CN117174900A - Lead-graphene negative electrode lead paste and preparation method thereof - Google Patents
Lead-graphene negative electrode lead paste and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 113
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000002156 mixing Methods 0.000 claims abstract description 52
- 239000011505 plaster Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 238000005520 cutting process Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 26
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 22
- 229910000464 lead oxide Inorganic materials 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007580 dry-mixing Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 12
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004021 humic acid Substances 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000003805 vibration mixing Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 2
- 238000005670 sulfation reaction Methods 0.000 abstract description 8
- 230000019635 sulfation Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 4
- 208000032953 Device battery issue Diseases 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 10
- 239000000956 alloy Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical group O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910006529 α-PbO Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013532 brandy Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses lead-graphene negative electrode lead paste and a preparation method thereof, and belongs to the technical field of lead-acid storage batteries; the technical problems that the battery failure caused by the sulfation of the negative electrode is reduced and the cycle service life of the battery is prolonged due to poor mixing uniformity of the components of the traditional negative electrode lead plaster are solved. The lead-graphene negative electrode lead plaster and the preparation method thereof comprise the following steps: step 1, preparing a lead graphene lead ingot; step 2, preparing lead-lead oxide-graphene lead powder; cutting the lead graphene lead ingot cast in the step 1 into blocks, cutting the pure lead ingot into blocks, then putting the lead graphene lead ingot blocks and the pure lead ingot blocks into a ball mill together, introducing air and grinding to obtain lead-lead oxide-graphene lead powder; and 3, preparing the lead-graphene composite negative electrode lead plaster. The battery prepared from the negative electrode lead plaster prepared by the method has the cycle life of more than 500 times, and solves the sulfation problem of the negative electrode.
Description
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to lead-graphene negative electrode lead paste and a preparation method thereof.
Background
Lead-acid batteries (Lead-acid batteries) were invented by france brandy (plant) in 1859, and mainly consist of positive plates, negative plates, electrolyte, separators, electrolytic cells, battery covers, poles, etc. The main active component of the positive electrode is lead dioxide, the main active component of the negative electrode is lead, and the electrolyte is sulfuric acid solution. The chemical reactions involved in discharging are as follows:
and (3) discharging an anode: pbO (PbO) 2 +4H + +SO 4 2- +2e-＝PbSO 4 +2H 2 O；
Discharge negative electrode: pb+SO 4 2- -2e - ＝PbSO 4 ；
The lead-acid storage battery has good charge and discharge performance, safety, stability and low price, and is widely applied to electric power-assisted vehicles and used as a starting power supply of the vehicles at present. Although lead-acid batteries are very widely used, specific energy and cycle life have yet to be improved, particularly in terms of battery capacity and battery life. These properties are generally determined by the plate active material, and what affects the plate active material is the formulation of the lead paste, which can affect the capacity, life, and other properties of the battery.
At present, lead plaster formulas of most lead storage battery production factories adopt lead powder, conductive agent, adhesive and material components of fibers, and the initial performance of the battery can be improved by increasing the contents of the conductive agent, the adhesive and the fibers in the formulas, but the adhesive strength of active substances is reduced, and the service life of the battery is reduced. The problems of conversion efficiency, discharge capacity of a battery and the like in the formation, charge and discharge processes are solved by adopting graphite as the electric conductor in the formula, but the problems of high density difference, poor mixing uniformity, incapability of solving the problem of bonding strength between a grid corrosion layer and lead plaster in a curing process when the graphite electric conductor, other formula materials and lead powder are mixed in the paste mixing process are not considered, the problem of electrochemical polarization increase caused by infirm bonding between the lead plaster and the grid in the later charge and discharge cycle process is caused, the later charge and discharge efficiency is influenced, and the service life of the battery is influenced by the fact that the lead plaster is easily muddy and falls off due to the bonding problem.
Disclosure of Invention
In view of the above analysis, the invention aims to provide a lead-graphene negative electrode lead plaster and a preparation method thereof, which are used for solving the technical problems that the mixing uniformity of components of the existing negative electrode lead plaster is poor, and the battery failure caused by negative electrode sulfation reduces the cycle service life of the battery.
