CN110729461B - Negative lead paste for lead-acid storage battery and preparation method thereof - Google Patents
Negative lead paste for lead-acid storage battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of storage batteries, and provides a negative electrode lead plaster for a lead-acid storage battery and a preparation method thereof, aiming at solving the problem that the performance of the battery is reduced because lignin in the traditional negative electrode lead plaster for the lead-acid storage battery is easy to dissolve out and reduce in the battery formation and subsequent use processes, wherein the negative electrode lead plaster for the lead-acid storage battery is prepared from the following components in parts by weight: 1000 parts of lead powder, 12-25 parts of lignin functionalized carbon nanotube dispersion liquid, 2-3 parts of humic acid, 2-3 parts of acetylene black, 10-12 parts of barium sulfate, 100-120 parts of deionized water, 80-100 parts of sulfuric acid and 0.5-1 part of short fibers. The lignin used in the negative electrode lead plaster for the lead-acid storage battery is anchored by the carbon nano tubes, so that the battery has better low-temperature performance and cycle life, and the carbon nano tubes can be more uniformly distributed in the negative electrode lead plaster after being functionalized by the lignin, so that the rate capability of the battery is improved.
Description
Technical Field
The invention relates to the technical field of storage batteries, in particular to negative lead plaster for a lead-acid storage battery and a preparation method thereof.
Background
Lignosulfonate (hereinafter referred to as lignin) is a common organic expanding agent in lead-acid storage batteries, has good dispersibility, is an anionic surfactant, and can reduce the surface tension of water and change the properties of an electrode and a solution interface. The lignin in the negative electrode of the lead-acid battery can effectively inhibit the surface shrinkage of the negative active material in the charging and discharging processes, and is beneficial to the storage of the capacity of the battery in the using process. Meanwhile, a large number of researches prove that the lignin can improve the low-temperature performance of the battery. Lignin is a derivative which is various, has a complex structure and uncertain components, but contains functional groups such as hydroxyl group HO-, carbonyl-C ═ O and the like through organic chemical analysis, and is dissolved out to the positive electrode of the battery due to the change of temperature and pH value in the process of forming the battery, and is oxidized and decomposed in the charging process of subsequent use, so that the effect of the lignin gradually disappears, and the performance of the battery is reduced.
The carbon nano tube is used as a one-dimensional nano material, the hexagonal structure connection is perfect, and the carbon nano tube has excellent mechanical, electrical and chemical properties. The carbon nano tube has excellent conductivity, can remarkably improve the low-temperature large-current discharge performance of the battery, and is favorable for recovering the charge of the battery after discharge.
Chinese patent literature discloses 'a negative pole lead plaster and a preparation method thereof', and the application publication number is CN107611426A, the invention is beneficial to improving the strength, the toughness and the conductivity of the lead plaster by adding carbon nano tubes into the lead plaster; the corrosion resistance of the lead plaster is improved by adding the polypropylene fiber into the lead plaster; the service life of the storage battery is prolonged by adding lignin into the lead plaster. However, the carbon nanotubes in the invention are added together with other additives (such as barium sulfate, humic acid, carbon black and the like) in the paste mixing process in the form of powder, but the carbon nanotubes have small size and large specific surface area, and are locally agglomerated and not easy to disperse in the lead paste. Meanwhile, the added lignin is not treated, and a large amount of lignin is dissolved out in the formation process due to the reduction of the pH value of the electrolyte and the increase of the temperature of the battery in the formation process, so that the original effect of the lignin is lost.
Disclosure of Invention
The invention provides the negative electrode lead paste for the lead-acid storage battery, which contains lignin functionalized carbon nanotubes and is beneficial to improving the rate capability of the battery, in order to solve the problem that the battery performance is reduced because lignin in the negative electrode lead paste for the traditional lead-acid storage battery is easy to dissolve out and reduce in the battery formation and subsequent use processes.
