CN113782747B - High-calcium alloy for lead-acid storage battery grid and preparation method thereof - Google Patents
High-calcium alloy for lead-acid storage battery grid and preparation method thereof Download PDFInfo
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- CN113782747B CN113782747B CN202111063642.2A CN202111063642A CN113782747B CN 113782747 B CN113782747 B CN 113782747B CN 202111063642 A CN202111063642 A CN 202111063642A CN 113782747 B CN113782747 B CN 113782747B
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- 239000002253 acid Substances 0.000 title claims abstract description 56
- 229910000882 Ca alloy Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 15
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims abstract description 28
- UFTQLBVSSQWOKD-UHFFFAOYSA-N tellanylidenecalcium Chemical compound [Te]=[Ca] UFTQLBVSSQWOKD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000011505 plaster Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000002142 lead-calcium alloy Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001999 grid alloy Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010998 test method Methods 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
Abstract
The invention provides a lead-acid storage battery grid high-calcium alloy and a preparation method thereof, wherein the lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.12 to 0.18 percent of Ca, 1.1 to 1.7 percent of Sn, 0.07 to 0.13 percent of calcium telluride, 0.8 to 1.4 percent of cuprous sulfide and the balance of Pb. The high content of calcium and intermetallic compound calcium telluride in the high-calcium alloy can improve the corrosion resistance of the grid; the addition of the calcium telluride can further improve the corrosion resistance of the grid, improve the hardness and strength of the grid, prevent lead plaster from falling off due to grid creep, and prolong the service life of the lead-acid storage battery. The addition of cuprous sulfide can prevent the reduction of the charge acceptance of the battery and cause rapid capacity decay. The calcium telluride and the cuprous sulfide can improve the potential of grid hydrogen evolution, inhibit the water loss in the electrode liquid and prolong the service life.
Description
Technical Field
The invention relates to the field of lead-acid storage batteries, in particular to a high-calcium alloy for a grid of a lead-acid storage battery and a preparation method thereof.
Background
The grid is an important component in a lead-acid storage battery, and although the grid has no direct capacity improvement effect, the grid plays a role in skeleton supporting as an active substance and conducting and uniformly distributing current in the charge and discharge processes of the battery, and the performances directly limit the capacity and the cycle life of the battery, and whether the performances are superior or not depends on the alloy used by the grid.
The lead-acid storage battery used in the current market adopts positive grid lead alloy which can be divided into lead-antimony alloy and lead-calcium alloy. The lead-calcium alloy has excellent maintenance-free performance, high oxygen evolution overpotential and less water loss, but the lead-acid storage battery is easy to generate early capacity attenuation and poor deep discharge cycle performance and has poor grid deformation resistance due to the poor conductivity of a corrosion film formed by calcium and the like. In the current practical application, the lead-acid storage battery has higher requirements on maintenance-free performance, environmental protection performance and deep cycle life, the existing battery can not meet the requirements, and particularly the positive grid alloy of the battery is urgently needed to be improved.
Disclosure of Invention
Based on the technical problems, the invention provides a lead-acid storage battery grid high-calcium alloy and a preparation method thereof.
The invention adopts the following technical scheme: a lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.12 to 0.18 percent of Ca, 1.1 to 1.7 percent of Sn, 0.07 to 0.13 percent of calcium telluride, 0.8 to 1.4 percent of cuprous sulfide and the balance of Pb.
Specifically, the high-calcium alloy for the grid of the lead-acid storage battery comprises the following components in percentage by weight: 0.14 to 0.16 percent of Ca, 1.3 to 1.5 percent of Sn, 0.09 to 1.11 percent of calcium telluride, 1.0 to 1.2 percent of cuprous sulfide and the balance of Pb.
The invention also provides a preparation method of the lead-acid storage battery grid high-calcium alloy, which comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 450-470 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 700-800 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 850-950 ℃, ca is added, after the Pb is completely melted, the temperature is raised to 1150-1250 ℃, cuprous sulfide is added, after the Pb is completely melted, stirring is carried out uniformly for 10min, and then the Pb is cooled to 300-400 ℃, and the Pb is discharged from the furnace to obtain the lead-acid storage battery grid high-calcium alloy.
Specifically, pb is melted in a melting furnace under the protection of argon at 460-465 ℃, sn is added after Pb is melted, after the Pb is completely melted, calcium telluride is added after the Pb is heated to 740-770 ℃, ca is added after the Pb is completely melted, the Ca is added after the Pb is heated to 880-920 ℃, after the Pb is completely melted, the cuprous sulfide is added after the Pb is heated to 1180-1220 ℃, the Pb is uniformly stirred after the Pb is completely melted, the Pb is kept for 10min, and then the Pb is cooled to 330-370 ℃, and the Pb is discharged from the furnace to obtain the high-calcium alloy of the grid of the lead-acid storage battery.
