CN118684264B - A method for preparing lead oxide powder containing barium element using lead alloy - Google Patents
A method for preparing lead oxide powder containing barium element using lead alloy Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 162
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 50
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910000464 lead oxide Inorganic materials 0.000 title claims abstract description 26
- 229910000978 Pb alloy Inorganic materials 0.000 title 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 56
- 239000000956 alloy Substances 0.000 claims abstract description 56
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 229910002056 binary alloy Inorganic materials 0.000 claims description 18
- 229910006529 α-PbO Inorganic materials 0.000 claims description 14
- 238000010298 pulverizing process Methods 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000002161 passivation Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 229910000600 Ba alloy Inorganic materials 0.000 abstract description 3
- 238000004886 process control Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract 1
- 230000001934 delay Effects 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 238000003860 storage Methods 0.000 description 20
- 239000000835 fiber Substances 0.000 description 9
- 229920005610 lignin Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000010575 Pueraria lobata Nutrition 0.000 description 5
- 241000219781 Pueraria montana var. lobata Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010926 waste battery Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/06—Lead monoxide [PbO]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/10—Red lead [Pb3O4]
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B7/001—Dry processes
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- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/02—Alloys based on lead with an alkali or an alkaline earth metal as the next major constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- 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
- H01M2004/027—Negative electrodes
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Abstract
本发明公开了一种使用合金铅制备含有钡元素氧化铅粉体的方法，属于铅蓄电池生产技术领域。本发明通过制得铅钡合金，采用该合金，通过工艺控制，制备成为含有钡元素的PbO粉体，通过使用这种粉体和膏，铅粉具备非常好的分散性能，不易团聚，电池批次一致性非常理想，同时又实现了钡元素的引入，而且通过这种方式引入的钡元素，因为嵌入在PbO晶体结构中，在循环过程中不易脱离开活性物质，延缓了负极的钝化过程，在整个寿命期间，能够提升电池初期低温性能和循环过程中低温保持能力。The invention discloses a method for preparing lead oxide powder containing barium element by using alloy lead, and belongs to the technical field of lead-acid battery production. The invention prepares PbO powder containing barium element by preparing lead-barium alloy and using the alloy through process control. By using the powder and paste, the lead powder has very good dispersion performance, is not easy to agglomerate, and the battery batch consistency is very ideal. At the same time, the introduction of barium element is realized. Moreover, the barium element introduced in this way is not easy to separate from the active material during the cycle because it is embedded in the PbO crystal structure, which delays the passivation process of the negative electrode. During the entire life, the initial low temperature performance of the battery and the low temperature retention ability during the cycle can be improved.
Description
Technical Field
The invention belongs to the technical field of lead storage battery production, and particularly relates to a method for preparing barium element-containing lead oxide powder by using alloy lead.
Background
The low-temperature capacity is a key performance index of the lead storage power battery for the electric bicycle, particularly the low-temperature maintaining capacity in the use process determines the public praise of users on the product quality, and in order to improve the low-temperature performance of the battery, expanding agent materials such as lignin, carbon materials, barium sulfate and the like are added into a negative electrode formula material. Barium sulfate is a class of inorganic additive materials. The lattice parameters of barium sulfate and lead sulfate are similar, the barium sulfate is a isomorphous substance, the highly dispersed barium sulfate exists in the anode active substance, the barium sulfate can be used as a crystallization center of lead sulfate during discharge, and since the lead sulfate can be crystallized and separated out on the isomorphous barium sulfate, lead sulfate crystal nucleus does not need to be formed, the supersaturation degree necessary for forming the crystal nucleus can not be generated, the lead sulfate generated under the condition of low supersaturation degree is loose and porous, the diffusion of sulfuric acid is facilitated, the active substance is not covered by a lead sulfate passivation layer, the passivation of a polar plate is delayed, and the method is closely related to the low-temperature holding capability of a battery.
