CN111704158A - Low-cost PbO for promoting formation of positive plate of lead-acid storage battery2Preparation of conductive materials - Google Patents
Low-cost PbO for promoting formation of positive plate of lead-acid storage battery2Preparation of conductive materials Download PDFInfo
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- CN111704158A CN111704158A CN201910738167.0A CN201910738167A CN111704158A CN 111704158 A CN111704158 A CN 111704158A CN 201910738167 A CN201910738167 A CN 201910738167A CN 111704158 A CN111704158 A CN 111704158A
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- 239000002253 acid Substances 0.000 title claims abstract description 44
- 238000003860 storage Methods 0.000 title claims abstract description 33
- 239000004020 conductor Substances 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 18
- 230000001737 promoting effect Effects 0.000 title claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000013543 active substance Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002224 dissection Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000002048 anodisation reaction Methods 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- -1 generally Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C01G21/08—Lead dioxide [PbO2]
-
- 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
-
- 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
-
- 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
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a low-cost PbO for promoting formation of a positive plate of a lead-acid storage battery2The preparation of conductive material includes the steps of recovering battery selection, screening old battery, overcharging screened old battery, dissecting battery, cleaning positive plate, drying and storing positive plate and preparing positive plate according to technological regulation2The conductive material has the advantages of low cost, high efficiency and low production cost.
Description
Technical Field
The invention relates to the field of battery plate manufacturing, in particular to a low-cost PbO for promoting formation of a positive plate of a lead-acid storage battery2And (4) preparing a conductive material.
Background
The lead-acid storage battery has the advantages of wide raw material sources, low price, mature process, stable performance, wide use temperature range, high safety and reliability, can still work at minus 30-40 ℃, is widely applied to various application power supplies such as electric mopeds, electric motorcycles, low-speed tricycles, automobile starting, communication standby and the like, is mainly applied to various batteries with high capacity at present, has the service life mostly limited by a positive plate, and is mainly caused by the failure of the positive plate due to the corrosion of the positive plate grid, the softening and falling of active substances and the interface barrier layer of the positive plate grid/the active substances, and depends on the material and the manufacturing conditions of the positive plate grid and the manufacturing process of lead powder and the positive plate; the formation of the positive plate is an important link in battery production, the water consumption for external formation is large, and lead-containing wastewater is discharged, so that the majority of the conventional methods adopt the internal batteryAnd (5) formation process. However, the formation time of the battery is long, the main reason is that the formation of the positive plate is difficult, especially the formation of a thick polar plate, a poor solution battery and a large battery, especially the formation of a tubular positive plate is difficult, the difficult formation of the positive plate is mainly a positive active material, generally, additives are rarely used, in order to promote the formation of the charge, a large amount of red lead is generally added into the positive active material, and other conductive materials such as carbon materials and SnO are also used2，TiO2And the like, these materials are relatively expensive to produce. Red lead (Pb)3O4) Is composed of PbO2And PbO, of which only half of PbO is present2The conductive PbO has conductivity, and the other half of PbO has no conductivity, and the cost is higher by adopting a large amount of red lead.
