CN110767955A - Activation method of waste lead paste of lead-acid battery - Google Patents
Activation method of waste lead paste of lead-acid battery Download PDFInfo
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- CN110767955A CN110767955A CN201911060190.5A CN201911060190A CN110767955A CN 110767955 A CN110767955 A CN 110767955A CN 201911060190 A CN201911060190 A CN 201911060190A CN 110767955 A CN110767955 A CN 110767955A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- 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
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- 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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention belongs to the technical field of recycling of waste lead paste of lead-acid batteries, and particularly relates to an activation method of waste lead paste of lead-acid batteries, which comprises the following steps: (1) respectively carrying out grid paste separation on positive and negative plates of the waste lead-acid battery, respectively separating out positive lead paste and negative lead paste, and respectively drying the separated positive lead paste and negative lead paste until the moisture content is less than 0.5%; (2) respectively hammer-grinding the dried positive lead plaster and the dried negative lead plaster to be refined to the particle size of 5-10 mu m; (3) and (3) respectively grinding the positive lead plaster and the negative lead plaster which are subjected to the hammer grinding in the step (2) to be refined to the particle size of 1-5 microns. The activation method of the waste lead plaster of the lead-acid storage battery provided by the invention is based on the damage mechanism of the lead-acid storage battery, adopts a common mechanical method to change coarse-grain lead sulfate into active fine-grain lead sulfate, and achieves the purpose of activating the lead sulfate by controlling the grain size.
Description
Technical Field
The invention belongs to the technical field of recycling of waste lead paste of lead-acid batteries, and particularly relates to an activation method of waste lead paste of lead-acid batteries.
Background
The waste lead plaster is a main component separated from the lead-acid storage battery, and because the waste lead plaster contains a large amount of sulfate and lead oxides with different valence states, the recycling of the lead plaster is generally a difficult point requiring intensive research on recycling of the waste lead-acid storage battery.
For the recovery of waste lead plaster, the metal lead is generally recovered by adopting a pyrometallurgical technique, a hydrometallurgical technique, a solid-phase electrolysis process and the like at present. Wherein pyrometallurgical techniques may produce SO2Secondary pollution such as high-temperature lead dust and the like, high energy consumption and low utilization rate; the wet smelting technique is that waste lead paste is desulfurized by alkali metal carbonate, and PbO is desulfurized by reducing agent2After being converted into PbO, lead is transferred into lead-rich electrolyte under the action of a leaching agent, and then electrolytic deposition is carried out to obtain refined lead; the electrolytic deposition technology avoids the high-temperature condition of the pyrogenic recovery technology from generating no smoke dust and SO2But the energy consumption is still quite high, and the power consumption of 1kg lead is about 12 k.Wh which is higher than that of a pyrometallurgical method; the solid phase electrolysis process adopts NaOH solution as electrolyte, a stainless steel plate with a folding groove on the surface is used as a cathode and an anode, lead plaster slurried by 8mol/L NaOH solution is filled in the folding groove, and a lead-containing compound is obtained from a cathode during electrification and electrolysis and is directly reduced into metallic lead.
In addition, the process of pre-desulfurization and low-temperature smelting of the waste lead paste is an artificial lead clean recovery process, so that the prior art generally starts from waste lead paste desulfurization (such as Xuxin 'utilization of the regenerated lead paste in the production process of lead-acid storage batteries' (J. Guangdong chemical industry 2015,4(42): 31-34; and such as bamboo waves and other 'desulfurization experiments by the internal circulation particle grinding method of the waste lead paste' (J. industrial safety and environmental protection 2018,2(44): 93-96), and such as Taiwan patent with the publication number of TW 201541685A), the next step of treatment is carried out after the desulfurization pretreatment is carried out, so that the energy consumption is increased, and secondary pollution is also generated in the desulfurization process.
In the prior art, the activation method mainly comprises five methods, namely a heavy current charging method, a negative pulse charging method, a method of adding an active agent (such as a patent with the application publication number of CN 105870530A), a high-frequency pulse charging method and a composite pulse resonance method, wherein the heavy current charging method can only obtain temporary effect when the vulcanization is eliminated, and can aggravate water loss and softening of the positive plate; the negative pulse charging method has no obvious effect, and the method for adding the active agent has high cost and short service life after activation; the high-frequency pulse charging method has long charging time, low working efficiency and poor effect when the vulcanization is serious; the composite pulse resonance method has high cost and complex technology and equipment, and the five activation methods are all used for activating and repairing the whole system of the vulcanized and damaged finished battery, are the activation and repair completed under the common cooperation of various components in the battery, and are not used for activating the components of the waste lead paste independently.