In the paste mixing process, firstly, the dispersing effect of the barium sulfate determines the performance of the battery, in the paste mixing stage, the barium sulfate is easy to agglomerate, so that the addition is uneven, secondly, the particle size of the barium sulfate also has a larger influence on the battery performance, the particle sizes of the barium sulfate in different batches often cause the difference in the battery performance of the batches due to the uneven particle sizes, and finally, the barium sulfate is continuously precipitated and embedded in the process of participating in the construction of the anode active material structure because of being an inert material, and the barium sulfate is continuously lost along with formation and recycling, so that the local passivation of a negative plate is caused, the low-temperature performance of the battery is reduced, and along with recycling, the low-temperature performance is gradually reduced.
In the existing recycling system of waste batteries, after the batteries are recycled and smelted, the barium element is extracted, and at the battery manufacturing end, as described above, the barium element needs to be added into the batteries in the form of barium sulfate because of the key influence on the battery performance.
For example, patent application publication No. CN110649345A discloses a method for recycling waste lead paste of a lead-acid storage battery and application of the recycled product. The method for recycling the waste lead paste of the lead-acid storage battery comprises the following steps of (1) crushing the waste lead paste by using a hammer mill until the granularity of the waste lead paste is 5-10 mu m, (2) sintering the crushed waste lead paste in the step (1) to prepare an additive 4BS-BaPbO 3, (3) grinding the additive 4BS-BaPbO 3 obtained in the step (2) until the fineness of the additive is 1-5 mu m, and (4) adding the additive 4BS-BaPbO 3 obtained in the step (3) into the positive lead paste according to 1-8% of the weight of positive lead powder. The method provided by the invention can be used for recycling the waste lead paste in the production process of the lead-acid storage battery, and the barium sulfate in the waste lead paste is prevented from entering the positive lead paste to influence the performance of the positive electrode plate by converting the barium sulfate into the lead-acid barium.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a method for preparing the lead oxide powder containing the barium element by using alloy lead, the invention starts from the whole lead recovery industrial chain, the barium element is not extracted, the regenerated lead is only subjected to a relatively low-cost impurity removal and purification process to prepare the lead-barium alloy, and the alloy is adopted to prepare the PbO powder containing the barium element through process control, and the powder can be used for preparing the low-temperature-resistant lead storage battery.
The specific technical scheme of the invention is as follows:
The invention provides a method for preparing barium element-containing lead oxide powder by using alloy lead, wherein the alloy lead is obtained by recycling a lead storage battery, the barium element-containing lead oxide powder is used as a raw material of a low-temperature-resistant lead storage battery, and the method comprises the following steps of:
(1) In the lead storage battery recovery process, in the lead recovery smelting stage, barium is not removed, and the lead-barium binary alloy is prepared through impurity removal and purification processes;
(2) Melting the lead-barium binary alloy obtained in the step (1) into a liquid state, wherein the melting temperature is 450-490 ℃;
(3) Pulverizing the liquid lead-barium binary alloy obtained in the step (2) to obtain powder, wherein the temperature is controlled to be 450-490 ℃ in the pulverizing process;
(4) And (3) crushing and screening the powder obtained in the step (3), and then, collecting the powder in a powder bin to obtain the barium-element-containing lead oxide powder.
Preferably, the proportion of lead and barium in the lead-barium binary alloy is regulated and controlled according to a formula when preparing a negative plate of the low-temperature-resistant lead storage battery;
wherein the content of barium element in the lead-barium binary alloy is not less than 1.0 percent. According to the embodiment of the invention, the content of the barium element in the lead-barium binary alloy is 1.0% -1.2%, but the lead-barium binary alloy is not limited to the above.
Specifically, in step (2), the melting temperature is 485 ℃.
Preferably, in the step (3), the temperature is controlled to be 470-490 ℃ in the pulverizing process. The powder obtained after primary oxidation in the powder making furnace is irregular lead oxide powder;
specifically, in the step (3), a powder preparation furnace is used for powder preparation, the powder preparation furnace is preheated before the liquid lead-barium binary alloy flows in, the preheating temperature is set to 450 ℃, the powder preparation furnace is not required to be heated in the powder preparation stage, and the temperature in the powder preparation furnace is controlled within the powder preparation temperature range in the powder preparation process.