The invention also provides a preparation method of the negative lead plaster for the lead-acid storage battery, which avoids directly mixing the raw materials, increases the dispersion effect of the carbon nano tube in the lead plaster, and simultaneously can reduce the shrinkage of a negative active substance and the reduction of low-temperature performance and battery capacity caused by the dissolution of lignin during the use of the battery, thereby playing the synergistic effect of the negative active substance and the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the negative lead plaster for the lead-acid storage battery is prepared from the following components in parts by weight: 1000 parts of lead powder, 12-25 parts of lignin functionalized carbon nano tube, 2-3 parts of humic acid, 2-3 parts of acetylene black, 10-12 parts of barium sulfate, 100-120 parts of deionized water, 80-100 parts of sulfuric acid and 0.5-1 part of short fiber.
The invention uses lignosulfonate to functionalize the carbon nano-tubes in advance through a non-covalent bond method, the carbon nano-tubes functionalized by lignin are dispersed in water in the form of solution, and the lignosulfonate and the carbon nano-tubes are interacted through pi-pi conjugation and hydrophobic bonds, so that the carbon nano-tubes have better dispersibility, and meanwhile, the anchoring effect of the nano-tubes inhibits the dissolution and reduction of the lignin in the battery formation and the subsequent use process. The lignin functionalized carbon nanotubes can be beneficial to the uniform distribution of the carbon nanotubes in active substances, and can inhibit the dissolution of lignin in the processes of formation and battery use.
Preferably, the short fiber is selected from one or more of polyacrylonitrile fiber, polypropylene fiber and polyester fiber.
Preferably, the preparation method of the lignin functionalized carbon nanotube comprises the following steps: uniformly mixing carbon nanotubes, lignin and deionized water according to a mass ratio of (1-5) to (20-30) to (100-300), and performing ball milling treatment to obtain lignin functionalized carbon nanotubes. The deionized water is counted into the total water consumption.
The lignin and the carbon nano tube are adopted for ball milling, so that the dispersion effect of the carbon nano tube in the lead paste can be improved, the solubility of the lignin and the carbon nano tube is rapidly reduced after the lignin and the carbon nano tube are functionalized, the effect of the lignin and the carbon nano tube in a battery is favorably maintained, and therefore the shrinkage of a negative active substance, the low-temperature performance and the capacity of the battery caused by the dissolution of the lignin in the use process of the battery are reduced. The types and the amount of the materials of the formula can be adjusted according to actual conditions, but the process steps of the lignin functionalized carbon nano tube are not adjusted.
Preferably, the carbon nanotubes are multiwalled carbon nanotubes and have a battery grade purity. The electrical conductivity of the polar plate can be improved by selecting the multi-walled carbon nano tube, and the low-temperature performance and the cycle life of the battery are facilitated; the interlayer spacing of the multi-walled carbon nanotube is 0.3-0.5 nm.
Preferably, the outer diameter of the multi-walled carbon nanotube is 5-50 nm, and if the outer diameter is too small, the carbon nanotube is knotted and agglomerated; an excessively large outer diameter results in a small contact area with the active material.
A preparation method of negative lead plaster for a lead-acid storage battery comprises the following steps:
(1) respectively adding deionized water I, carbon nano tubes and lignin into a high-energy nano-scale dispersion ball mill;
(2) adding grinding beads into a high-energy nanoscale dispersion ball mill, performing ball milling and mixing, and filtering the grinding beads to obtain lignin functionalized carbon nanotubes for later use;
(3) adding lead powder, humic acid, acetylene black, barium sulfate and short fibers into a paste mixing machine according to the proportion, and carrying out dry mixing;
(4) quickly adding the lignin functionalized carbon nano tube obtained in the step (2) into a paste mixing machine at one time, and supplementing deionized water II for wet mixing;
(5) and slowly adding the sulfuric acid solution into the paste combining machine while stirring, and continuously stirring after the sulfuric acid is completely added to obtain paste, thus obtaining the negative lead paste for the lead-acid storage battery. The apparent density of the negative electrode lead paste for the lead-acid storage battery is 4.40-4.60 g/cm3。
The lignin and the carbon nano tube are common additives in the cathode formula, and if the carbon nano tube and the lignin are directly added into the third step for dry mixing in the conventional adding mode (without the first step and the second step), the carbon nano tube is difficult to disperse, the lignin is easy to dissolve out, and the effects of the lignin and the carbon nano tube cannot be fully exerted. The lignin functionalized carbon nano tube is adopted, the dispersion effect of the carbon nano tube in the lead paste is improved, the shrinkage of a negative active material caused by the dissolution of the lignin in the use process of the battery can be reduced, the low-temperature performance and the capacity of the battery are reduced, and the synergistic effect of the lignin functionalized carbon nano tube and the battery can be fully exerted.