Disclosure of Invention
The invention aims to provide a method for activating waste lead plaster of a lead-acid storage battery, so as to solve one or more of the problems.
According to one aspect of the invention, the method for activating the waste lead paste of the lead-acid battery comprises the following steps:
(1) respectively drying the positive lead plaster and the negative lead plaster of the waste lead-acid battery until the moisture content is less than 0.5%;
(2) respectively hammer-grinding the dried positive lead plaster and the dried negative lead plaster to be refined to the particle size of 5-10 mu m;
(3) and (3) respectively grinding the positive lead plaster and the negative lead plaster which are subjected to the hammer grinding in the step (2) until the particle size is 1-5 mu m.
The activation method of the waste lead plaster of the lead-acid storage battery provided by the invention provides a brand new angle and idea to solve the problem of recycling the waste lead plaster, because the lead plaster components of the scrapped storage battery generally contain active fine-grain lead sulfate, salinized coarse-grain lead sulfate, lead dioxide, lead oxide and lead, and the active fine-grain lead sulfate, lead dioxide, lead oxide and lead are effective substances in a storage battery polar plate and can be added into the lead plaster produced by a new storage battery for recycling; the salinized coarse-grained lead sulfate is white coarse-grained lead sulfate generated on a lead-acid storage battery pole plate, is called lead sulfate hardening or crystallization, and is called vulcanization or polarization or sulfation for short, the coarse-grained lead sulfate has large particles, small contact area with electrolyte and poor conductivity, is difficult to convert into lead dioxide and sponge-like pure lead during normal charging, can block pores of active materials, hinders the permeation of the electrolyte, obviously increases the internal resistance of the storage battery, and affects the performance of the storage battery. It is generally accepted in the industry that the lead paste of the discarded storage battery contains coarse-grained lead sulfate, and the waste lead paste cannot be recycled, but the invention recycles the waste lead paste from the perspective of activating the coarse-grained lead sulfate.
Specifically, the activation method of the lead-acid storage battery waste lead plaster provided by the invention is based on the lead-acid storage battery damage mechanism, adopts a common mechanical method to change coarse-grain lead sulfate into active fine-grain lead sulfate aiming at the waste lead plaster, and achieves the purpose of activating the lead sulfate by controlling the grain size; the activation method has simple steps, easy operation and high feasibility, can directly utilize the existing equipment of manufacturers to carry out activation treatment, can directly use the treated waste lead plaster for preparing the lead plaster, and provides a brand new angle and thought for the recycling of the waste lead plaster. It is worth to say that the activation according to the invention is the conversion of lead sulphate to lead dioxide or spongy lead during charging of the battery and vice versa during discharging.
In some embodiments, the drying step (1) comprises the following steps: putting the lead plaster into a stainless steel tank, stacking to a thickness of less than 10mm, placing in a drying chamber, and drying at 100 +/-10 ℃ until the moisture content is less than 0.5%.
In some embodiments, the positive lead plaster and the negative lead plaster in the step (2) are both 5-10 μm in particle size after being subjected to hammer milling; in the specific operation process, a negative pressure air cloth bag powder collector is used for achieving the fineness, the aperture of the cloth bag is less than 10 mu m, and the air pressure hammer mill is in a micro negative pressure state.
In some embodiments, the positive lead plaster and the negative lead plaster in the step (3) have the grain diameter of 1-5 μm after being ground and refined, and the apparent specific gravity is 1.10-1.30g/cm3。
According to one aspect of the invention, the application of the positive electrode lead plaster powder activated by the activation method in preparing the positive electrode lead plaster is provided, wherein the addition amount of the activated positive electrode lead plaster powder is 20-25% of the weight of the lead powder.
The activated anode lead plaster powder is used for preparing anode lead plaster, and PbO can be controlled2The crystal form ensures that the performance indexes of the storage battery, such as initial capacity, cycle service life and the like, meet the national standard requirements.
It is worth to say thatThe lead plaster powder activated by the activation method of the invention is one of key technologies when being used for producing a new storage battery and the formula of the plaster, and because the waste plaster powder contains PbSO4Recalculating the addition amount of the paste sulfuric acid according to the amount of the sulfate radical to ensure that the sulfuric acid content meets the acid content requirement; PbO2Middle α -PbO2And β -PbO2The proportion of the lead-acid mixed powder is changed, and the crystal-changing agent needs to be added to meet the performance requirement of a new storage battery, so that the formula of the auxiliary material of the positive electrode and the formula of the acid content of the positive electrode and the negative electrode need to be adjusted by adding the waste lead plaster powder.