Specifically, the temperature of the powder making furnace is controlled by controlling the speed of air inlet in the powder making process, and when the temperature of the powder making furnace cannot be controlled by controlling the speed of air inlet, the speed of flowing the liquid lead-barium binary alloy into the powder making furnace is reduced.
Preferably, in the process of pulverizing, when the temperature in the pulverizing furnace is lower than 450 ℃, air is introduced at a speed lower than 8L/min, when the temperature in the furnace is kept at 450-490 ℃, air is introduced at a speed not lower than 8L/min, when the temperature in the furnace is rapidly increased to above 490 ℃, the air introducing speed is continuously increased, and when the temperature in the pulverizing furnace cannot be controlled, the speed of the semi-liquid lead-barium binary alloy flowing into the pulverizing furnace is reduced except the air introducing speed.
In the step (4), the irregular lead oxide powder is crushed and then screened by a secondary cyclone separator and a cloth bag dust collector pipeline to obtain the lead oxide powder without obvious large blocks, and the powder enters a powder bin to be collected;
After the powder is placed in a powder bin for 48 hours, screening the powder by a 200-mesh sieve, and conveying the screened finished product to a storage bin for storage through a secondary cyclone separator and a cloth bag dust collector pipeline for production;
the temperature of the lead melting furnace and the airflow speed of the pulverizing furnace are controlled, so that the temperature control in the furnace is realized. The PbO powder embedded with the key element barium is prepared, the oxidation degree content of the powder is not more than 80%, preferably, the mass percentage of beta-PbO in the powder is controlled within the range of 20% -30%, and the ratio of alpha-PbO/beta-PbO is controlled within the range of 1.5-3.2.
The invention also provides application of the barium-element-containing lead oxide powder prepared by the method in preparation of low-temperature-resistant lead storage batteries, and the barium-element-containing lead oxide powder is used for preparing negative lead paste.
The invention also provides a negative pole plate, which is coated with the negative lead paste prepared from the barium-containing lead oxide powder prepared by the method.
The invention also provides a low temperature resistant lead storage battery, which comprises the negative electrode plate.
The method comprises the following steps:
In the paste mixing stage, powder is automatically weighed according to a production plan, other additive materials including fibers, lignin and the like are increased according to corresponding proportions, no additional additive materials containing barium are needed, the whole paste mixing process is not needed to be subjected to targeted adjustment, the whole curing process is not needed to be subjected to targeted adjustment, and the formation stage is not needed to be subjected to additional increase of formation electric quantity.
The invention has the beneficial effects that:
The invention prepares the Pb-Ba alloy, adopts the alloy, prepares the PbO powder containing the Ba element through process control, and by using the powder and the paste, the Pb powder has very good dispersion performance, is not easy to agglomerate, has very ideal consistency of battery batch, simultaneously realizes the introduction of the Ba element, the barium element introduced in the mode is embedded in the PbO crystal structure, so that active substances are not easy to separate in the circulating process, the passivation process of the anode is delayed, and the initial low-temperature performance and the low-temperature holding capacity in the circulating process of the battery can be improved during the whole service life.
Detailed Description
Example 1
The waste batteries are recovered, crushed, smelted, purified and decontaminated, the element proportion is controlled, alloy is prepared, each element component is 99.0% Pb-1.0% Ba, alloy lead is conveyed into a lead melting furnace to be melted through a transmission belt, the melting furnace is heated to 450 ℃, the temperature is reduced after alloy lead strips are added, the lead melting furnace begins to heat and raise the temperature, the process temperature is controlled to be not more than 490 ℃, the final holding temperature is 485 ℃, alloy lead is melted into liquid, lead ingots are sampled from 3 different positions of a lead pot respectively, and are used for alloy spectral analysis, and the burning loss condition of the alloy elements is confirmed, as shown in table 1.
TABLE 1 alloy spectra (1)
From the spectral results in table 1, after the alloy lead strip is melted, a large amount of lead slag does not appear on the surface of the lead furnace, and under the temperature control range, obvious burning loss of elements does not appear, and the alloy lead strip is basically kept close to the alloy lead strip.