The aim of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides a preparation method of lead-graphene negative electrode lead paste, which comprises the following steps:
step 1, preparing a lead graphene lead ingot;
uniformly stirring and mixing graphene and sodium hydroxide, then placing the graphene and sodium hydroxide and the metal lead in an atmosphere furnace, introducing protective gas for protection, heating to 600-800 ℃, performing ultrasonic vibration and mixing, and casting the mixed graphene and sodium hydroxide into lead ingots;
step 2, preparing lead-lead oxide-graphene lead powder;
cutting the lead graphene lead ingot cast in the step 1 into blocks, cutting the pure lead ingot into blocks, then putting the lead graphene lead ingot blocks and the pure lead ingot blocks into a ball mill together, introducing air and grinding to obtain lead-lead oxide-graphene lead powder;
step 3, preparing lead-graphene composite negative electrode lead plaster;
and (3) adding a part of the lead-lead oxide-graphene lead powder prepared in the step (2) into a paste mixing machine, adding barium sulfate, lignin, humic acid and conductive fibers, continuously adding the rest of the lead-lead oxide-graphene lead powder for dry mixing, adding pure water for wet mixing and stirring after mixing, slowly dropwise adding a dilute sulfuric acid solution, and continuously mixing and stirring after adding the dilute sulfuric acid solution, so as to obtain the high-performance lead-graphene composite negative electrode lead paste.
Further, in the step 1, 1-50 layers of graphene with the weight ratio of 5-10% and 1-5% of sodium hydroxide are stirred and mixed uniformly, and then are placed into an atmosphere furnace together with 80-90% of metallic lead with the weight ratio, and nitrogen or argon is introduced for protection.
Further, in the step 1, the frequency of ultrasonic vibration mixing is 20-40hz, and the ultrasonic vibration mixing time is 0.5-1h.
Further, in the step 2, the input mass ratio of the lead graphene lead ingot cut pieces to the pure lead ingot cut pieces is 1:5-10.
Further, in the step 2, the grinding temperature of the lead graphene lead ingot dicing and the pure lead ingot dicing is 180-200 ℃, the grinding time is 1-10h, and the grain size of the prepared lead-lead oxide-graphene lead powder is 1-5 mu m.
Further, in step 2, the lead-lead oxide-graphene lead powder is core-shell structure lead powder having an inner core, a middle shell structure and an outer shell structure; the lead powder with the core-shell structure takes lead as an inner core, a middle-layer shell structure is formed by wrapping lead oxide on the periphery of the lead inner core, and an outer-layer shell structure is formed by wrapping graphene on the periphery of the lead oxide.
Further, in step 2, the oxidation degree of the lead-lead oxide-graphene lead powder is 70-80%.
Further, in the step 3, based on 100 parts of lead-lead oxide-graphene lead powder, the addition amount of barium sulfate is 0.8-1.5 parts, the addition amount of lignin is 0.1-0.5 part, the addition amount of humic acid is 0.1-0.5 part, and the addition amount of conductive fibers is 0.01-0.06 part.
Further, in the step 3, the dry mixing time is 5-10min; after the dry mixing is finished, 10-12 parts of pure water with the conductivity less than 2 mu s/cm is quickly added in 1-5min, wet mixing and stirring are carried out for 5-10min, and then 6-10 parts of dilute sulfuric acid solution with the density of 1.4g/ml is slowly added dropwise in 10-15 min.
On the other hand, the invention also provides the lead-graphene negative electrode lead plaster, which is prepared by adopting the lead-graphene negative electrode lead plaster and the preparation method thereof.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) According to the invention, the mass ratio of the diced lead graphene lead ingots to the pure lead ingots is controlled within the range of 1:5-10, so that the ratio of graphene in a lead plaster formula is controlled within 0.1-1%, the framework of the negative electrode can be maintained to the maximum extent, the conductivity is enhanced, and the sulfation resistance of the negative electrode plate is greatly improved.
(2) The grain diameter of the lead-lead oxide-graphene lead powder is controlled within 1-5 mu m, the specific surface area of the lead-lead oxide-graphene lead powder is large, the porosity of a polar plate prepared by using the lead-lead oxide-graphene lead powder is moderate, and the electrical property of the battery can be the most excellent on the premise of ensuring the cycle life of the battery.
(3) The negative electrode lead plaster prepared by the preparation method provided by the invention is used for preparing a battery, the cycle life of the battery is up to more than 500 times, and the sulfation problem of the negative electrode is solved.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the embodiments of the invention particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
Fig. 1 is a graph comparing cycle life of a battery prepared using the lead-graphene negative electrode lead paste of the present invention with a battery prepared using a conventional formulation.
Detailed Description
The following detailed description of preferred embodiments of the invention is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the invention, are used to explain the principles of the invention and are not intended to limit the scope of the invention.
