.5%, nanometer tungsten carbide 0.3%, lead are surplus.
Comprise the following steps:
(1) according to said ratio, each raw material are weighed;
(2) lead button for accounting for leady raw materialses gross mass 70~80% is added in intermediate frequency furnace and is heated to 350 DEG C, lead button is fully melted
Change;
(3) continue to be heated to 380 DEG C of foundry alloys for adding the required quality of proportioning to melt, stir 30min, make foundry alloy complete
Running down is simultaneously well mixed;
(4) remaining lead button is added, melt is stirred;
(5) slag-cleaning agent is spread to bath surface, stirs 20min, then remove scum silica frost;
(6) alloying component is measured, cast alloys ingot after setting proportioning is reached.
3rd, lead accumulator grid performance detection
A, timeliness hardness
After 5 days timeliness of alloy, using 0.098N (0.01kg) experiment power, more than retention time 30s detects Vickers hardness
Value.
B, analysis oxygen current density
Using alloy as positive pole, platinum electrode is negative pole, three-electrode system lower linear electric potential scanning is carried out, when electrode potential is
1.50V(vs.Hg/Hg2SO4) when, detect the analysis oxygen current density of alloy.
C, corrosion resistance
Under the conditions of 50 DEG C, using length and width, thickness as 10 × 1 × 0.2cm alloy for positive pole, stereotype is negative pole, constant current
For 0.8A, weight pulling force is 550g, the time that alloy sample corrosion disconnects.
As a result as shown in table 1, alloy made from the present embodiment is obtained in terms of timeliness hardness, creep-resistant property, corrosion resistance
To significantly improving.
Table 1
The alloy formula of above-mentioned control 1 uses plato grid alloy formulation to be conventional:Calcium 0.08%, tin 1.0%, aluminium 0.05%,
Lead is surplus.
Control 2 alloy formula be:Tin 0.5%, lead are surplus.
Embodiment 2
By weight percentage, constitute and be:Tin 0.5%, nanometer tungsten carbide 0.5%, lead are surplus.
Preparation method and method of testing be the same as Example 1, as a result as shown in table 2.
Table 2
The alloy formula of above-mentioned control 1 uses plato grid alloy formulation to be conventional:Calcium 0.08%, tin 1.0%, aluminium 0.05%,
Lead is surplus.
Embodiment 3
By weight percentage, constitute and be:Tin 0.5%, nanometer tungsten carbide 0.1%, lead are surplus.
Preparation method and method of testing be the same as Example 1, as a result as shown in table 3.
Table 3
The alloy formula of above-mentioned control 1 uses plato grid alloy formulation to be conventional:Calcium 0.08%, tin 1.0%, aluminium 0.05%,
Lead is surplus.
Claims (8)
1. a kind of lead accumulator grid alloy comprising nanometer tungsten carbide material, it is characterised in that by weight percentage, its group
Turn into:Tin 0.1~0.8%, nanometer tungsten carbide 0.05~0.5%, lead are surplus.
2. the lead accumulator grid alloy as claimed in claim 1 for including nanometer tungsten carbide material, it is characterised in that with weight
Percentages, constitute and are:Tin 0.2~0.5%, nanometer tungsten carbide 0.2~0.5%, lead are surplus.
3. the lead accumulator grid alloy as claimed in claim 1 or 2 for including nanometer tungsten carbide material, it is characterised in that institute
The particle diameter for stating nanometer tungsten carbide is 10~100nm, wherein carbon mass percentage content >=5.0%.
4. the preparation method of the lead accumulator grid alloy of nanometer tungsten carbide material is included as claimed in claim 1, including:
(1) foundry alloy is prepared
A) metallic tin is added in the lead liquid of fusing, heating is melted and stirred, and obtains aluminium alloy;
B) the sheet lead bag for being enclosed with nano powder of tungsten carbide is pressed into aluminium alloy, stirring makes nanometer by temperature control to 350~400 DEG C
Tungsten-carbide powder is dispersed in aluminium alloy, is cast into master alloy ingot;
(2) grid alloy is prepared
I) lead pig for accounting for lead gross mass 70~80% is added in intermediate frequency furnace, heating fusing;
II) control temperature is in 380~450 DEG C of master alloy ingots that into melt prepared by addition step (1), and stirring makes foundry alloy complete
Melt and be well mixed;
III) add remaining lead pig, fusing, stirring, cast alloys ingot after scarfing cinder.