In some embodiments, the positive lead paste comprises 0.1% -0.15% Sb by weight of lead powder2O30.5% -0.6% of phosphoric acid and 0.02% -0.03% of magnesium sulfate. Wherein:
Sb2O3(antimony trioxide) is used as a crystal modifier, and antimony ions play an electrocatalysis role in the basic lead sulfate conversion process in the formation charging process of the storage battery manufacture, so that the formation resistance is reduced, the formation temperature is reduced, and β -PbO is effectively reduced2Generating; in addition, antimony ions can also improve PbO during charging of the storage battery2The electronic conductive property of the crystal gel area stabilizes the crystal gel concentration during the reaction of the crystal gel area, thereby improving the conductivity of the electrode in the later reaction stage and stabilizing α -PbO2The ratio of (a) to (b). This is because PbO is contained in the components of the waste lead paste2From activated PbO2And softening PbO2Composition of active PbO2Can directly participate in the charge-discharge reaction of the storage battery to soften PbO2Is α -PbO2Conversion to β -PbO2As a result, the main components of the positive plate of the storage battery are scrapped in deep discharge and large-current discharge; softening PbO2The positive plate of the new storage battery needs to be added with a crystal modifier to ensure α -PbO2The content satisfies the supporting function in the battery.
Adding phosphoric acid (H) into the positive lead plaster3PO4) The lead and lead alloy can then react with phosphoric acid to form an intermediate product Pb3(PO4)2，Pb3(PO4)2The existence of the positive plate prevents the grid alloy and the positive plate active substance PbO2PbO at the interface2Reduction to PbSO4Speed, especially of the plateA transition layer between the grid alloy and corrosion products, and α -PbO between the grid alloy and the corrosion products inner layer when the transition layer is present2The binding force between the two plates is improved, so that the corrosion product has a better protective layer, and the service life of the grid can be prolonged. Intermediate product Pb3(PO4)2Also improves the grid corrosion inner layer α -PbO2β -PbO with outer layer2The binding force between the active substances and the grid is improved, and the falling of the active substances is reduced; in addition, the addition of phosphoric acid is to PbO2+H2SO4→PbSO4+H2O+1/2O2Has a certain inhibiting effect on the discharge reaction process, thereby reducing PbO2Self-discharge of (1).
Therefore, 0.5 to 0.6 percent of phosphoric acid is added into the positive lead paste, so that the positive lead paste has the following effects of (1) improving the binding force of a grid material and a corrosion product, and reducing the formation of a blocking layer during grid alloy corrosion and deep discharge of a lead-calcium alloy grid; (2) reduction of positive electrode active material PbO2The softening speed of the battery reduces the falling of the battery, thereby prolonging the cycle life of the battery; (3) inhibiting self-discharge of the storage battery; (4) reduce the sulfation of the polar plate when the plate is placed after deep discharge. The amount of the added phosphoric acid is well controlled, and if the amount of the added phosphoric acid is more than the required amount, the negative effect on the capacity, the starting capability and other properties of the storage battery can be generated.
Magnesium sulfate (MgSO)4) The magnesium sulfate is added into the positive lead plaster in 0.02-0.03% to generate a lead oxide hydrate, the lead oxide hydrate is glued like gypsum, and the substance generates a crystal structure in the lead plaster when the pole plate is dried, so that the pole plate has good bonding effect, and when the solidification effect is completely finished, the substance can be leached from the active substance (dissolved in water) in the standing process to be separated from the lead plaster, so that pores are left, and the porosity of the pole plate is improved.
Further, when the activated positive electrode lead paste powder is added to the positive electrode lead paste, the positive electrode lead paste may have a formula of: 100kg (containing activated anode paste powder 20-25kg) lead powder, 9.6-10.0kg density of 1.32 + -0.005 g/cm360 g. + -. 5g of staple fibres60g +/-5 g of carbon black, 0.10-0.15kg of antimony trioxide, 0.02-0.03kg of magnesium sulfate, 0.5-0.6kg of phosphoric acid and 9.6-10.4kg of water; the apparent density of the positive electrode lead paste obtained by the existing preparation method is 4.1-4.2g/cm3。
According to one aspect of the invention, the application of the negative electrode lead plaster powder activated by the activation method in preparing the negative electrode lead plaster is further provided, wherein the addition amount of the activated negative electrode lead plaster powder is 15-20% of the weight of the lead plaster.