The beneficial effects are that:
the high-calcium alloy of the lead-acid storage battery grid provided by the invention has higher calcium content, and can improve the corrosion resistance of the lead-acid storage battery grid in the use process; the addition of the intermetallic compound calcium telluride can further improve the corrosion resistance of the grid, improve the hardness and strength of the grid, prevent lead plaster from falling off caused by creep of the grid and prolong the service life of the lead-acid storage battery. The addition of cuprous sulfide can inhibit the formation of PbSO 4、CaSO4 and other substances at the interface of the grid and the active substance, prevent the reduction of the charge acceptance of the battery and cause the rapid decay of the capacity. The calcium telluride and the cuprous sulfide can improve the potential of grid hydrogen evolution, inhibit the water loss in the electrode liquid and prolong the service life.
Detailed Description
Example 1:
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.12% of Ca, 1.1% of Sn, 0.07% of calcium telluride, 0.8% of cuprous sulfide and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 450 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 700 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 850 ℃, ca is added, after the Pb is completely melted, the temperature is raised to 1150 ℃, cuprous sulfide is added, after the Pb is completely melted, the Pb is uniformly stirred for 10min, and then the Pb is cooled to 300 ℃, and the Pb-acid storage battery grid high-calcium alloy is obtained after discharging.
Example 2:
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.14% of Ca, 1.3% of Sn, 0.09% of calcium telluride, 1.0% of cuprous sulfide and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 460 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 740 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 880 ℃, ca is added, after the Pb is completely melted, the temperature is raised to 1180 ℃, cuprous sulfide is added, after the Pb is completely melted, the Pb is uniformly stirred for 10min, and then the Pb is cooled to 330 ℃, and the Pb-acid storage battery grid high-calcium alloy is obtained after discharging.
Example 3:
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.16% of Ca, 1.5% of Sn, 0.11% of calcium telluride, 1.2% of cuprous sulfide and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 465 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 770 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 920 ℃, ca is added, after the Pb is completely melted, the temperature is raised to 1220 ℃, cuprous sulfide is added, after the Pb is completely melted, the stirring is uniform for 10min, and then the temperature is lowered to 370 ℃, and the lead-acid storage battery grid high-calcium alloy is obtained after discharging.
Example 4
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.18% of Ca, 1.7% of Sn, 0.13% of calcium telluride, 1.4% of cuprous sulfide and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 470 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 800 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 950 ℃, ca is added, after the Pb is completely melted, the temperature is raised to 1250 ℃, cuprous sulfide is added, after the Pb is completely melted, the Pb is uniformly stirred for 10min, and then the Pb is cooled to 400 ℃, and the Pb-acid storage battery grid high-calcium alloy is obtained after discharging.
Comparative example 1
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.18% of Ca, 1.7% of Sn, 1.4% of cuprous sulfide and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 470 ℃, sn is added after Pb is melted, ca is added after the Pb is completely melted, the temperature is raised to 950 ℃, the Ca is added after the Pb is completely melted, the temperature is raised to 1250 ℃, cuprous sulfide is added, the stirring is carried out after the Pb is completely melted, the stirring is carried out for 10min, and then the Pb is cooled to 400 ℃, and the Pb is discharged to obtain the lead-acid storage battery grid high-calcium alloy.
Comparative example 2
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.18% of Ca, 1.7% of Sn, 0.13% of calcium telluride and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
under the protection of argon, pb is melted in a melting furnace at 470 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 800 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 950 ℃, ca is added, after the Pb is completely melted, the Ca is uniformly stirred, the temperature is kept for 10min, and then the Pb is cooled to 400 ℃, and the Pb is discharged from the furnace to obtain the high-calcium alloy of the grid of the lead-acid storage battery.
Comparative example 3
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.18% of Ca, 1.7% of Sn and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 470 ℃, sn is added after Pb is melted, after the Pb is completely melted, ca is added after the Pb is completely melted, the temperature is raised to 950 ℃, the Ca is stirred uniformly after the Pb is completely melted, the stirring is kept for 10min, and then the Pb is cooled to 400 ℃, and the Pb is discharged from the melting furnace to obtain the high-calcium alloy of the grid of the lead-acid storage battery.
Comparative example 4
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.18% of Ca, 1.7% of Sn, 0.13% of tellurium dioxide, 1.4% of cuprous sulfide and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 470 ℃, sn is added after Pb is melted, tellurium dioxide is added after the Pb is completely melted, ca is added after the Pb is completely melted, the temperature is raised to 950 ℃, the temperature is raised to 1250 ℃ after the Pb is completely melted, cuprous sulfide is added, the Pb is uniformly stirred after the Pb is completely melted, the Pb is kept for 10min, and then the Pb is cooled to 400 ℃, and the Pb is discharged to obtain the high-calcium alloy of the lead-acid storage battery grid.
Comparative example 5
A lead-acid storage battery grid high-calcium alloy comprises the following components in percentage by weight: 0.18% of Ca, 1.7% of Sn, 0.13% of Te, 1.4% of cuprous sulfide and the balance of Pb.
A preparation method of a lead-acid storage battery grid high-calcium alloy comprises the following steps:
Under the protection of argon, pb is melted in a melting furnace at 470 ℃, sn is added after Pb is melted, te is added after the Pb is completely melted, ca is added after the Pb is completely melted, the temperature is raised to 950 ℃, the Ca is added after the Pb is completely melted, the temperature is raised to 1250 ℃, cuprous sulfide is added, the Pb is uniformly stirred after the Pb is completely melted, the Pb is kept for 10min, and then the Pb is cooled to 400 ℃, and the Pb is discharged from the furnace to obtain the high-calcium alloy of the grid of the lead-acid storage battery.