Disclosure of Invention
Aiming at the problems, the invention provides a low-cost PbO for promoting formation of a positive plate of a lead-acid storage battery2And (4) preparing a conductive material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: 1. firstly, selecting batteries needing to be recycled: the used lead-acid storage battery can be single or multiple batteries; 2. the old batteries were then charged and screened: firstly, 2.50-2.60V constant voltage and 0.4-0.8C limitation are adopted for a single 2V lead-acid storage battery2Charging the current until the voltage reaches 2.50-2.60V, and then continuing to charge. Removing the battery of which the cell voltage is lower than 2.4V within 6h after charging or the cell voltage is lower than 2.20V within 2h after charging; 3. overcharging the screened cells: 0.3-0.6C is adopted for the lead-acid storage battery2Continuously charging the current; for open cells with openable lids, deionized water can be added until the level of the liquid exceeds the pole group before overcharging; 4. dissecting the battery to separate the positive plate from the negative plate, the separator and the plastic shell; 5. washing the positive plate with water, removing the residual negative plate active substance and separator on the positive plate, soaking in ionized water, taking out the positive plate, drying at 60 deg.C for 10-15 hr until the positive plate is dried thoroughly, and storing the dried positive plate in a drying environment with humidity below 15-20%; 6. the dry positive plate adopts a special device for a paste-grid separator, and is sequentially fed into a lead paste-grid separator and a positive plateRolling the plate by roller and separating by grid mesh to obtain block and powder positive plate active material (PbO)2) Separated from the grid, and positive active material (PbO) in a paste-grid separator2) Feeding into a grinder, pulverizing the block and coarse powder active substances in the grinder, grinding into micron-sized powder, and sieving with a 300-mesh sieve to obtain PbO2A conductive material stored in a dry environment for later use; 7. when applied, PbO2The conductive material is dry-mixed with lead powder and other positive electrode additives according to the proportion of 1.5-5% of the amount of the lead powder, and then water and acid are added according to the process specification to prepare the positive plate.
Preferably, the battery in step 1 comprises an electric moped, an electric motorcycle lead-acid battery, an automobile starting lead-acid battery and a communication standby lead-acid battery.
Preferably, the continuous charging time of the lead-acid storage battery in the step 2 is 3-5 h.
Preferably, the monomer lead-acid storage battery in the step 3 is continuously charged for 10-15 h.
Preferably, the dissection process of step 4 should avoid short-circuit discharge of the positive and negative electrodes.
Preferably, the soaking time in the step 5 is 0.5-1h by using ionized water.
Preferably, the humidity of the drying environment in step 6 is less than 15-20%.
As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following advantages:
the invention relates to a low-cost PbO for promoting formation of a positive plate of a lead-acid storage battery2The invention relates to a preparation method of a conductive material, which recycles active substances on a positive plate from a recycled waste battery positive plate and prepares PbO with better conductivity than red lead2The conductive material has the advantages of low cost and high efficiency, and the production cost is reduced; compared with the method, the method obviously has higher cost and lower conductivity than the method, and the method changes the original PbO which is produced by recovering the waste batteries to smelt the lead ingots again and then producing the lead ingots into red lead2To a problem of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Low-cost PbO for promoting formation of positive plate of lead-acid storage battery2Preparing a conductive material, namely selecting a battery to be recovered: the adopted old lead-acid storage battery can be single or multiple batteries, and the batteries comprise an electric moped, a lead-acid storage battery for electric motorcycle starting, a lead-acid storage battery for automobile starting and a lead-acid storage battery for communication standby; the old batteries were then charged and screened: firstly, 2.50-2.60V constant voltage and 0.4-0.8C limitation are adopted for a single 2V lead-acid storage battery2Charging the current until the voltage reaches 2.50-2.60V, and then continuously charging for 3-5 h; removing the battery which is charged for 6 hours, wherein the voltage of the battery cell is lower than 2.4V, or the voltage of the battery cell is lower than 2.20V within 2 hours after the charging is finished; the screened battery is subjected to 0.3-0.6C treatment2Current overcharge was carried out for 10-15 h: for open cells with openable lids, deionized water can be added until the level of the liquid exceeds the pole group before overcharging; the dissecting battery separates the positive plate from the negative plate, the partition plate and the plastic shell, and the dissecting process should avoid short-circuit discharge of the positive and negative electrodes; washing the positive plate with water, removing the residual negative plate active substance and separator on the positive plate, soaking in ionic water