Preferably, in the step (2), the material of the grinding beads is zirconia, silica or agate.
Preferably, in the step (2), the rotating speed of the high-energy nanoscale dispersion ball mill is controlled to be 300-800 r/min; the ball milling and mixing time is controlled to be 10-30 min. The rotating speed is too high, so that the lignin structure is damaged; the carbon nano tube can not be functionalized due to too low rotating speed; the ball milling time is not easy to overlong, on one hand, the production efficiency is influenced, and on the other hand, heat can be generated to destroy the structure of the material.
Preferably, in the step (3), the dry mixing time is controlled to be 3-7 min.
Preferably, in the step (4), the wet mixing time is controlled to be 3-7 min.
Preferably, in the step (5), the density of the sulfuric acid solution is 1.3-1.5 g/ml; controlling the addition of the sulfuric acid solution within 10-15 min; the time for continuous stirring is controlled to be 5-10 min.
Therefore, the invention has the following beneficial effects:
(1) the lignin used in the negative electrode lead plaster for the lead-acid storage battery is anchored by the carbon nano tube, so that the uniform distribution of the carbon nano tube in an active substance is facilitated, meanwhile, the dissolution of the lignin in the formation and battery use processes can be inhibited, the battery has better low-temperature performance and cycle life, the carbon nano tube can be more uniformly distributed in the negative electrode lead plaster after the lignin is functionalized, and the rate capability of the battery is promoted;
(2) the preparation method is simple, has no special requirements on equipment, avoids directly mixing raw materials, increases the dispersion effect of the carbon nano tube in the lead paste, and simultaneously can reduce the shrinkage of a negative active material and the reduction of low-temperature performance and battery capacity caused by the dissolution of lignin in the use process of the battery, thereby playing the synergistic effect of the two on the battery.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
In the following examples, the multi-walled carbon nanotubes used were obtained from Peking Tiannai technologies, Inc. under the model Flotube9210 and the lignin from Borregaard, Norway under the model Vanisperse HT-1.
Example 1
(1) According to a formula table of table 1, respectively adding 10kg of deionized water I, 0.2kg of multi-walled carbon nano-tubes with the outer diameter of 5nm and the interlayer spacing of 0.3nm and 2kg of lignin into a high-energy nano-scale dispersion ball mill;
(2) adding zirconium oxide grinding beads for grinding, ball-milling and mixing for 30min at the rotating speed of 300r/min, and filtering the grinding beads to obtain lignin functionalized carbon nanotubes for later use;
(3) adding 1000kg of lead powder, 3kg of humic acid, 2kg of acetylene black, 10kg of barium sulfate and 0.5kg of polyacrylonitrile fiber into a paste mixing machine, and carrying out dry mixing for 7 min;
(4) quickly adding the lignin-functionalized carbon nanotube dispersion liquid obtained in the step (2) into a paste mixing machine at one time, supplementing 100kg of deionized water II, and wet-mixing for 5 min;
(5) slowly adding 1.4g/ml sulfuric acid solution into paste mixing machine, stirring while adding, controlling the adding within 15min, and continuously stirring for 5min after all the sulfuric acid is added to obtain the negative pole lead paste containing the lignin functionalized carbon nano tube with apparent density of 4.50g/cm3。
Example 2
(1) According to a formula table in table 1, 10kg of deionized water I, 0.3kg of multi-walled carbon nano-tubes with the outer diameter of 50nm and the interlayer spacing of 0.5nm and 2kg of lignin are respectively added into a high-energy nano-scale dispersion ball mill;