The lead liquid is used for powder making, and no abnormal condition occurs.
Example 2
The waste batteries are recovered, crushed, smelted, purified and decontaminated, the element proportion is controlled, alloy is prepared, each element component is 99.2 percent Pb-0.8 percent Ba, alloy lead is conveyed into a lead melting furnace to be melted through a transmission belt, the melting furnace is heated to 450 ℃, the temperature is reduced after alloy lead strips are added, the lead melting furnace begins to heat and raise the temperature, the process temperature is controlled to be not more than 490 ℃, the final holding temperature is 485 ℃, alloy lead is melted into liquid, lead ingots are sampled from 3 different positions of a lead pot respectively, and are used for alloy spectral analysis, and the burning loss condition of the alloy elements is confirmed, as shown in table 2.
Table 2 alloy spectrum (2)
From the analysis of the spectrum results, after the alloy lead strip is melted, a large amount of lead slag does not appear on the surface of the lead furnace, and under the temperature control range, obvious burning loss of elements does not appear, so that the alloy lead strip is basically kept close to the alloy lead strip.
The use of the lead liquid for powder production has poor fluidity, and the powder production efficiency is reduced by about 13% compared with that of the embodiment 1.
Example 3
The waste batteries are recovered, crushed, smelted, purified and decontaminated, the element proportion is controlled, alloy is prepared, each element component is 99.5 percent Pb-0.5 percent Ba, alloy lead is conveyed into a lead melting furnace to be melted through a transmission belt, the melting furnace is heated to 450 ℃, the temperature is reduced after alloy lead strips are added, the lead melting furnace begins to heat and raise the temperature, the process temperature is controlled to be not more than 490 ℃, the final holding temperature is 485 ℃, alloy lead is melted into liquid, lead ingots are sampled from 3 different positions of a lead pot respectively, and are used for alloy spectral analysis, and the burning loss condition of the alloy elements is confirmed, as shown in table 3.
TABLE 3 alloy spectra (3)
From the analysis of the spectrum results, after the alloy lead strip is melted, a large amount of lead slag does not appear on the surface of the lead furnace, and under the temperature control range, obvious burning loss of elements does not appear, so that the alloy lead strip is basically kept close to the alloy lead strip.
The use of the lead liquid for powder production has poor fluidity, and the powder production efficiency is reduced by about 30% compared with that of the embodiment 1.
Example 4
The waste batteries are recovered, crushed, smelted, purified and decontaminated, the element proportion is controlled, alloy is prepared, the element components are 98.8 percent Pb-1.2 percent Ba respectively, alloy lead is conveyed into a lead melting furnace to be melted through a transmission belt, the melting furnace is heated to 450 ℃, the temperature is reduced after alloy lead strips are added, the lead melting furnace begins to heat and raise the temperature, the process temperature is controlled to be not more than 490 ℃, the final holding temperature is 485 ℃, the alloy lead is melted into a liquid state, the lead liquid is stirred, lead ingots are sampled from 3 different positions of a lead pot respectively and are used for alloy spectral analysis, and the burning loss condition of the alloy elements is confirmed, as shown in table 4.
Table 4 alloy spectrum (4)
From the analysis of the spectrum results, after the alloy lead strip is melted, a large amount of lead slag does not appear on the surface of the lead furnace, and under the temperature control range, obvious burning loss of elements does not appear, so that the alloy lead strip is basically kept close to the alloy lead strip.
The lead liquid is used for powder making, and no abnormal condition occurs.
Example 5
The powder making furnace is preheated, the temperature in the furnace reaches 450 ℃, high-speed centrifugal stirring rotation is started, negative air pressure is started, lead liquid in the embodiment 1 is selected to start flowing into the powder making furnace, meanwhile, air is introduced at the speed of 8L/min, the temperature in the furnace starts to gradually rise, the temperature reaches 470 ℃, air is introduced at the speed of 10L/min, the temperature slowly drops, the temperature in the furnace is kept in the range of 450-470 ℃, the flow rate of the lead liquid is kept, after the powder making, crushing and screening processes, the powder enters a powder bin for collection, after cooling is finished, 3 samples are sampled according to the feeding time sequence of the powder bin for XRD test, and the results are shown in table 5.