The invention provides a lead-graphene negative electrode lead paste and a preparation method thereof, comprising the following steps:
step 1, preparing a lead graphene lead ingot;
and (3) uniformly stirring and mixing 1-50 layers of graphene with the weight ratio of 5-10% and sodium hydroxide with the weight ratio of 1-5%, placing the mixture and 80-90% of metallic lead in an atmosphere furnace, introducing nitrogen or argon for protection, slowly heating to 600-800 ℃, stirring, ultrasonically vibrating and mixing for 0.5-1h, and casting to obtain lead graphene lead ingots after the mixing.
In the step 1, the weight ratio of the graphene, the sodium hydroxide and the metallic lead is controlled within the range, so that the lead graphene alloy of the graphene modified lead can be prepared. After the lead is modified by the graphene, the layered graphene is coated outside the metal lead, so that the lead and the graphene are not mixed unevenly due to overlarge density difference in the process of ball milling the lead graphene alloy into lead powder.
In the step 1, graphene, sodium hydroxide and metallic lead are placed in an atmosphere furnace and heated to 600-800 ℃, so that a mixture alloy formed by the graphene, the sodium hydroxide and the metallic lead is quickly dissolved, the viscosity is moderate, and the alloy is easy to fully mix; when the temperature is higher than 800 ℃, the energy consumption of the mixture alloy is high and lead slag is generated more; when the temperature is less than 600 ℃, the dissolution rate in the alloy preparation process of the mixture is low, the dissolution time is long, the productivity is low, and meanwhile, the alloy viscosity is high and the mixing uniformity is poor.
In the step 1, the frequency of ultrasonic oscillation is 20-40hz, and the lead graphene alloy can be ensured to be mixed more uniformly by adopting ultrasonic oscillation and controlling the oscillation frequency of the ultrasonic oscillation within the range of 20-40 hz.
Step 2, preparing lead-lead oxide-graphene lead powder;
cutting the lead graphene lead ingot cast in the step 1 into blocks, cutting the pure lead ingot into blocks, putting the blocks into a ball mill according to the mass ratio of 1:5-10, introducing air, and grinding for 1-10h at 180-200 ℃ to prepare the lead-lead oxide-graphene lead powder with the particle size of 1-5 mu m.
The lead-lead oxide-graphene lead powder is core-shell structure lead powder with an inner core, a middle-layer shell structure and an outer-layer shell structure, wherein the core-shell structure lead powder takes lead as the inner core, lead oxide wraps the periphery of the lead inner core to form the middle-layer shell structure, and graphene lead powder wraps the periphery of the lead oxide to form the outer-layer shell structure.
Compared with the prior art, the lead powder with the core-shell structure is designed by the lead-lead oxide-graphene lead powder, wherein the middle shell structure and the outer shell structure can protect the inner core, so that the inner core is more stable; the surface of the graphene is modified (lead modified graphene is modified due to defects at the edge of the graphene, and lead is combined with the edge for modification), the shell is very active, and the core-shell structure can also compound various performances.
In the step 2, the mass ratio of the diced lead graphene lead ingot to the pure lead ingot is controlled within the range of 1:5-10, so as to ensure that the ratio of graphene in the lead paste formula is controlled within 0.1-1%, the framework of the negative electrode can be maintained to the maximum extent (the graphene is adsorbed or embedded into the negative electrode active substance lead crystal, the basic attribute of the negative electrode plate is changed, and a lead graphene electrode is formed), the anti-sulfation capability of the negative electrode plate is greatly improved by enhancing the electric conduction, and the lead graphene lead ingot and the pure lead ingot alloy are in the range of 1: the range of 5-10 can meet the above requirements.
In the step 2, the higher the content of alpha lead oxide (alpha-PbO) in the lead powder is, the most excellent performance of the battery prepared by the paste is when the oxidation degree of the lead powder is 70-80%; when the grinding temperature is higher than 200 ℃, the oxidation degree of lead powder is easy to be too high, and the high temperature easily causes the problem that the conversion of alpha lead oxide (alpha-PbO) in the lead powder into beta lead oxide (beta-PbO) affects the battery performance, and meanwhile, the high temperature can cause the problems of high energy consumption, high equipment maintenance cost and the like of the manufacturing, so that the ball milling temperature is controlled to be 180-200 ℃.
The chemical reaction occurring during ball milling is as follows:
2Pb+O 2 →2PbO (1)
the particle size of the lead-lead oxide-graphene lead powder is controlled to be 1-5 mu m, and the lead-lead oxide-graphene lead powder is large in specific surface area, so that the prepared polar plate is moderate in porosity, and the electric performance of the battery can be the most excellent on the premise of ensuring the cycle life of the battery.
