CN112420996A - Method for preparing power battery by utilizing recycled lead powder, positive plate and power battery - Google Patents
Method for preparing power battery by utilizing recycled lead powder, positive plate and power battery Download PDFInfo
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- CN112420996A CN112420996A CN202011180978.2A CN202011180978A CN112420996A CN 112420996 A CN112420996 A CN 112420996A CN 202011180978 A CN202011180978 A CN 202011180978A CN 112420996 A CN112420996 A CN 112420996A
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- power battery
- antimony
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 41
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 33
- 229910052718 tin Inorganic materials 0.000 claims abstract description 33
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 21
- 239000004332 silver Substances 0.000 claims abstract description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- 239000011505 plaster Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 8
- 230000005484 gravity Effects 0.000 claims description 7
- 230000002950 deficient Effects 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 15
- 239000000654 additive Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010949 copper Substances 0.000 description 13
- 239000002699 waste material Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 229910052785 arsenic Inorganic materials 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 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
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 1
- UDRRLPGVCZOTQW-UHFFFAOYSA-N bismuth lead Chemical compound [Pb].[Bi] UDRRLPGVCZOTQW-UHFFFAOYSA-N 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-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
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a power battery positive plate by utilizing recycled lead powder, which comprises the following steps: (1) smelting the recycled power battery in a smelting furnace to prepare primary crude lead, reserving components of bismuth, antimony, tin and silver in the primary crude lead, and removing impurities of other impurities according to requirements to enable the impurities to meet the standard; (2) measuring components and adjusting content; (3) and casting ingots by using recovered crude lead, cutting into pieces to prepare positive lead powder, preparing positive lead paste by using the positive lead powder, coating a plate to prepare a positive plate, assembling the positive plate into a green plate battery, and forming the battery into a power battery. When the lead storage battery is recovered, beneficial elements are directly utilized without removing impurities in the recovered lead, and the content of metal additives such as antimony, tin, bismuth and the like is adjusted, so that the lead powder is prepared after ingot casting and is used for preparing the positive electrode active substance, and as a result, the distribution of the metal additives such as antimony, tin, bismuth and the like is more uniform, and the cycle life of the prepared battery is also prolonged.
Description
Technical Field
The invention relates to the technical field of lead storage batteries, in particular to a method for preparing a power battery by utilizing recycled lead powder, a positive plate and the power battery.
Background
The traditional lead powder for the positive electrode of the lead-acid battery generally uses No. 1 lead, and can be obtained by electrolyzing crude lead or carrying out pyrogenic treatment on the crude lead to the No. 1 lead, so that metals such as antimony, tin, bismuth and the like in the crude lead are treated, the treatment method has complex flow and high energy consumption, and the cost of the No. 1 lead is higher. Meanwhile, the lead powder made of No. 1 lead has short battery cycle life under the condition of deep cycle when the lead-calcium-tin-aluminum alloy is used.
For example, the invention with the publication number of CN101173326 discloses a method for recycling acidic waste liquid generated in the process of recycling lead from a waste lead-acid storage battery, which can well recycle ions such as lead, cadmium, antimony, tin, bismuth, copper, zinc, silver and the like in the waste lead-acid storage battery lead recycling waste liquid by adding a whole set of technologies such as ammonia water neutralization, sulfide precipitation, nitric acid acidification, solvent extraction and the like, thereby greatly improving the comprehensive recycling rate of resources, and simultaneously eliminating the pollution of relevant heavy metal ions to the environment, and having very important practical significance.
The invention with publication number CN108539315A discloses a new process for recovering lead plaster of waste lead storage batteries, which is to mix Pb-Sb crude alloy with antimony content of 46% and desulfurized lead plaster (PbCO)3) The reaction under vacuum conditions converts the lead paste into metallic lead, and the antimony in the Pb-Sb crude alloy is converted into antimony trioxide. The technology for separating antimony from the Pb-Sb crude alloy by coupling the vacuum regeneration of the lead plaster and the separation of the Pb-Sb crude alloy is realized.