(2) adding silicon oxide grinding beads for grinding, ball-milling and mixing for 20min at the rotating speed of 500r/min, and filtering off the grinding beads to obtain lignin functionalized carbon nanotubes for later use;
(3) adding 1000kg of lead powder, 2kg of humic acid, 3kg of acetylene black, 10kg of barium sulfate and 0.75kg of polypropylene fiber into a paste combining machine, and carrying out dry mixing for 5 min;
(4) quickly adding the lignin-functionalized carbon nanotube dispersion liquid obtained in the step (2) into a paste mixing machine at one time, supplementing 100kg of deionized water II, and wet-mixing for 3 min;
(5) slowly adding 1.3g/ml sulfuric acid solution into paste mixing machine, stirring while controlling the adding within 12min, and continuously stirring for 8min after the sulfuric acid is completely added to obtain the negative pole lead paste containing the lignin functionalized carbon nano tube with apparent density of 4.40g/cm3。
Example 3
(1) According to the formula table of table 1, 20kg of deionized water I, 0.5kg of multiwall carbon nanotube with the carbon outer diameter of 25nm and the interlayer spacing of 0.4nm and 3kg of lignin are respectively added into a high-energy nanoscale dispersion ball mill;
(2) adding agate beads for grinding, ball-milling and mixing for 10min at the rotating speed of 800r/min, and filtering off the grinding beads to obtain lignin functionalized carbon nanotubes for later use;
(3) adding 1000kg of lead powder, 2kg of humic acid, 2kg of acetylene black, 10kg of barium sulfate, 0.25kg of polypropylene fiber and 0.5kg of polyester fiber into a paste combining machine, and carrying out dry mixing for 3 min;
(4) quickly adding the lignin-functionalized carbon nano tubes obtained in the step (2) into a paste mixing machine at one time, supplementing 95kg of deionized water II, and wet-mixing for 7 min;
(5) slowly adding 1.4g/ml sulfuric acid solution into paste mixing machine, stirring while adding, controlling the adding within 10min, and continuously stirring for 10min after all the sulfuric acid is added to obtain the negative pole lead paste containing the lignin functionalized carbon nano tube with apparent density of 4.60g/cm3。
Example 4
Example 4 differs from example 1 in the formulation of the negative electrode lead paste containing lignin-functionalized carbon nanotubes, as detailed in table 1, and the rest of the process is identical.
TABLE 1 formulation of negative electrode lead paste for lead-acid batteries of examples 1 to 4
Comparative example
(1) Respectively metering lead powder, humic acid, barium sulfate, lignin, short fibers, carbon black (and/or carbon nano tubes), sulfuric acid and deionized water according to a conventional formula, adding the metered humic acid, barium sulfate, lignin, short fibers and carbon black (and/or carbon nano tubes) into a paste combining machine, tightly covering a pot cover, adding the metered lead powder, and dry-mixing for 5-8 min. Rapidly pouring a certain amount of deionized water into the pan while stirring, adding water, and wet-stirring for 5 min. Once the temperature exceeds 35 ℃ in the stirring process, circulating water is opened for cooling.
(2) Dilute sulfuric acid metered according to the formula is added into the pot at a constant speed while stirring, and the circulating cooling water is completely opened and added at a constant speed within a specified time (15-20 min).
(3) And (3) starting air cooling equipment for auxiliary cooling when the temperature of the lead paste exceeds 58 ℃ in the acid adding process, and stirring for 5-8 min after the sulfuric acid is added.
(4) And after stirring is finished, detecting the apparent density of the lead paste until the apparent density meets the process requirements, and obtaining the negative lead paste for the lead-acid storage battery.