for 0.5-1h, taking out the positive plate, drying at 60 deg.C for 10-15h until the positive plate is dried thoroughly, and storing the dried positive plate in a drying environment with humidity below 15-20%; the dry positive plate adopts a special device for a paste-grid separator, the positive plate is sequentially fed into the lead paste-grid separator, and is rolled by a roller and separated by a grid net to separate active substances (PbO) of the blocky and powdery positive plates2) Separated from the grid, and positive active material (PbO) in a paste-grid separator2) Feeding into a grinder, pulverizing the block and coarse powder active substances in the grinder, grinding into micron-sized powder, and sieving with a 300-mesh sieve to obtain PbO2The conductive material is stored in a dry environment with the humidity lower than 15-20% for later use; when applied, PbO2The conductive material is lead powderMixing 1.5-5% of the positive electrode paste with lead powder and other positive electrode additives in a dry mode, adding water and acid according to the process specification, and preparing the positive electrode plate by paste;
example 2
Low-cost PbO for promoting formation of positive plate of lead-acid storage battery2Preparing a conductive material: in order to reduce the cost of materials, the selected materials are waste lead-acid storage batteries, the recovered lead-acid storage batteries of different types can be used, the recovered waste lead-acid storage batteries are charged firstly, the single 12V20Ah lead-acid storage battery is charged for 3-5 h by adopting a constant voltage limit of 15.0-15.6V and 4A current, and then the charging is carried out for 8h by adopting 4A current; after the charging is stopped for 2 hours, dissecting the battery with the voltage higher than 13.2V, and separating the positive plate, the negative plate, the partition plate and the plastic shell; soaking the positive plate in water for 1h, cleaning to remove residual negative active substances and a separator, soaking in ionized water for 1h, taking out the positive plate, drying at 60 ℃ for 10-15h, and storing the dried positive plate in a drying environment with the humidity lower than 15-20%; separating active substance of the dry positive plate from the grid by a paste-grid separator, and separating the positive active substance (PbO) in the paste-grid separator2) Simultaneously crushing and grinding the raw materials into micron-sized powder, and sieving the micron-sized powder with a 300-mesh sieve to obtain PbO2And the conductive material is stored in a dry environment with the humidity lower than 15-20% for later use.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. Low-cost PbO for promoting formation of positive plate of lead-acid storage battery2The preparation method of the conductive material comprises the following steps:
(1) firstly, selecting the batteries needing to be recovered: the used lead-acid storage battery can be single or multiple batteries;
(2) then charging and screening the old battery: firstly, 2.50-2.60V constant voltage and 0.4-0.8C limitation are adopted for a single 2V lead-acid storage battery2Charging the current until the voltage reaches 2.50-260V, and then charging is continued. Removing the battery of which the cell voltage is lower than 2.4V within 6h after charging or the cell voltage is lower than 2.20V within 2h after charging;
(3) and overcharging the screened battery: 0.3-0.6C is adopted for the lead-acid storage battery2Continuously charging the current; for open cells with openable lids, deionized water can be added until the level of the liquid exceeds the pole group before overcharging;
(4) dissecting the battery to separate the positive plate from the negative plate, the separator and the plastic shell;
(5) washing the positive plate with water, removing the residual negative plate active substances and the separator on the positive plate, soaking the positive plate in ionized water, taking out the positive plate, drying at the temperature of 60 ℃ for 10-15h until the positive plate is dried completely, and then storing the dried positive plate in a drying environment with the humidity of less than 15-20%;
(6) the dry positive plate adopts special equipment for a paste-grid separator, the positive plate is sequentially fed into the lead paste-grid separator, and is rolled by a roller and separated by a grid net to separate active substances (PbO) of the blocky and powdery positive plates2) Separated from the grid, and positive active material (PbO) in a paste-grid separator2) Feeding into a grinder, pulverizing the block and coarse powder active substances in the grinder, grinding into micron-sized powder, and sieving with a 300-mesh sieve to obtain PbO2A conductive material stored in a dry environment for later use;
(7) when applied, PbO2The conductive material is dry-mixed with lead powder and other positive electrode additives according to the proportion of 1.5-5% of the amount of the lead powder, and then water and acid are added according to the process specification to prepare the positive plate.
2. Low cost PbO for facilitating positive anodization of lead acid batteries according to claim 12The preparation of the conductive material is characterized in that: the battery in the step (1) comprises an electric moped, a lead-acid storage battery for electric motorcycle, a lead-acid storage battery for automobile starting and a lead-acid storage battery for communication standby.