TABLE 5 powder XRD (1)
XRD results show that the powder is mainly alpha-PbO and beta-PbO, the total content of the alpha-PbO and the beta-PbO is over 70%, the content of free lead is over 20%, the content of the residual lead tetraoxide is low, the 1# sample is a first feeding sample, the 3# sample is a last feeding sample, and the content of the 3 samples is basically kept close.
Example 6
The powder making furnace is preheated, the temperature in the furnace reaches 450 ℃, high-speed centrifugal stirring rotation is started, negative air pressure is started, lead liquid in the embodiment 1 is selected to start flowing into the powder making furnace, meanwhile, air is introduced at the speed of 8L/min, the temperature in the furnace starts to gradually rise, the temperature reaches 490 ℃, air is introduced at the speed of 10L/min, the temperature slowly drops, the temperature in the furnace is kept in the range of 470-490 ℃, the flow rate of the lead liquid is kept, after the powder making, crushing and screening processes, the powder enters a powder bin for collection, after cooling is finished, 3 samples are sampled according to the feeding time sequence of the powder bin for XRD test, and the results are shown in table 6.
TABLE 6 powder XRD (2)
XRD results show that the powder is mainly alpha-PbO and beta-PbO, the total content of the alpha-PbO and the beta-PbO is more than 75%, the content of free lead is less than 20%, the content of the residual lead tetraoxide is lower, the 4# sample is a first feeding sample, the 6# sample is a last feeding sample, and the content of the 3 samples is basically kept close.
Example 7
The powder making furnace is preheated, the temperature in the furnace reaches 500 ℃, high-speed centrifugal stirring rotation is started, negative air pressure is started, lead liquid in the embodiment 1 is selected to start flowing into the powder making furnace, meanwhile, air is introduced at the speed of 8L/min, the temperature in the furnace starts to gradually rise, the temperature reaches 520 ℃, air is introduced at the speed of 12L/min, the temperature slowly drops, the temperature in the furnace is kept within the range of 490-510 ℃, the flow rate of the lead liquid is kept, after the powder making, crushing and screening processes, the powder enters a powder bin for collection, after cooling is finished, 3 samples are sampled according to the feeding time sequence of the powder bin for XRD test, and the results are shown in table 7.
TABLE 7 powder XRD (3)
XRD results show that the measured powder is mainly composed of alpha-PbO and beta-PbO, the total content of the alpha-PbO and the beta-PbO is more than 85%, the content of beta-PbO starts to increase, the content of free lead is less than 10%, the content of the residual lead tetraoxide component also starts to increase, a No. 7 sample is a first feeding sample, a No. 9 sample is a last feeding sample, and the No. 9 sample entering a powder bin later in the stage is obviously different in phase compared with the No. 7 sample, and the difference of the front and rear powder is unfavorable for the consistency of subsequent batteries.
Example 8
The powder making furnace is preheated, the temperature in the furnace reaches 450 ℃, high-speed centrifugal stirring rotation is started, negative air pressure is started, lead liquid in the embodiment 4 is selected to start flowing into the powder making furnace, meanwhile, air is introduced at the speed of 8L/min, the temperature in the furnace starts to gradually rise, the temperature reaches 470 ℃, air is introduced at the speed of 10L/min, the temperature slowly drops, the temperature in the furnace is kept in the range of 450-470 ℃, the flow rate of the lead liquid is kept, after the powder making, crushing and screening processes, the powder enters a powder bin for collection, after cooling is finished, 3 samples are sampled according to the feeding time sequence of the powder bin for XRD test, and the results are shown in table 8.
TABLE 8 powder XRD (4)
XRD results show that the powder is mainly alpha-PbO and beta-PbO, the total content of the alpha-PbO and the beta-PbO is about 60%, the content of free lead is about 40%, the content of lead tetraoxide is extremely low, almost none of the lead tetraoxide is contained, the 10# sample is the first feeding sample, the 12# sample is the last feeding sample, and the content of the 3 samples is basically kept close.