5. preparation method as claimed in claim 4, it is characterised in that in step a), lead pig is added in intermediate frequency furnace add first
Heat makes it fully melt to 480~520 DEG C, then adds metallic tin, stirs 5~60min, is completely melt metallic tin.
6. stir 1~3h after preparation method as claimed in claim 4, it is characterised in that in step b), press-in sheet lead bag.
7. preparation method as claimed in claim 4, it is characterised in that step I) in, being heated to 320~350 DEG C melts lead pig
Change.
8. preparation method as claimed in claim 4, it is characterised in that step II) in, add stirring 5 after master alloy ingot~
60min。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710380920.4A CN107287470B (en) | 2017-05-25 | 2017-05-25 | A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710380920.4A CN107287470B (en) | 2017-05-25 | 2017-05-25 | A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107287470A true CN107287470A (en) | 2017-10-24 |
CN107287470B CN107287470B (en) | 2019-02-15 |
Family
ID=60095300
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710380920.4A Active CN107287470B (en) | 2017-05-25 | 2017-05-25 | A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107287470B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111647769A (en) * | 2020-06-18 | 2020-09-11 | 超威电源集团有限公司 | Storage battery grid alloy and preparation method thereof |
CN114134538A (en) * | 2021-12-08 | 2022-03-04 | 昆明理工恒达科技股份有限公司 | A zinc electrodeposition system suitable for high current density |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4839332B1 (en) * | 1968-10-31 | 1973-11-22 | ||
US3879217A (en) * | 1973-03-15 | 1975-04-22 | Electric Power Storage Ltd | Electric storage battery grids |
EP1093674A1 (en) * | 1998-06-17 | 2001-04-25 | C & D Technologies, Inc. | Catalyst equipped vapor-communicating multi-cell valve regulated lead-acid battery |
CN104073683A (en) * | 2014-06-27 | 2014-10-01 | 天能集团江苏科技有限公司 | Low-temperature deep-cycle positive grid alloy and preparation method thereof |
CN104073682A (en) * | 2014-06-27 | 2014-10-01 | 浙江天能电池(江苏)有限公司 | Long-service-life deep-cycle positive grid alloy and preparation method thereof |
CN105648268A (en) * | 2016-04-12 | 2016-06-08 | 李程 | Radiation-shielding high-voltage grid power distribution cabinet |
CN105671362A (en) * | 2016-03-22 | 2016-06-15 | 安徽华铂再生资源科技有限公司 | Lanthanum mother alloy for positive electrode grid of lead-acid storage battery and preparation process |
-
2017
- 2017-05-25 CN CN201710380920.4A patent/CN107287470B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4839332B1 (en) * | 1968-10-31 | 1973-11-22 | ||
US3879217A (en) * | 1973-03-15 | 1975-04-22 | Electric Power Storage Ltd | Electric storage battery grids |
EP1093674A1 (en) * | 1998-06-17 | 2001-04-25 | C & D Technologies, Inc. | Catalyst equipped vapor-communicating multi-cell valve regulated lead-acid battery |
CN104073683A (en) * | 2014-06-27 | 2014-10-01 | 天能集团江苏科技有限公司 | Low-temperature deep-cycle positive grid alloy and preparation method thereof |
CN104073682A (en) * | 2014-06-27 | 2014-10-01 | 浙江天能电池(江苏)有限公司 | Long-service-life deep-cycle positive grid alloy and preparation method thereof |
CN105671362A (en) * | 2016-03-22 | 2016-06-15 | 安徽华铂再生资源科技有限公司 | Lanthanum mother alloy for positive electrode grid of lead-acid storage battery and preparation process |
CN105648268A (en) * | 2016-04-12 | 2016-06-08 | 李程 | Radiation-shielding high-voltage grid power distribution cabinet |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111647769A (en) * | 2020-06-18 | 2020-09-11 | 超威电源集团有限公司 | Storage battery grid alloy and preparation method thereof |
CN111647769B (en) * | 2020-06-18 | 2021-03-30 | 超威电源集团有限公司 | A kind of battery grid alloy and preparation method thereof |