Taking a 6-DZF-20 battery as an example according to GB/T22199-2017 tests, the negative lead paste for the lead-acid storage battery prepared by the embodiments 1-4 and the comparative example is applied to the lead-acid storage battery, and the electrochemical properties of the prepared lead-acid storage battery are shown in Table 2:
TABLE 2 electrochemical Performance test results
| Performance index | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| 2hr capacity | 134min | 133min | 135min | 134min | 132min |
| High current capability | 33min | 32min | 32min | 32min | 26min |
| -18 ℃ capacity | 103min | 103min | 104min | 103min | 97min |
| Cycle life | 369 times | 378 times | 405 times | 390 times | 252 times |
As can be seen from table 2, the lead-acid storage battery prepared by using the negative electrode lead paste containing the lignin-functionalized carbon nanotubes of the present invention has excellent high-current discharge performance, low-temperature performance and cycle performance, and thus, the lignin-functionalized carbon nanotubes increase the dispersion effect of the carbon nanotubes in the lead paste, reduce the resistivity of the plate, and significantly improve the high-current discharge performance of the battery; meanwhile, the shrinkage of the negative active material caused by the dissolution of lignin in the use process of the battery can be reduced, the reduction of low-temperature performance and battery capacity can be inhibited, and the synergistic effect of the two can be fully exerted. On the contrary, the lead-acid storage battery prepared from the negative lead plaster prepared by the conventional formula and the process of the comparative example has poor low-temperature and cycle performance because the carbon nano tubes are not uniformly dispersed in the lead plaster, so that the internal resistance of the battery is high, and on the other hand, the low-temperature performance is poor due to the fact that a large amount of lignin is dissolved out in the battery pickling and acidifying process, the battery is quickly attenuated in the subsequent use process, and the cycle life of the battery is poor.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. The negative electrode lead plaster for the lead-acid storage battery is characterized by being prepared from the following components in parts by weight: 1000 parts of lead powder, 12-25 parts of lignin functionalized carbon nano tubes, 2-3 parts of humic acid, 2-3 parts of acetylene black, 10-12 parts of barium sulfate, 100-120 parts of deionized water, 80-100 parts of sulfuric acid and 0.5-1 part of short fibers;
the preparation method of the lignin functionalized carbon nano tube comprises the following steps: uniformly mixing carbon nanotubes, lignin and deionized water according to a mass ratio of (1-5) to (20-30) to (100-300), and performing ball milling treatment to obtain lignin functionalized carbon nanotubes; the carbon nano tube is a multi-wall carbon nano tube; the outer diameter of the multi-walled carbon nanotube is 5-50 nm; the interlayer spacing of the multi-walled carbon nano-tube is 0.3-0.5 nm.
2. The preparation method of the negative electrode lead paste for the lead-acid storage battery according to claim 1, characterized by comprising the following steps:
(1) respectively adding deionized water I, carbon nano tubes and lignin into a high-energy nano-scale dispersion ball mill;
(2) adding grinding beads into a high-energy nanoscale dispersion ball mill, performing ball milling and mixing, and filtering the grinding beads to obtain lignin functionalized carbon nanotubes for later use;
(3) adding lead powder, humic acid, acetylene black, barium sulfate and short fibers into a paste mixing machine according to the proportion, and carrying out dry mixing;
(4) quickly adding the lignin functionalized carbon nano tube obtained in the step (2) into a paste mixing machine at one time, and supplementing deionized water II for wet mixing;
(5) slowly adding sulfuric acid into the paste combining machine while stirring, continuously stirring after the sulfuric acid is completely added, and discharging paste to obtain the negative lead paste for the lead-acid storage battery.
3. The method for preparing the negative electrode lead paste for the lead-acid storage battery according to claim 2, wherein in the step (2), the material of the grinding beads is zirconia, silica or agate.
4. The preparation method of the negative electrode lead plaster for the lead-acid storage battery according to claim 2, characterized in that in the step (2), the rotating speed of the high-energy nanoscale dispersion ball mill is controlled to be 300-800 r/min; the ball milling and mixing time is controlled to be 10-30 min.
5. The preparation method of the negative electrode lead paste for the lead-acid storage battery according to claim 2, wherein in the step (3), the dry mixing time is controlled to be 3-7 min.
6. The preparation method of the negative electrode lead paste for the lead-acid storage battery according to claim 2, wherein in the step (4), the wet mixing time is controlled to be 3-7 min.
7. The preparation method of the negative electrode lead paste for the lead-acid storage battery according to claim 2, wherein in the step (5), the density of the sulfuric acid is 1.3-1.4 g/ml; controlling the addition of the sulfuric acid to be finished within 10-15 min; and the time for continuously stirring is controlled to be 5-10 min.
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