From the results, under the same pulverizing process conditions, the content of Ba element is increased, the oxidation efficiency is obviously reduced, and the powder has lower oxidation degree and is unfavorable for battery production.
Example 9
The powder making furnace is preheated, the temperature in the furnace reaches 450 ℃, high-speed centrifugal stirring rotation is started, negative air pressure is started, lead liquid in the embodiment 4 is selected to start flowing into the powder making furnace, meanwhile, air is introduced at the speed of 8L/min, the temperature in the furnace starts to gradually rise, the temperature reaches 490 ℃, air is introduced at the speed of 10L/min, the temperature slowly drops, the temperature in the furnace is kept in the range of 470-490 ℃, the flow rate of the lead liquid is kept, after the powder making, crushing and screening processes, the powder enters a powder bin for collection, after cooling is finished, 3 samples are sampled according to the feeding time sequence of the powder bin for XRD test, and the results are shown in table 9.
TABLE 9 powder XRD (5)
XRD results show that the powder is mainly alpha-PbO and beta-PbO, the total content of the alpha-PbO and the beta-PbO is more than 75%, the content of free lead is less than 20%, the content of the residual lead tetraoxide is lower, the 13# sample is a first feeding sample, the 15# sample is a last feeding sample, and the content of 3 samples is basically kept close.
As can be seen from the results, compared with example 8, the oxidation efficiency is obviously improved by adjusting the pulverizing process, and the oxidation degree of the powder meets the production process requirements of the storage battery.
Example 10
The powder making furnace is preheated, the temperature in the furnace reaches 500 ℃, high-speed centrifugal stirring rotation is started, negative air pressure is started, lead liquid in the embodiment 4 is selected to start flowing into the powder making furnace, meanwhile, air is introduced at the speed of 8L/min, the temperature in the furnace starts to gradually rise, the temperature reaches 520 ℃, air is introduced at the speed of 12L/min, the temperature slowly drops, the temperature in the furnace is kept within the range of 490-510 ℃, the flow rate of the lead liquid is kept, after the powder making, crushing and screening processes, the powder enters a powder bin for collection, after cooling is finished, 3 samples are sampled according to the feeding time sequence of the powder bin for XRD test, and the results are shown in table 10.
TABLE 10 powder XRD (6)
XRD results show that the measured powder is mainly composed of alpha-PbO and beta-PbO, the total content of the alpha-PbO and the beta-PbO is about 85%, the content of beta-PbO starts to increase, the content of free lead is less than 10%, the content of the residual lead tetraoxide component also starts to increase, a 16# sample is a first feeding sample, a 18# sample is a last feeding sample, and the 18# sample entering a powder bin later in the stage is obviously different from the 16# sample in phase, and the difference of the front and rear powder is unfavorable for the consistency of the subsequent batteries.
Example 11
(1) Preparation of Experimental cell # 1
The powder prepared in example 5 was selected, and a battery test was performed, and a vacuum paste mixer was used to prepare a lead paste, a negative plate, and a total of 60.2kg sulfuric acid (density: 1.4g/cm 3) and 66.5kg pure water were added to the powder having a weight of 700 kg.
Based on the prior formula, according to the weight of 700kg of lead powder,
1.4Kg of lignin, which is produced by Norway Bolichi Kudzuvine company and has the name VA,
0.49Kg of short fibers was added.
And coating, curing and slicing in a conventional manner to finish the preparation of the negative electrode plate. The positive plate is a matched corresponding plate, the external dimension is the same as that of the negative electrode, 0.5 percent of antimonous oxide is added, 0.5 percent of stannous sulfate is added, 0.07 percent of short fiber is added, the lead paste is prepared by vacuum mixing paste, pure water and sulfuric acid are used in the paste mixing process, the adding amount is 9.2 percent of sulfuric acid, and the sulfuric acid density is 1.4g/cm 3 (25 ℃) and 9.3 percent of pure water according to the mass percent of lead powder in a positive electrode formula. After the coating, curing and slicing are finished, the preparation of the positive electrode plate is completed, and the two electrode plates are assembled into the 6-DZF-20 battery.