On the other hand, in the prior art, in order to prolong the service life of the battery, stannous sulfate, antimony trioxide and the like are added when lead powder neutralization paste made of No. 1 lead is used, and due to the obvious difference of specific gravity of the additive and the lead powder, the uniform mixing is difficult to achieve by a stirring mode of a paste mixing machine, so that the consistency of the battery is poor, the early capacity attenuation phenomenon still occurs in part of the batteries under the condition of deep circulation, and the problem of short service life of the batteries is not fundamentally solved. In addition, antimony trioxide is toxic, is added on an operation platform manually, easily causes environmental pollution and harm to human bodies, and the price of stannous sulfate and antimony trioxide is about 5 times that of corresponding metals, so that the cost is very high.
Therefore, how to effectively improve the environment of a paste mixing platform, reduce the harm to the human body, eliminate early capacity attenuation, reduce the cost of a formula and improve the deep cycle performance of a power battery is a problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention provides a method for preparing a power battery positive plate by utilizing recycled lead powder, the positive plate and a power battery, aiming at the problems that in the prior art, the removal of metal additives such as high antimony, tin, bismuth and the like is difficult and the consumption of manpower and material resources is high when a power lead storage battery containing the metal additives is recycled.
A method for preparing a power battery positive plate by using recycled lead powder comprises the following steps:
(1) smelting the recycled power battery in a smelting furnace to prepare primary crude lead, keeping components of bismuth, antimony, tin and silver in the primary crude lead, and removing impurities of other impurities according to requirements to enable the impurities to meet the standard of No. 1 electrolytic lead, so as to prepare recycled crude lead;
(2) measuring the components of the recovered crude lead, adjusting the contents of the four elements of bismuth, antimony, tin and silver in the recovered crude lead according to the positive pole lead plaster formula of the power battery positive plate,
(3) and (3) directly casting ingots by using the adjusted recovered crude lead to prepare lead ingots, cutting the lead ingots into blocks to prepare positive lead powder, preparing positive lead paste by using the positive lead powder, coating plates to prepare positive plates, assembling a green plate battery, and forming the battery into a power battery.
Preferably, in the recovered crude lead after the adjustment in the step (2), the mass concentration of the metallic antimony is 0.001-0.5000%, the mass concentration of the metallic tin is 0.0010-1.2000%, the mass concentration of the metallic bismuth is 0.0005-0.0500%, and the mass concentration of the metallic silver is 0.0005-0.0200%. When the step (2) is adjusted, pure bismuth, antimony, tin or silver is additionally added to the deficient content; if the content exceeds the above range, the electrolytic lead is diluted by No. 1 electrolytic lead.
Preferably, the fiber, the sulfuric acid solution and the water are also added when the positive lead paste is prepared in the step (3). More preferably, when the positive electrode lead paste is prepared in the step (3), 70g of the fiber, 12kg to 16kg of water and 10kg of the lead powder having a density of 1.4g/cm are added to 100kg of the lead powder3Sulfuric acid solution of (1). Further preferably, when the positive electrode lead paste is prepared in the step (3), the apparent specific gravity of the prepared wet lead paste is 4.3-4.6g/cm3。
The invention also provides the positive plate prepared by the method.
The invention also provides a power battery using the positive plate.
When the lead storage battery is recovered, beneficial elements are directly utilized without removing impurities in the recovered lead, and the content of metal additives such as antimony, tin, bismuth and the like is adjusted, so that the lead powder is prepared after ingot casting and is used for preparing the positive electrode active substance, and as a result, the distribution of the metal additives such as antimony, tin, bismuth and the like is more uniform, and the cycle life of the prepared battery is also prolonged.
Drawings
FIG. 1 is a flow chart of a process for the earlier stage of recycling waste lead-acid batteries.
FIG. 2 is a schematic diagram of a sample position of the plate.
Fig. 3 is a view showing the result of electron microscope examination of the positive active material prepared in comparative example 1.
Fig. 4 is a graph showing the electron microscope detection result of the positive active material prepared in example 1.
Fig. 5 is a graph showing the electron microscope detection result of the positive active material prepared in example 2.
Fig. 6 is a graph showing the electron microscope detection result of the positive active material prepared in example 3.