Step 3, preparing lead-graphene composite negative electrode lead plaster;
taking 100 parts of lead-lead oxide-graphene lead powder, adding 50 parts of lead-lead oxide-graphene lead powder into a paste mixing machine, adding 0.8-1.5 parts of barium sulfate, 0.1-0.5 part of lignin, 0.1-0.5 part of humic acid and 0.01-0.06 part of conductive fiber, continuously adding the rest 50 parts of lead-lead oxide-graphene lead powder, dry mixing for 5-10min, quickly adding 10-12 parts of pure water with conductivity less than 2 mu s/cm within 1-5min after mixing, wet mixing and stirring for 5-10min, slowly dropwise adding 6-10 parts of dilute sulfuric acid solution with density of 1.4g/ml within 10-15min, and continuously mixing and stirring for 5-10min after sulfuric acid addition to obtain the high-performance lead-graphene composite negative lead paste.
In the step 3, the effect of adding 0.8 to 1.5 parts of barium sulfate is that: the barium sulfate is used as an expanding agent and a lead sulfate nucleating agent on the negative electrode, so that a porous small lead sulfate crystal layer is formed on the surface of the lead electrode, excessive shrinkage in the processes of depositing a lead sulfate passivation layer and overcharging a negative plate is restrained, and the discharge capacity of the negative electrode is improved.
In the step 3, 0.1-0.5 part of lignin is added for improving the high-rate discharge performance of the battery.
In the above step 3, 0.1 to 0.5 part of humic acid is added in order to improve the discharge capacity and low-temperature discharge performance of the battery.
In the step 3, 0.01 to 0.06 part of conductive fiber is added to increase the mechanical strength and the conductivity of the polar plate, prevent the active substances from falling off and prolong the cycle service life of the battery.
In the step 3, 50 parts of lead-lead oxide-graphene lead powder is added first, and then the rest 50 parts of lead-lead oxide-graphene lead powder is continuously added, wherein the aim of the batch addition is that: lead plaster to be mixed more uniformly, lead plaster has high consistency of apparent specific gravity, improves the battery matching rate, and reduces the single-battery lag phenomenon in the circulation process.
In the step 3, the purpose of dry mixing is to pre-mix lead powder more battery negative electrode additive uniformly in advance, and then add pure water for wetting, so that the lead plaster has plasticity and filling property.
In the step 3, the effect of dropwise adding 6-10 parts of dilute sulfuric acid solution with the density of 1.4g/ml is as follows: lead oxide and dilute sulfuric acid in the lead plaster are enabled to generate lead sulfate, and in the process of plaster combination and solidification, the polar plate is enabled to generate a net structure of tribasic lead sulfate, so that the binding force and the mechanical strength of the polar plate with the grid are improved, and meanwhile, the electrochemical activity of the electrode after battery formation can be promoted.
Compared with the prior art, the invention solves the problem of poor mixing uniformity of the existing lead powder and carbon materials such as graphite, graphene and the like; the conductive performance of the negative electrode lead plaster is improved, the combination capability of the grid and the lead plaster is improved, the battery failure caused by negative electrode sulfation is solved, and the cycle service life of the battery is prolonged.
The invention also provides the lead-graphene negative electrode lead plaster, which is prepared by the preparation method of the lead-graphene negative electrode lead plaster. The lead-graphene negative electrode lead paste is used for preparing a battery, the cycle life of the battery is up to more than 500 times (as shown in figure 1), and the sulfation problem of the negative electrode is solved.
Example 1
Step 1, preparing a lead graphene lead ingot;
and (3) uniformly stirring and mixing 5-10 layers of graphene with the weight ratio of 6% and sodium hydroxide with the weight ratio of 2%, then placing the mixture and metal lead with the weight ratio of 81% in an atmosphere furnace, introducing nitrogen or argon for protection, slowly heating to 610 ℃, stirring, ultrasonically oscillating and mixing for 0.6h, and casting to obtain lead graphene lead ingots after mixing.
Step 2, preparing lead-lead oxide-graphene lead powder;
dicing the cast lead graphene lead ingot, dicing the lead graphene lead ingot and the pure lead ingot according to the mass ratio of 1:5, putting the mixture into a ball mill, introducing air, and grinding the mixture at 180 ℃ for 2 hours to prepare the lead-lead oxide-graphene lead powder with the average particle size of 2.18 mu m.