(2) Preparation of No. 2 Experimental cell
The powder prepared in example 6 was selected, and a battery test was performed, and a vacuum paste mixer was used to prepare a lead paste, a negative plate, and a total of 60.2kg sulfuric acid (density: 1.4g/cm 3) and 66.5kg pure water were added to the powder having a weight of 700 kg.
Based on the prior formula, according to the weight of 700kg of lead powder,
1.4Kg of lignin, which is produced by Norway Bolichi Kudzuvine company and has the name VA,
0.49Kg of short fibers was added.
And coating, curing and slicing in a conventional manner to finish the preparation of the negative electrode plate.
The same batch of positive plates as the No. 1 experimental battery was used to assemble a 6-DZF-20 battery.
(3) Preparation of 3# Experimental Battery
The powder prepared in example 7 was selected, subjected to battery test, and stirred in a paste mixer to ensure that the phase composition of the powder was close, and a vacuum paste mixer was used to prepare a lead paste, the weight of the negative plate was 700kg, and a total of 60.2kg sulfuric acid (density: 1.4g/cm 3) and 66.5kg pure water were added.
Based on the prior formula, according to the weight of 700kg of lead powder,
1.4Kg of lignin, which is produced by Norway Bolichi Kudzuvine Co., ltd., brand VA, is added
0.49Kg of short fibers was added.
And coating, curing and slicing in a conventional manner to finish the preparation of the negative electrode plate.
The same batch of positive plates as the No. 1 experimental battery was used to assemble a 6-DZF-20 battery.
(4) Preparation of No. 4 Experimental Battery
The powder prepared in example 8 was selected, and a battery test was performed, and a vacuum paste mixer was used to prepare a lead paste, and a negative plate, the weight of the powder was 700kg, and 60.2kg of sulfuric acid (density: 1.4g/cm 3) and 66.5kg of pure water were added in total.
Based on the prior formula, according to the weight of 700kg of lead powder,
1.4Kg of lignin, which is produced by Norway Bolichi Kudzuvine company and has the name VA,
0.49Kg of short fibers was added.
The same batch of positive plates as the No. 1 experimental battery was used to assemble a 6-DZF-20 battery.
(5) Preparation of 5# Experimental cell
The powder prepared in example 9 was selected, and a battery test was performed, and a vacuum paste mixer was used to prepare a lead paste, a negative plate, and a total of 60.2kg sulfuric acid (density: 1.4g/cm 3) and 66.5kg pure water were added to the powder having a weight of 700 kg.
Based on the prior formula, according to the weight of 700kg of lead powder,
1.4Kg of lignin, which is produced by Norway Bolichi Kudzuvine company and has the name VA,
0.49Kg of short fibers was added.
And coating, curing and slicing in a conventional manner to finish the preparation of the negative electrode plate.
The same batch of positive plates as the No. 1 experimental battery was used to assemble a 6-DZF-20 battery.
(6) Preparation of 6# Experimental cell
The powder prepared in example 10 was selected, subjected to battery test, and stirred in a paste mixer to ensure that the phase composition of the powder was close, and a vacuum paste mixer was used to prepare a lead paste, the weight of the negative plate was 700kg, and a total of 60.2kg sulfuric acid (density: 1.4g/cm 3) and 66.5kg pure water were added.
Based on the prior formula, according to the weight of 700kg of lead powder,
1.4Kg of lignin, which is produced by Norway Bolichi Kudzuvine Co., ltd., brand VA, is added
0.49Kg of short fibers was added.
And coating, curing and slicing in a conventional manner to finish the preparation of the negative electrode plate.
The same batch of positive plates as the No. 1 experimental battery was used to assemble a 6-DZF-20 battery.
(7) Preparation of comparative cells
The lead plaster is prepared by adopting a vacuum plaster mixing machine, the lead powder is produced by a conventional Shimadzu powder mode, the weight of the lead powder is 700kg,60.2kg of sulfuric acid (density is 1.4g/cm 3), and 66.5kg of pure water.