Detailed Description
Comparative example 1, example 1 (high antimony alloy)
1. Preparation of lead for positive electrode
The method comprises the following steps: the method comprises the following steps of (1) treating the high-antimony-alloy-content storage battery type batteries (containing tin, antimony, silver and other oxide additives in the industry) such as power batteries, deep-cycle marine high-antimony-alloy-content storage batteries and the like recovered in the market according to the early-stage treatment process flow of recovery of the waste lead storage battery in the figure 1 to obtain lead paste primary lead bullion;
step two: the lead paste primary crude lead prepared in the first step is treated in the way of table 1, the operation of removing antimony, tin, bismuth and silver is not carried out on the lead powder of the positive electrode in the example 1, and the lead of the positive electrode in the comparative example 1 is treated into the standard of No. 1 lead.
The composition of the prepared lead powder of comparative example 1 was measured by using the lead-1 liquid of No. 1 alloy and the lead powder of example 1 was measured by using the lead-1 liquid of No. 1 alloy, and the results are shown in Table 2.
TABLE 1
| Process steps | Comparative example 1 Process | Example 1 |
|
| 1 | Melting by heating | Melting by |
|
| 2 | Slagging | Slagging reduction | |
| 3 | Refining | Refining | |
| 4 | Silver removal | Without removing |
|
| 5 | Copper removal | Copper removal | |
| 6 | Tin removal | Without removing tin | |
| 7 | Sulphur removal | Sulphur removal | |
| 8 | Removing tin and antimony | Without removing tin and antimony | |
| 9 | Bismuth removal | Without removing bismuth | |
| 10 | Removing impurities such as arsenic | Removing impurities such as arsenic | |
| 11 | Deoxidation | Deoxidation |
TABLE 2 (mass%)
Step three: and (3) carrying out ingot casting on the 1# lead-lead liquid for the lead powder of the comparative example 1 prepared in the step two and the 1# alloy lead-lead liquid for the lead powder of the example 1 to obtain a 1# lead ingot for the lead powder of the comparative example 1 and an alloy 1# lead ingot for the lead powder of the example 1.
2. Preparation of lead powder
The lead powder of comparative example 1# lead powder and the lead powder of example 1# lead powder were prepared by using the same lead powder process for the lead powder of comparative example 1# lead ingot and the lead powder of example 1# alloy ingot.
3. Preparation of positive lead plaster
Comparative example 1 lead paste preparation: 100Kg of the lead powder of comparative example No. 1 prepared above was added to a paste mixer, 70g of the dry fiber mixture was added for 5 minutes, 12Kg of water was added for 5 minutes, and 10Kg of the mixture was added to a mixer having a density of 1.4g/cm3Controlling the acid adding speed of the sulfuric acid, finishing adding within 15min, controlling the temperature of the lead plaster below 50 ℃ in the acid adding process, and stirring for 3 min after the acid is added. The apparent specific gravity of the obtained lead paste is 4.4g/cm3。
Example 1 lead paste preparation: 100Kg of the lead powder of example 1 prepared above was added to a paste mixer, 70g of the dry fiber was added and mixed for 5 minutes, 12Kg of water was added for 5 minutes, and 10Kg of water having a density of 1.4g/cm was added3The sulfuric acid is added in the reaction kettle at a controlled speed,adding the lead paste within 15min, controlling the temperature of the lead paste below 50 ℃ in the process of adding acid, and stirring for 3 min after adding the acid. The apparent specific gravity of the obtained lead paste is 4.4g/cm3。
4. Coated sheet
The positive plate of comparative example 1 and the positive plate of example 1 were obtained using a positive plate grid coating of 6-DZM-20 cell.
5. Curing and battery assembly
Curing at 55 deg.C and relative humidity of 85% or more for 48 hr, and drying at 80-90 deg.C and relative humidity below 30% for 24 hr. The plates were separated and assembled to give semi-finished cells of comparative example 1 and example 1, 6-DZM-20.
6. Container formation process
Adding the mixture into the battery with the density of 1.25g/cm3The temperature of the sulfuric acid solution is-5 ℃, the battery is placed in a water-cooling tank at the temperature of 25 ℃ after vacuum acid addition, and charging is carried out according to the following process after standing for 1 h. The pre-formation current density is 8mA/cm2Charging for 7h and later 5mA/cm2And the charging time is 36.8 h. Finished cells of comparative example 1 and example 1 were obtained.
Example 2 (high bismuth lead)
It is often difficult or costly to remove less than 0.1% bismuth, and studies have shown that bismuth contributes to the formation of fine/needle-like and interconnected lead dioxide, thereby strengthening the porous mass of the positive electrode and improving battery life, and that some manufacturers add bismuth trioxide during the paste process to improve battery performance.