CN114134538A (en) * | 2021-12-08 | 2022-03-04 | 昆明理工恒达科技股份有限公司 | A zinc electrodeposition system suitable for high current density |
CN114134538B (en) * | 2021-12-08 | 2024-03-26 | 昆明理工恒达科技股份有限公司 | Zinc electrowinning system suitable for high current density |
Also Published As
Publication number | Publication date |
---|---|
CN107287470B (en) | 2019-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101886197B (en) | Aluminum-lithium-samarium alloy and fused salt electrolysis preparation method thereof | |
CN108467968A (en) | A kind of preparation method of lead accumulator grid alloy | |
CN109321766B (en) | A kind of aluminum-air battery anode material and preparation method thereof | |
CN106893897A (en) | A kind of heat-resistant rare earth aluminium alloy conductor and its manufacture method | |
CN105925846B (en) | A kind of Zr Sn Nb Hf alloy bar materials and preparation method thereof | |
CN103146943A (en) | Red impure copper refining agent and preparation method thereof | |
CN110714156A (en) | A kind of light-weight high-strength corrosion-resistant high-entropy alloy and preparation method thereof | |
CN109694964A (en) | A kind of preparation method of aluminium-air cell anode material | |
CN109913910B (en) | A kind of method for preparing titanium-iron alloy by ilmenite carbothermal-electrolysis | |
CN111074089A (en) | Wear-resistant corrosion-resistant multi-element manganese aluminum bronze brazing alloy and preparation method thereof | |
CN106868350B (en) | Strong heat-resistant aluminum alloy wire and its manufacture method in one kind | |
CN107287470B (en) | A kind of lead storage battery grid alloy and preparation method comprising nanometer tungsten carbide material | |
CN105977496B (en) | Include slicker solder-rare earth-graphene lead storage battery grid alloy preparation method | |
CN115821125A (en) | High-conductivity hard aluminum alloy wire and manufacturing method thereof | |
CN107164657B (en) | A kind of preparation method of graphene/La-Fe-B systems low temperature hydrogen storage composite material | |
WO2013185539A1 (en) | Inert alloy anode used for aluminum electrolysis and preparation method therefor | |
CN103397217B (en) | A nanoporous Pd material with electro-oxidation catalytic performance and preparation method thereof | |
CN111471888A (en) | Nano intermetallic compound dispersion strengthening high-conductivity wear-resistant copper alloy and manufacturing method and application thereof | |
CN110042278A (en) | A kind of aluminium-air cell anode material and preparation method thereof | |
CN108808010A (en) | A kind of Moped Scooter positive electrode grid of lead storage battery alloy and preparation method thereof | |
CN109338375A (en) | A kind of high-performance Al-Zn-In series sacrificial anode material and preparation method thereof | |
CN106887266B (en) | A kind of manufacturing method of high strength heat resistant alloy conducting wire | |
CN109762959B (en) | A kind of smelting method of special steel and special steel | |
CN105908001A (en) | A kind of Si-containing nanoporous Pd material and preparation method thereof | |
CN103484895B (en) | A kind of electrolgtic aluminium inert alloy anode and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CP01 | Change in the name or title of a patent holder | ||
CP01 | Change in the name or title of a patent holder |
Address after: 313100 Coal Mountain Industrial Park, Changxing County, Huzhou City, Zhejiang Province Patentee after: Tianneng Battery Group Co., Ltd. Address before: 313100 Coal Mountain Industrial Park, Changxing County, Huzhou City, Zhejiang Province Patentee before: Tianneng Battery Group Co., Ltd. |