3. The promoted lead-acid of claim 1Low-cost PbO formed by positive plate of storage battery2The preparation of the conductive material is characterized in that: and (3) continuously charging the lead-acid storage battery in the step (2) for 3-5 h.
4. Low cost PbO for facilitating positive anodization of lead acid batteries according to claim 12The preparation of the conductive material is characterized in that: and (4) continuously charging the monomer lead-acid storage battery for 10-15h in the step (3).
5. Low cost PbO for facilitating positive anodization of lead acid batteries according to claim 12The preparation of the conductive material is characterized in that: the dissection process of the step (4) should avoid short-circuit discharge of the positive electrode and the negative electrode.
6. Low cost PbO for facilitating positive anodization of lead acid batteries according to claim 12The preparation of the conductive material is characterized in that: in the step (5), the soaking time is 0.5-1h by adopting the ionized water.
7. Low cost PbO for facilitating positive anodization of lead acid batteries according to claim 12The preparation of the conductive material is characterized in that: and (4) the humidity of the drying environment in the step (6) is lower than 15-20%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910738167.0A CN111704158A (en) | 2019-08-12 | 2019-08-12 | Low-cost PbO for promoting formation of positive plate of lead-acid storage battery2Preparation of conductive materials |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910738167.0A CN111704158A (en) | 2019-08-12 | 2019-08-12 | Low-cost PbO for promoting formation of positive plate of lead-acid storage battery2Preparation of conductive materials |
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| CN111704158A true CN111704158A (en) | 2020-09-25 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1283699C (en) * | 1986-01-06 | 1991-04-30 | Basanta K. Mahato | Method of improving the formation efficiency of positive plates of a lead-acid battery |
| CN101286583A (en) * | 2008-05-22 | 2008-10-15 | 潘孝坤 | Recycling and re-using process for waste lead acid accumulator |
| CN101388479A (en) * | 2008-11-07 | 2009-03-18 | 莫绚宗 | Renovating method for lead-acid accumulator |
| CN102347516A (en) * | 2011-10-26 | 2012-02-08 | 浙江天能电池江苏新能源有限公司 | Inner forming process of tubular lead-acid storage battery |
| CN105870527A (en) * | 2016-03-30 | 2016-08-17 | 超威电源有限公司 | Treatment method for positive plate lead paste in waste lead-acid battery |
| CN106920998A (en) * | 2017-03-22 | 2017-07-04 | 超威电源有限公司 | The method for preparing metallic lead containing scrap lead using old and useless battery |
| CN107749504A (en) * | 2017-10-09 | 2018-03-02 | 超威电源有限公司 | A kind of waste and old lead acid accumulator recycling processing method |
-
2019
- 2019-08-12 CN CN201910738167.0A patent/CN111704158A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1283699C (en) * | 1986-01-06 | 1991-04-30 | Basanta K. Mahato | Method of improving the formation efficiency of positive plates of a lead-acid battery |
| CN101286583A (en) * | 2008-05-22 | 2008-10-15 | 潘孝坤 | Recycling and re-using process for waste lead acid accumulator |
| CN101388479A (en) * | 2008-11-07 | 2009-03-18 | 莫绚宗 | Renovating method for lead-acid accumulator |
| CN102347516A (en) * | 2011-10-26 | 2012-02-08 | 浙江天能电池江苏新能源有限公司 | Inner forming process of tubular lead-acid storage battery |
| CN105870527A (en) * | 2016-03-30 | 2016-08-17 | 超威电源有限公司 | Treatment method for positive plate lead paste in waste lead-acid battery |
| CN106920998A (en) * | 2017-03-22 | 2017-07-04 | 超威电源有限公司 | The method for preparing metallic lead containing scrap lead using old and useless battery |
| CN107749504A (en) * | 2017-10-09 | 2018-03-02 | 超威电源有限公司 | A kind of waste and old lead acid accumulator recycling processing method |
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Application publication date: 20200925 |