The method comprises the following steps: treating the waste lead storage battery in the prior recovery treatment process flow of the waste lead storage battery in the figure 1 by using the liquid adding type lead-acid battery recovered in the market to obtain lead plaster crude lead No. 2 (lead plaster primary crude lead and lead plaster secondary crude lead);
step two: and (3) detecting the components of the lead plaster crude lead 2# obtained in the step one by using a direct-reading spectrometer, wherein the detection results are shown in table 3.
TABLE 3
| Element(s) | Mass fraction% |
| Lead (II) | 98.8854 |
| Antimony (Sb) | 0.0043 |
| Tin (Sn) | 0.0024 |
| Bismuth (III) | 0.0021 |
| Silver (Ag) | 0.0013 |
| Aluminium | 0.0004 |
| Calcium carbonate | 0.0008 |
| Arsenic (As) | 0.0004 |
| Iron | 0.0014 |
| Copper (Cu) | 0.0011 |
| Others | 1.1017 |
Step three: the lead plaster crude lead liquid prepared in the above table is further refined to obtain refined lead liquid 2#, as shown in table 4.
TABLE 4
| Process steps | EXAMPLE 2 |
| 1 | Melting by |
| 2 | |
| 3 | |
| 4 | Without removing |
| 5 | Copper removal |
| 6 | Without removing tin |
| 7 | Sulphur removal |
| 8 | Without removing tin and antimony |
| 9 | Without removing bismuth |
| 10 | Removing impurities such as arsenic |
| 11 | Deoxidation |
Step four: the refined lead-lead liquid 2# obtained by refining in table 4 was sampled and subjected to composition measurement, and the measurement results are shown in table 5.
TABLE 5 (mass%)
| Element(s) | EXAMPLE 2 refined lead and lead liquor No. 2 |
| Lead (II) | 99.9892 |
| Antimony (Sb) | 0.0036 |
| Tin (Sn) | 0.0023 |
| Bismuth (III) | 0.0018 |
| Silver (Ag) | 0.0009 |
| Aluminium | 0.0005 |
| Calcium carbonate | 0.0006 |
| Arsenic (As) | 0.0005 |
| Iron | 0.0003 |
| Copper (Cu) | 0.0004 |
| Others | 0.0008 |
Step five: alloy components were adjusted by adding pure tin, pure antimony and pure bismuth to the refined lead liquid 2# in example 2, and the lead powder 2# in example 2 was prepared again as shown in table 6.
TABLE 6 (mass%)
Step six: and (4) carrying out ingot casting on the lead powder obtained in the fifth step and the 2# alloy lead-lead liquid to obtain an alloy 2# lead ingot for the lead powder obtained in the example 2.
2. Preparation of lead powder
Example 2# lead powder was prepared by using the alloy for lead powder No. 2 ingot of example 2 and a lead powder machine.
3. Preparation of positive lead plaster
100Kg of the lead powder of example 2 prepared above was added to a paste mixer, 70g of the dry fiber was added and mixed for 5 minutes, 12Kg of water was added for 5 minutes, and 10Kg of water having a density of 1.4g/cm was added3Controlling the acid adding speed of the sulfuric acid, controlling the temperature of the lead plaster to be below 50 ℃ in the acid adding process within 15min, and adding the sulfuric acid after the acid is addedStirred for 3 minutes. The apparent specific gravity of the obtained lead paste is 4.4g/cm3。
4. Coated sheet
The positive plate of example 2 was obtained using a 6-DZM-20 cell positive plate grid coating.
5. Curing and battery assembly
Curing at 55 deg.C and relative humidity of 85% or more for 48 hr, and drying at 80-90 deg.C and relative humidity below 30% for 24 hr. The plates were separated and assembled to obtain a semi-finished cell of example 2, 6-DZM-20.
6. Container formation process
Adding the mixture into the battery with the density of 1.25g/cm3The temperature of the sulfuric acid solution is-5 ℃, the battery is placed in a water-cooling tank at the temperature of 25 ℃ after vacuum acid addition, and charging is carried out according to the following process after standing for 1 h. The pre-formation current density is 8mA/cm2Charging for 7h and later 5mA/cm2And the charging time is 36.8 h. A finished cell of example 2 was obtained.