Specifically, when the activated negative electrode lead paste powder is added to the negative electrode lead paste, the formula of the negative electrode lead paste is as follows: 100kg (containing activated negative electrode paste powder 15-20kg) lead powder 8.4-8.6kg with density of 1.32 + -0.005 g/cm350g plus or minus 5g of short fiber, 600g plus or minus 5g of barium sulfate, 0.16 to 0.18kg of acetylene black, 0.2 to 0.3kg of sodium lignosulphonate and 8.4 to 9.2kg of water; the apparent density of the negative pole lead paste obtained by the prior preparation method is 4.2-4.4g/cm3。
The activated lead plaster powder is used for preparing lead plaster, so that the initial capacity of the storage battery can be increased, the charging ampere hour of the storage battery formation can be reduced, the charging time can be shortened, and the electric energy can be saved.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention;
FIG. 2 is an SEM image of the lead paste powder at 5K before and after activation, wherein the left image is before activation and the right image is after activation;
FIG. 3 is an SEM image of the lead paste powder at 15K before and after activation, wherein the left image is before activation and the right image is after activation;
FIG. 4 is a morphology of a positive grid containing activated positive lead paste powder after charging and discharging;
fig. 5 is a diagram showing a negative plate grid containing activated negative lead paste powder after charging and discharging.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A method for activating waste lead plaster of a lead-acid battery comprises the following specific steps:
(1) disassembling a waste lead-acid storage battery, separating the storage battery conveyed at a constant speed along a polar plate lug by using a band saw parallel to the ground, taking out a polar group after separation, and separately placing and respectively processing a positive plate, a negative plate and a partition plate, wherein the purpose of the separate processing of the positive plate and the negative plate is to respectively add the positive plate and the negative plate into positive lead paste and negative lead paste during the production and the use of a new storage battery, so that the influence of auxiliary materials in the negative plate on the polar plate is avoided;
(2) separating the positive plate and the negative plate, and storing, processing and using the positive plate and the negative plate separately;
(3) separating grid paste by using a grid paste separator, putting a polar plate on a stainless steel conveying grid belt, wherein the polar plate cannot be superposed, pressing the polar plate by using a pair of rollers, feeding the polar plate into a two-stage grid belt and extruding the polar plate by using a convex tooth rolling shaft to separate lead paste from a grid, and screening the lead paste by using a vibrating screen;
(4) respectively drying the positive and negative lead pastes, putting the dried positive and negative lead pastes into respective stainless steel grooves, stacking the positive and negative lead pastes to a thickness of less than 10mm, putting the positive and negative lead pastes in a drying chamber, and drying the positive and negative lead pastes at a temperature of 100 ℃ for 24 hours until the water content is less than 0.5%;
(5) drying the positive and negative lead pastes with qualified water content, storing the positive and negative lead pastes in a powder bin, respectively performing hammer milling on the positive and negative lead pastes by using a hammer mill to refine the lead pastes, and winnowing the lead paste powder with the particle size of less than 10 mu m;
(6) respectively refining the positive and negative lead pastes processed in the step (5) for the second time by using a grinder to obtain activated positive lead paste powder and activated negative lead paste powder, wherein the particle diameters of the positive lead paste powder and the negative lead paste powder are 1-5 mu m, and the apparent specific gravity is 1.10-1.30g/cm3。
Adding the activated positive lead paste powder prepared by the activation method of example 1 into positive lead paste according to 20% of the weight of the lead powder, adding the activated negative lead paste powder into negative lead paste according to 15% of the weight of the lead powder, preparing the positive lead paste containing the activated positive lead paste powder and the negative lead paste containing the activated negative lead paste powder into a positive plate and a negative plate according to the existing method for preparing a lead-acid battery, and preparing a lead-acid battery; the size of the positive plate is 100mm 142mm 1.6/1.8mm, the size of the negative plate is 100mm 142mm 1.2/1.4mm, the lead-acid battery comprises 8 positive plates, 9 negative plates and a PE separator with the thickness of 1.0 mm.
The battery numbers A01, A02, A03, A04, A05 and A06 respectively represent the batteries prepared by adding 20% of activated lead paste powder to the positive electrode and 15% of activated lead paste powder to the negative electrode according to the existing production process, and the batteries are tested according to the standard of lead-acid storage batteries for starting (GB/T5008-2013), and the test results are shown in Table 1.