The high-calcium alloy is made into a lead-acid storage battery grid and then a lead-acid storage battery, and the following performance test experiments are carried out:
1. Cycle life test
The cycle life test method comprises the following steps: in the 25 ℃ environment, the battery is charged for 16 hours at a constant voltage of 14.1V and a current limiting of 75A, and then discharged to a termination voltage of 11.0V at a constant current of 50A, and when the discharge capacity of the whole battery is lower than 80% of the rated capacity, the service life is terminated.
2. Capacity testing
Testing was performed using standard GB/T22199-2008.
TABLE 1 test results for samples of various embodiments
| Description of the embodiments | Number of cycles | Rate of capacity fade |
| Example 1 | 219 | 93.9％ |
| Example 2 | 222 | 94.4％ |
| Example 3 | 224 | 94.6％ |
| Example 4 | 220 | 93.8％ |
| Comparative example 1 | 196 | 92.0％ |
| Comparative example 2 | 211 | 84.3％ |
| Comparative example 3 | 171 | 79.8％ |
| Comparative example 4 | 205 | 91.8％ |
| Comparative example 5 | 198 | 92.1％ |
Note that: the capacity fade rate in the table is the fade value after 50 cycles.
As can be seen from Table 1, the lead-acid storage battery prepared by the high-calcium grid prepared by the method has higher cycle life and obviously reduced capacity fade rate. The reason for this is that calcium telluride improves the corrosion resistance and creep resistance of the grid, and cuprous sulfide inhibits the formation of substances such as PbSO 4、CaSO4 at the grid/active substance interface.
Claims (4)
1. The high-calcium alloy for the lead-acid storage battery grid is characterized by comprising the following components in percentage by weight: 0.12 to 0.18 percent of Ca, 1.1 to 1.7 percent of Sn, 0.07 to 0.13 percent of calcium telluride, 0.8 to 1.4 percent of cuprous sulfide and the balance of Pb.
2. The high-calcium alloy for lead-acid storage battery grids of claim 1, which is characterized by comprising the following components in percentage by weight: 0.14 to 0.16 percent of Ca, 1.3 to 1.5 percent of Sn, 0.09 to 0.11 percent of calcium telluride, 1.0 to 1.2 percent of cuprous sulfide and the balance of Pb.
3. The method for preparing the high-calcium alloy for the grid of the lead-acid storage battery according to claim 1 or 2, which is characterized by comprising the following steps: under the protection of argon, pb is melted in a melting furnace at 450-470 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 700-800 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 850-950 ℃, ca is added, after the Pb is completely melted, the temperature is raised to 1150-1250 ℃, cuprous sulfide is added, after the Pb is completely melted, stirring is carried out uniformly for 10min, and then the Pb is cooled to 300-400 ℃, and the Pb is discharged from the furnace to obtain the lead-acid storage battery grid high-calcium alloy.
4. The method for preparing the lead-acid storage battery grid high-calcium alloy according to claim 3, which is characterized by comprising the following steps: under the protection of argon, pb is melted in a melting furnace at 460-465 ℃, sn is added after Pb is melted, after the Pb is completely melted, the temperature is raised to 740-770 ℃, calcium telluride is added, after the Pb is completely melted, the temperature is raised to 880-920 ℃, ca is added, after the Pb is completely melted, the temperature is raised to 1180-1220 ℃, cuprous sulfide is added, after the Pb is completely melted, stirring is carried out uniformly for 10min, and then the Pb is cooled to 330-370 ℃, and the Pb is discharged from the furnace to obtain the lead-acid storage battery grid high-calcium alloy.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU366518A1 (en) * | 1971-04-22 | 1973-01-16 | GRID FOR ELECTRODE LEAD ACCUMULATOR | |
| CN101815774A (en) * | 2007-09-28 | 2010-08-25 | 纳米技术有限公司 | Core shell nanoparticles and preparation method thereof |
| CN105226284A (en) * | 2009-07-01 | 2016-01-06 | 巴斯夫欧洲公司 | Ultrapure synthetic carbon materials |
| CN109196688A (en) * | 2016-04-27 | 2019-01-11 | Rsr技术公司 | Lead-containing alloy and correlation technique and product |
-
2021
- 2021-09-10 CN CN202111063642.2A patent/CN113782747B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU366518A1 (en) * | 1971-04-22 | 1973-01-16 | GRID FOR ELECTRODE LEAD ACCUMULATOR | |
| CN101815774A (en) * | 2007-09-28 | 2010-08-25 | 纳米技术有限公司 | Core shell nanoparticles and preparation method thereof |
| CN105226284A (en) * | 2009-07-01 | 2016-01-06 | 巴斯夫欧洲公司 | Ultrapure synthetic carbon materials |
| CN109196688A (en) * | 2016-04-27 | 2019-01-11 | Rsr技术公司 | Lead-containing alloy and correlation technique and product |
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