Example 3 (high tin alloy)
In the current automobile lead-acid storage battery for the market, the polar plate of the energy storage battery basically adopts lead-calcium-tin-aluminum alloy, the content of tin is often higher and can reach more than 0.5%, and the step treatment is carried out according to the embodiment 3.
The method comprises the following steps: treating the automobile lead-acid storage battery and the energy storage battery which are recovered on the market according to the earlier-stage treatment process flow of the recovery of the waste lead storage battery in the figure 1 to obtain lead plaster crude lead No. 3 (primary crude lead of lead plaster and secondary crude lead of lead plaster);
step two: and (3) detecting the components of the lead plaster crude lead 3# obtained in the step one by using a direct-reading spectrometer, wherein the detection results are shown in table 7.
TABLE 7
| Element(s) | Mass fraction% |
| Lead (II) | 98.8941 |
| Antimony (Sb) | 0.0004 |
| Tin (Sn) | 1.1000 |
| Bismuth (III) | 0.0009 |
| Silver (Ag) | 0.0012 |
| Aluminium | 0.0004 |
| Calcium carbonate | 0.0008 |
| Arsenic (As) | 0.0004 |
| Iron | 0.0012 |
| Copper (Cu) | 0.0010 |
| Others | 0.0008 |
Step three: the lead plaster crude lead liquid obtained in the above table is further refined to obtain refined lead liquid # 3, as shown in table 8.
TABLE 8
| Process steps | EXAMPLE 3 |
| 1 | Melting by |
| 2 | |
| 3 | |
| 4 | Without removing |
| 5 | Copper removal |
| 6 | Without removing tin |
| 7 | Sulphur removal |
| 8 | Without removing tin and antimony |
| 9 | Without removing bismuth |
| 10 | Removing impurities such as arsenic |
| 11 | Deoxidation |
Step four: the refined lead-lead liquid 3# obtained by refining in table 8 was sampled and subjected to composition measurement, and the measurement results are shown in table 9.
TABLE 9 (mass%)
| Element(s) | EXAMPLE 3 refined lead and |
| Lead (II) | 98.9611 |
| Antimony (Sb) | 0.0004 |
| Tin (Sn) | 1.0348 |
| Bismuth (III) | 0.0008 |
| Silver (Ag) | 0.0011 |
| Aluminium | 0.0004 |
| Calcium carbonate | 0.0005 |
| Arsenic (As) | 0.0005 |
| Iron | 0.0005 |
| Copper (Cu) | 0.0005 |
| Others | 0.0005 |
Step five: alloy component adjustment, for the refined lead-lead liquid 3# in the example 3, pure lead is added to adjust the tin content to be too high, pure antimony and pure bismuth are added to adjust the antimony-bismuth content to be too low, and the alloy lead-lead liquid 3# for preparing the lead powder in the example 3 is shown in table 10.
TABLE 10 (mass%)
Step six: casting the lead powder of the fifth step with the 3# alloy lead-lead liquid to obtain the alloy 3# lead ingot for the lead powder of the fifth step
2. Preparation of lead powder
Example 3# lead powder was prepared by using the alloy for lead powder No. 2 ingot of example 3 described above and using a lead powder machine.
3. Preparation of positive lead plaster
100Kg of the lead powder of example 3 prepared above was added to a paste mixer, 70g of the dry fiber was added and mixed for 5 minutes, 12Kg of water was added for 5 minutes, and 10Kg of water having a density of 1.4g/cm was added3Controlling the acid adding speed of the sulfuric acid, finishing adding within 15min, controlling the temperature of the lead plaster below 50 ℃ in the acid adding process, and stirring for 3 min after the acid is added. The apparent specific gravity of the obtained lead paste is 4.4g/cm3。
4. Coated sheet
The positive plate of example 3 was obtained using a 6-DZM-20 cell positive plate grid coating.
5. Curing and battery assembly
Curing at 55 deg.C and relative humidity of 85% or more for 48 hr, and drying at 80-90 deg.C and relative humidity below 30% for 24 hr. The plates were separated and assembled to give a semi-finished cell of example 3, 6-DZM-20.