TABLE 1 Battery Performance test Table
The data in Table 1 show that all indexes of the battery can meet the national standard requirements of GB/T5008-2013, and the quality of the storage battery product is not influenced by the addition of the above amount.
Specifically, for the control of the grinding fineness, the invention realizes the following by controlling the adding amount of the waste lead plaster and the grinding time length:
taking a grinder with power of 30KW for grinding the waste lead paste powder as an example, 0.4 ton of paste powder is put into the grinder for 1 hour, the particle diameter of the paste powder before grinding is 5-10 μm, and the particle diameter after grinding is 1-3 μm. The particle size will vary with the grinding time, but the particle size will not change significantly after grinding with an increase of grinding time longer than 1 hour, and the specific grinding time for grinding paste powder with an average particle size of 10 μm will give the average particle size of the paste powder shown in Table 2.
TABLE 2 mean particle size of the paste powders obtained at different grinding times
| Length of grinding | 40min | 50min | 60min | 70min |
| Particle size of the paste after 0.3 ton grinding | 7μm | 6μm | 5μm | 4.5μm |
| Particle size of the paste after 0.4 ton grinding | 6μm | 4μm | 2μm | 2μm |
| Particle size of the paste after 0.5 ton grinding | 8μm | 6μm | 4.5μm | 4.3μm |
As can be seen from table 2, by controlling the amount of the waste lead paste and the grinding time, paste powder (i.e., activated paste powder) having a desired particle size range can be obtained.
The activated positive lead paste powder with different particle sizes was added to the positive lead paste to manufacture a new storage battery, and the content of lead dioxide in the positive plate was tested as shown in table 3.
TABLE 3 content of lead dioxide after applying activated anode lead plaster powder of different particle diameters to anode lead plaster
As can be seen from Table 3, the particle size of the activated positive electrode lead paste powder is less than 6 μm to meet the use requirement.
In addition, the activated anode lead plaster powder is used for preparing anode lead plaster, and PbO can be controlled2Crystal form of PbO2From α -PbO2And β -PbO2Composition α -PbO2Small charge capacity but large volume, ratio β -PbO2Hard and mainly plays a supporting role, β -PbO2Large charge capacity but small volume, ratio of α -PbO2The lead paste of the soft storage battery mainly plays a role of charging and the failure storage battery is softened, part of the lead paste falls off, and the lead paste α -PbO is softened2The content is low, when the lead plaster is recycled for producing a new storage battery, the formula of the lead plaster should be changed, the temperature of the lead plaster should be strictly controlled, the lead plaster should be reprogrammed to be a charging program, and finally α -PbO is realized2Ratio β -PbO2The battery capacity is between 0.7 and 0.8, so that the performance indexes of the initial capacity, the cycle service life and the like of the storage battery meet the national standard requirements.
Therefore, when the activated positive lead plaster powder is used for preparing positive lead plaster, 0.1-0.15% of Sb is added2O3As a crystal modifier, in the formation and charging process of the storage battery manufacture, antimony ions play an electrocatalysis role in the basic lead sulfate conversion process, the formation resistance is reduced, the formation temperature is reduced, and β -PbO is effectively reduced2And (4) generating. In addition, antimony ions can also improve PbO during charging of the storage battery2The electronic conductive property of the crystal gel area stabilizes the crystal gel concentration during the reaction of the crystal gel area, thereby improving the conductivity of the electrode in the later reaction stage and stabilizing α -PbO2The ratio of (a) to (b).
α -PbO control on the production process of the storage battery2And β -PbO2Ratio, to increase α -PbO2The lead paste is generated under the alkalescent condition when the lead paste is mixed, namely the temperature of the mixed paste is effectively controlled to be less than 40 ℃, so that PbO PbSO in the lead paste component is ensured4H2O and 3PbOPbSO4H2The content of O is increased, and the content of 4PbO PbSO is reduced4H2The process of multiple discharge, reducing polarization internal resistance and lowering formation charging temperature is adopted during the formation of the storage battery, so that the formation temperature of charging is easy to control below 40 ℃, and the anode α -PbO is facilitated2Is generated by α -PbO2The content of (B) meets the requirements of a new storage battery.