Based on the prior formula, according to the weight of 700kg of lead powder,
1.4Kg of lignin, which is produced by Norway Bolichi Kudzuvine company and has the name VA,
0.49Kg of short fibers was added.
And coating, curing and slicing in a conventional manner to finish the preparation of the negative electrode plate.
The same batch of positive plates as the No. 1 experimental battery was used to assemble a 6-DZF-20 battery.
(8) Battery performance detection
Sampling the lead storage batteries after the 6 examples and the comparative examples are formed respectively, extracting 10 lead storage batteries respectively in order to verify the consistency of the batteries, carrying out two-hour rate normal temperature capacity test according to GB/T22199.1-2017 valve-regulated lead storage battery for electric power vehicles, carrying out low temperature detection at-18 ℃ after the end of the test, extracting 3 lead storage batteries respectively from the test, and carrying out single life test according to the environment required by GB/T22199.1-2017, wherein the life test method comprises the following steps:
constant-current discharge, namely 10A constant-current discharge until the voltage reaches 10.5V, turning to a constant-voltage current-limiting charging stage;
constant voltage and current limiting charging, namely constant voltage is 14.8V, current limiting is 10A, charging time is limited to 5h, and full charging of the battery is carried out.
The above is a cycle, 100 times of cycles are taken as a unit, after each unit is finished, charging is completed, and low-temperature detection is carried out at-18 ℃ according to the environment required by GB/T22199.1-2017.
And when the discharge time of the battery is continuously 3 times and is lower than 96 minutes, judging that the battery fails, wherein the 3 times of circulation are not counted in an accumulated way, and performing low-temperature detection at-18 ℃ according to the environment required by GB/T22199.1-2017 after the circulation is finished.
Table 11 shows the average capacity comparison for the two hour rates of 7 cells.
Table 11 comparison of room temperature Capacity test
As can be seen from Table 11, the two hour rate discharge, the 1# and 2# are close to the comparative battery, the 5# battery is slightly higher, the 3# battery has reduced capacity each time, the normal temperature capacity of the 4# battery is obviously lower, the normal temperature capacity of the 6# battery has extremely fast reduction, and the quality defects of the several batteries are obviously generated, and the subsequent low temperature capacity and the cycle life are not continuously detected.
After the normal temperature capacity is finished, 40 batteries of No.1, no. 2, no. 5 and comparison are all subjected to-18 ℃ low temperature capacity detection, and the comparison results of the low temperature capacity of 4 batteries at-18 ℃ are shown in table 12.
TABLE 12 Low temperature Capacity (min) comparison
From the detection results, the 2# and 5# experimental batteries have the highest low-temperature capacity and the smallest variance value, which indicates that the batteries have the best consistency, the low-temperature capacity of the comparison battery is the lowest, and the consistency is poor. By analysis, the powder used for the negative electrode was the powder prepared in example 6, the powder used for the negative electrode was the powder prepared in example 9, and the powder used for the negative electrode was the powder prepared in example 5, and the powder used for the negative electrode was the powder prepared in example 1. From the above results, the experimental powder was used, the low temperature capacity was significantly improved, and the low temperature improvement of the powder of example 6 was the highest, and the uniformity was also the best.
After the low-temperature capacity was completed, 3 batteries having a low-temperature capacity close to each other were selected from among 3 batteries, and each battery was subjected to a single cycle, and after the completion of each unit, a low-temperature capacity test was performed, and after the end of the cycle life, a low-temperature capacity test was also performed, and the low-temperature average value was as shown in table 13 below:
TABLE 13 Low temperature Capacity comparison during cycling
From the above table, it can be seen that the cycle life of the 1# battery and the 2# battery using the experimental powder is also slightly increased, and the number of times of cycle life of the 5# battery using the experimental powder is lower than that of the comparative battery.
In the circulation process, the low-temperature attenuation of the 3 batteries adopting the experimental powder is obviously superior to that of the comparative batteries, which shows that the low-temperature holding capacity of the lead storage battery prepared by adopting the lead powder is greatly improved.
Claims (9)
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