6. Container formation process
Adding the mixture into the battery with the density of 1.25g/cm3The temperature of the sulfuric acid solution is-5 ℃, the battery is placed in a water-cooling tank at the temperature of 25 ℃ after vacuum acid addition, and charging is carried out according to the following process after standing for 1 h. The pre-formation current density is 8mA/cm2Charging for 7h and later 5mA/cm2And the charging time is 36.8 h. The finished cell of example 3 was obtained
Example 4
(1) And (5) consistency of the polar plates.
Different positions of the same polar plate: comparative example 1 and examples 1 to 3 were subjected to the same curing process in the same curing chamber, and the electrode plate was placed at the same position in the curing frame, and the ICP measurement was carried out on the Sn, Sb, Bi and Ag components at 5 points (the positions of the 5 points are shown in FIG. 2) of the electrode plate, and the measurement results are shown in Table 11.
TABLE 11 (mass% of each component)
As can be seen from Table 11, the ICP measurements of Sn, Sb and the same elements in examples 1-3 are much better than the uniformity of the comparative example, and have much smaller standard deviation with a difference of one order of magnitude
(2) And (5) detecting the performance of the battery.
The battery is charged and discharged circularly by the following steps: the 12V 20Ah battery has a constant voltage of 14.7V, is charged for 4 hours under a current limit of 10A, is discharged to 10.2V under a current of 10A, and is used as a condition for the end of the life of the battery when the discharge time reaches 96 minutes. The results are shown in Table 12.
TABLE 12
From the above results, it can be seen that the battery using the conventional method has high cost and poor cycle performance, and the positive active material formed by directly using the beneficial elements without removing impurities in the recovered lead has more uniform distribution of the beneficial components, as shown in fig. 3 (comparative example 1), fig. 4 (example 1), fig. 5 (example 2), and fig. 6 (example 3), thereby making the cycle life of the battery better.
Claims (8)
1. A method for preparing a power battery positive plate by using recycled lead powder is characterized by comprising the following steps:
(1) smelting the recycled power battery in a smelting furnace to prepare primary crude lead, keeping components of bismuth, antimony, tin and silver in the primary crude lead, and removing impurities of other impurities according to requirements to enable the impurities to meet the standard of No. 1 electrolytic lead, so as to prepare recycled crude lead;
(2) measuring the components of the recovered crude lead, adjusting the contents of the four elements of bismuth, antimony, tin and silver in the recovered crude lead according to the positive pole lead plaster formula of the power battery positive plate,
(3) and (3) directly casting ingots by using the adjusted recovered crude lead to prepare lead ingots, cutting the lead ingots into blocks to prepare positive lead powder, preparing positive lead paste by using the positive lead powder, coating plates to prepare positive plates, assembling a green plate battery, and forming the battery into a power battery.
2. The novel lead powder alloy lead as claimed in claim 1, wherein the recovered crude lead after adjustment in step (2) has a mass concentration of 0.001 to 0.5000% of metallic antimony, 0.0010 to 1.2000% of metallic tin, 0.0005 to 0.0500% of metallic bismuth and 0.0005 to 0.0200% of metallic silver.
3. The novel lead powder alloy lead of claim 2, wherein in the adjustment of step (2), pure bismuth, antimony, tin or silver is additionally added to the deficient lead powder alloy; if the content exceeds the above range, the electrolytic lead is diluted by No. 1 electrolytic lead.
4. The method of claim 1, wherein the step (3) of preparing the positive electrode lead paste further comprises adding fibers, a sulfuric acid solution and water.
5. The method of claim 4, wherein the positive electrode lead paste is prepared in the step (3) by adding 70g of the fiber, 12kg to 16kg of the water and 10kg of the lead powder having a density of 1.4g/cm to 100kg of the lead powder3Sulfuric acid solution of (1).
6. The method according to claim 5, wherein, when the positive electrode lead paste is prepared in the step (3), the wet lead paste is prepared to have an apparent specific gravity of 4.3 to 4.6g/cm3。
7. A positive plate produced by the method according to any one of claims 1 to 6.
8. A power battery using the positive electrode plate according to claim 7.
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Cited By (2)
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| CN118684264A (en) * | 2024-08-19 | 2024-09-24 | 天能电池集团股份有限公司 | A method for preparing lead oxide powder containing barium element using lead alloy |
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