Specifically, the formation charging procedure is as follows: the whole process is divided into 11 stages according to formation charging time, each stage is 2 hours, the charging current of the first stage is 30% I, the charging current of the middle three stages is 100% I, and the charging current of the rest stages is 80% I. The other stages except the first stage all need to discharge once in 20 minutes, the discharge current is 200% I, and the discharge time is 1 min. The current I is calculated from the plate area and the number of positive plates, i.e. the charging current I is equal to, the positive plates are high by wide 2 (both sides) by 10mA/cm2, the number of positive plates is e.g. 6-QW-100Ah cells are assembled with plates of height 100mm and width 142mm, 7 positive plates per cell, 8 negative plates for 6 cells, 12V accumulator. Calculating the charging current: i100 × 142 × 2 × 10 × 7/100000 ═ 19.88A, and the discharge current was equal to 19.88 × 2 ═ 39.76A.
The method comprises the steps of changing a formation charging procedure of a storage battery, carrying out a cyclic service life comparison test with an original formation charging procedure capacity, and testing the storage battery according to the standard of 'starting lead-acid storage battery' (GB/T5008-2013), wherein 1# -3# is a battery with an improved charging procedure, 4# is an original formation procedure battery, assembling 6-QW-100Ah batteries with the same number of plates (added with 20% of activation waste paste powder) and testing, wherein the testing results are shown in Table 4.
TABLE 4 comparison of Battery Performance before and after Change of formation charging procedure
| Index (I) | Standard of merit | 1# | 2# | 3# | 4# |
| Reserve capacity | ≥182min | 205 | 206 | 205 | 180 |
| Cyclic durability | Not less than 120 times | 131 | 129 | 130 | 119 |
As can be seen from Table 4, the reserve capacity of the battery with the improved charging procedure is far higher than that before the improvement, and the lifting rate is as high as 14.4%; the cycling durability of the battery with improved charging procedure is also greatly improved, with a 10.08% improvement over the battery before improvement.
The activation of the waste lead paste by the method of the present invention is illustrated by the following experiment.
First, determination of particle size
Firstly, physically disassembling the waste battery, taking out the positive and negative plates for respective treatment, washing the surfaces of the plates to remove part of the attached sulfuric acid, and air-drying until the surfaces are free of moisture; separating lead plaster from a grid by using a plaster grid separator, and hammering and grinding into lead plaster powder;
then, the lead paste powder was subjected to secondary grinding using a small mill (home flavor grinder), each for 10 minutes, about 1kg, particle size analysis as shown in Table 5, and median diameter (D50) was 4.077 μm.
TABLE 5 particle size distribution chart of lead plaster powder before and after activation
It can be seen from table 5 that the unrefined anode waste lead plaster powder has large particle size, the medium particle size reaches 11.02um, and the refined anode waste lead plaster powder (i.e. activated anode lead plaster powder) has a medium particle size of 4.07um, so that the crushing is effective, but not thorough, the fineness of the lead powder is not reached, and the crushing equipment needs to be continuously improved or the lead plaster powder crushing time needs to be prolonged to achieve the aim of normal lead powder fineness. Screening the activated positive lead paste powder to obtain positive lead paste powder with the particle size of less than or equal to 5 microns, and adding the positive lead paste powder into the positive lead paste.
Scanning electron micrographs of the lead paste powder before and after activation are shown in FIG. 2 (X5K) and FIG. 3 (X15K), and are shown by mirror images: the test results were in agreement with the results of the particle size analysis.
Second, battery assembly
1) Adding the activated negative lead plaster powder into the negative lead plaster to prepare a negative plate, and encapsulating the negative plate by using a PE partition plate with the base thickness of 0.25mm and the total thickness of 0.8 mm;
2) adding activated positive lead plaster powder into positive lead plaster to prepare a positive plate, wherein the positive plate uses 7 common AGM electrode plates, 13 single grid electrode plates are matched and then manually welded with a busbar, 6 groups are welded together and put into a 6-grid 12-volt L2(60Ah) battery shell, after the connection is confirmed to be correct, 6 grids are welded with flat tabs through a wall-penetrating welding machine, 6 grids are connected in series, and two poles of the positive electrode and the negative electrode are welded completely. The electrolysis experiment was carried out by directly adding acid without heat-sealing the large lid and the middle lid.
Third, electrolytic formation (2019/7/13 morning 9:00-2019/7/16 morning 4:00)
1) The preparation concentration is 1.06g/cm3Pouring the sulfuric acid electrolyte into 6 single-grid battery cells, so that each single-grid electrolyte is on the same horizontal plane and is 2cm away from the polar plate;
2) electrolytic tests were conducted using the confirmed charge and discharge electrolysis procedures for removing polarization and improving conversion efficiency of lead paste in the electrode plate, and the specific charge and discharge procedures are shown in table 6.
TABLE 6 Charge/discharge schedule for electrolytic test
After the charging and discharging are finished, the charging and discharging records are checked to be visible: the highest voltage of the single cell is 2.44V, so the solid phase electrolysis voltage can be selected to be 3V at most. According to the common AGM battery negative electrode-coated positive electrode plate, the effective positive electrode plate is 5, the capacity can be calculated to be 71AH by 114 g/5 pieces/8 g/Ah, and the total sufficient electricity quantity 400Ah is calculated from the table and is 5.6 times of the charge quantity of the battery. The plate size used was 129mm 148mm 19092mm2The maximum charging current is 9A, and the maximum value of the electrolytic formation current is 47.14mA/cm2。
3) Water loss occurs in the charging process, pure water is supplemented timely to ensure normal charging efficiency, and the minimum distance between the polar plate and the liquid level is ensured to be 1 cm. Therefore, pure water was added 4 times in total during charging, and 60ml was added to each cell, and the electrolyte level was maintained at the original level after the addition of pure water.
Four, plate assay
1) Measuring the sulfuric acid concentration after formation
The sulfuric acid concentration after the formation is shown in Table 7.
TABLE 7 sulfuric acid concentration after formation
| Battery cell | 1. Grid (C) | 2. Grid (C) | 3. Grid (C) | 4. Grid (C) | 5. Grid (C) | 6. Grid (C) |
| Density of | 1.351 | 1.357 | 1.366 | 1.365 | 1.385 | 1.355 |
| Temperature of | 33.0 | 33.9 | 34.3 | 33.9 | 33.8 | 33.3 |
The volume of the electrolyte is constant, the concentration of the sulfuric acid is increased, and the SO in the positive and negative polar plates can be proved4 2-The radical ions obtain electrons to generate sulfuric acid, and the density of the sulfuric acid entering the electrolyte is increased.
2) Detecting CCA values
The CCA value is a main index for measuring the starting capability of the storage battery, and is also one of the methods for judging the charging formation degree of the storage battery, according to the battery parameters of 7 positive and 6 negative AGM polar plates, the standard value voltage is 13.1-13.2V, and the CCA is more than 650A.
And (3) detection and display: the voltage of the test battery is 13.24V, and the CCA value is 745A, which indicates that the conversion of the active substances of the plate is complete and the conversion of the active substances reaches the standard level.
3) Measuring volume of sulfuric acid solution
And (3) disassembling the pole group in the single cell, putting the acid liquid in the partition plate into a beaker, extracting the acid liquid in the single cell of the storage battery by using a syringe, transferring the acid liquid into the beaker, and pouring the acid liquid in the beaker into a measuring cylinder to obtain the volume of the acid liquid in the single cell of 275 ml.
4) Detecting positive and negative plate components
Taking out each of the positive and negative plates, cleaning with clear water for 4 hours, drying in a drying device with a set temperature of 110 ℃ for 3 hours, and detecting each component.
Positive plate: PbO2The content is 87.9%, the positive grid is black, and the white substance on the edge is lead paste which is not completely reacted, as shown in figure 4.
Negative plate: the PbO content was 8.38%, the Pb content was 91.62%, and the negative plate was gray as shown in fig. 5, indicating that the waste lead paste mass had been converted to spongy lead. But the pole plate needs to be dried during inspection, and partial spongy lead is converted into PbO during drying.
Therefore, the waste lead paste contains PbO and PbO2、PbSO4Wherein PbSO4Because the crystal grains are agglomerated and enlarged in the use process of the storage battery, the crystal grains do not participate in charge-discharge cyclic reaction of the storage battery any more, namely the activity is lost. The method can refine the large-particle lead sulfate in the waste lead plaster through physical crushing treatment to have charging and discharging activity, so that the solid phase electrolysis efficiency is improved, and the conversion efficiency is improved. And after the waste lead paste powder is activated, PbO and PbO2、PbSO4Lead ions in the lead paste can be separated out at the cathode under a weak acid medium, and the waste lead paste is activated to form solid-phase electrolysis of the acid medium.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. The method for activating the waste lead plaster of the lead-acid battery is characterized by comprising the following steps of:
(1) respectively carrying out grid paste separation on positive and negative plates of the waste lead-acid battery, respectively separating out positive lead paste and negative lead paste, and respectively drying the separated positive lead paste and negative lead paste until the moisture content is less than 0.5%;
(2) respectively hammer-grinding the dried positive lead plaster and the dried negative lead plaster to be refined to the particle size of 5-10 mu m;
(3) and (3) respectively grinding the positive lead plaster and the negative lead plaster which are subjected to the hammer grinding in the step (2) to be refined to the particle size of 1-5 microns.
2. The method according to claim 1, wherein the drying step in the step (1) is as follows: and respectively putting the positive lead plaster and the negative lead plaster into a stainless steel tank, stacking the lead plaster to a thickness of less than 10mm, and placing the lead plaster in a drying chamber to be dried at a temperature of 100 +/-10 ℃ until the moisture content is less than 0.5%.
3. The preparation method according to claim 2, wherein the positive electrode lead paste and the negative electrode lead paste in the step (3) are ground and refined to have particle diameters of less than or equal to 5 μm, and apparent specific gravity of 1.10-1.30g/cm3。
4. The use of the positive lead paste powder activated by the activation method according to any one of claims 1 to 3 for preparing positive lead paste, wherein the amount of the activated positive lead paste powder is 20 to 25 percent of the weight of the lead powder.
5. The use according to claim 4, wherein the positive lead paste further comprises 0.1-0.15% Sb by weight of lead powder2O30.5% -0.6% of phosphoric acid and 0.02% -0.03% of magnesium sulfate.
6. The use according to claim 4, characterized in that the positive lead paste consists of the following components: 100kg of lead powder, 9.6-10.0kg of lead powder with the density of 1.32 +/-0.005 g/cm360g plus or minus 5g of short fiber, 60g plus or minus 5g of carbon black, 0.10 to 0.15kg of antimony trioxide, 0.02 to 0.03kg of magnesium sulfate, 0.5 to 0.6kg of phosphoric acid and 9.6 to 10.4kg of water; the 100kg of lead powder contains 20-25kg of activated positive paste powder.
7. According toUse according to claim 5 or 6, characterised in that the positive electrode lead paste has an apparent density of 4.1-4.2g/cm3。
8. Use of the negative electrode lead paste powder activated by the activation method according to any one of claims 1 to 3 in the preparation of negative electrode lead paste, wherein the amount of the activated negative electrode lead paste powder is 15 to 20 percent of the weight of the lead powder.
9. Use according to claim 8, characterized in that the negative lead paste consists of: 100kg of lead powder, 8.4-8.6kg of lead powder with the density of 1.32 +/-0.005 g/cm350g plus or minus 5g of short fiber, 600g plus or minus 5g of barium sulfate, 0.16 to 0.18kg of acetylene black, 0.2 to 0.3kg of sodium lignosulphonate and 8.4 to 9.2kg of water; the 100kg of lead powder contains 15-20kg of activated negative electrode paste powder.
10. Use according to claim 9, wherein the negative lead paste has an apparent density of 4.2-4.4g/cm3。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112420996A (en) * | 2020-10-29 | 2021-02-26 | 天能电池集团股份有限公司 | Method for preparing power battery by utilizing recycled lead powder, positive plate and power battery |
| WO2023014533A1 (en) * | 2021-08-03 | 2023-02-09 | Quanverge Inc. | Serviceable batteries with reusable electrodes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10223264A (en) * | 1997-02-10 | 1998-08-21 | Asaka Riken Kogyo Kk | Deactivating method of used lithium-cobalt secondary battery and cobalt recovering method from used lithium -cobalt secondary battery using the method |
| CN103184340A (en) * | 2011-12-31 | 2013-07-03 | 深圳市雄韬电源科技股份有限公司 | Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster |
| 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 |
| CN106252746A (en) * | 2016-08-25 | 2016-12-21 | 浙江天地之光电池制造有限公司 | A kind of lead crystal accumulator |
-
2019
- 2019-11-01 CN CN201911060190.5A patent/CN110767955A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10223264A (en) * | 1997-02-10 | 1998-08-21 | Asaka Riken Kogyo Kk | Deactivating method of used lithium-cobalt secondary battery and cobalt recovering method from used lithium -cobalt secondary battery using the method |
| CN103184340A (en) * | 2011-12-31 | 2013-07-03 | 深圳市雄韬电源科技股份有限公司 | Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster |
| 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 |
| CN106252746A (en) * | 2016-08-25 | 2016-12-21 | 浙江天地之光电池制造有限公司 | A kind of lead crystal accumulator |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112420996A (en) * | 2020-10-29 | 2021-02-26 | 天能电池集团股份有限公司 | Method for preparing power battery by utilizing recycled lead powder, positive plate and power battery |
| WO2023014533A1 (en) * | 2021-08-03 | 2023-02-09 | Quanverge Inc. | Serviceable batteries with reusable electrodes |
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