Step 3, preparing lead-graphene composite negative electrode lead plaster;
50 parts of the lead-lead oxide-graphene lead powder with the particle size of 2.18 mu m are taken and added into a paste mixing machine, 1 part of barium sulfate, 0.2 part of lignin, 0.1 part of humic acid and 0.02 part of conductive fiber are added, then the rest 50 parts of lead-lead oxide-graphene lead powder is continuously added for dry mixing for 10min, 10 parts of pure water with the conductivity of less than 2 mu s/cm is rapidly added for wet mixing and stirring for 5min after the mixing is finished, then 6 parts of dilute sulfuric acid solution with the density of 1.4g/ml is slowly added within 10min, and the mixing and stirring are continuously carried out for 5min after the sulfuric acid is added, so that the lead-graphene composite negative lead paste with high performance is obtained.
The cycle life of the battery assembled by the negative plate and the conventional positive plate prepared by the method of the embodiment reaches 534 times.
Example 2
Step 1, preparing a lead graphene lead ingot;
and (3) uniformly stirring and mixing 5-10 layers of graphene with the weight ratio of 8% and 3% sodium hydroxide, then placing the mixture and 85% of metal lead in an atmosphere furnace, introducing nitrogen or argon for protection, slowly heating to 700 ℃, stirring, ultrasonically oscillating and mixing for 0.7h, and casting to obtain lead graphene lead ingots after mixing.
Step 2, preparing lead-lead oxide-graphene lead powder;
dicing the cast lead graphene lead ingot, dicing the lead graphene lead ingot and the pure lead ingot according to the mass ratio of 1:8, putting the mixture into a ball mill, introducing air, and grinding the mixture at 190 ℃ for 5 hours to prepare the lead-lead oxide-graphene lead powder with the average particle size of 4.2 mu m.
Step 3, preparing lead-graphene composite negative electrode lead plaster;
50 parts of lead-lead oxide-graphene lead powder with the particle size of 4.2 mu m are taken and added into a paste mixing machine, 1.2 parts of barium sulfate, 0.3 part of lignin, 0.3 part of humic acid and 0.04 part of conductive fiber are added, then the rest 50 parts of lead-lead oxide-graphene lead powder is continuously added for dry mixing for 10min, 11 parts of pure water with the conductivity of less than 2 mu s/cm is rapidly added after the mixing is completed, wet mixing and stirring are carried out for 7min, then 8 parts of dilute sulfuric acid solution with the density of 1.4g/ml is slowly added dropwise within 13min, and mixing and stirring are continuously carried out for 8min after the sulfuric acid is added, so that the lead-graphene composite negative lead paste with high performance is obtained.
The cycle life of the battery assembled by the negative plate prepared by the method of the embodiment and the conventional positive plate reaches 540 times.
Example 3
Step 1, preparing a lead graphene lead ingot;
and (3) uniformly stirring and mixing 5-10 layers of graphene with the weight ratio of 9% and 5% sodium hydroxide, then placing the mixture and metal lead with the weight ratio of 90% in an atmosphere furnace, introducing nitrogen or argon for protection, slowly heating to 800 ℃, stirring, ultrasonically oscillating and mixing for 0.9h, and casting to obtain lead graphene lead ingots after mixing.
Step 2, preparing lead-lead oxide-graphene lead powder;
dicing the cast lead graphene lead ingot, dicing the lead graphene lead ingot and the pure lead ingot according to the mass ratio of 1:9, putting the mixture into a ball mill, introducing air, and grinding the mixture at 200 ℃ for 9 hours to prepare the lead-lead oxide-graphene lead powder with the average particle size of 4.8 mu m.
Step 3, preparing lead-graphene composite negative electrode lead plaster;
50 parts of the lead-lead oxide-graphene lead powder with the particle size of 4.8 mu m are taken and added into a paste mixing machine, 1.4 parts of barium sulfate, 0.4 part of lignin, 0.5 part of humic acid and 0.06 part of conductive fiber are added, then the rest 50 parts of lead-lead oxide-graphene lead powder is continuously added for dry mixing for 10min, 12 parts of pure water with the conductivity of less than 2 mu s/cm is rapidly added for wet mixing and stirring for 10min after mixing, then 10 parts of dilute sulfuric acid solution with the density of 1.4g/ml is slowly added dropwise within 15min, and the mixing and stirring are continuously carried out for 9min after sulfuric acid addition is finished, so that the lead-graphene composite negative lead paste with high performance is obtained.
The cycle life of the battery assembled by the negative plate prepared by the method of the embodiment and the conventional positive plate reaches 530 times.
Comparative example 1
Step 1, preparing lead-lead oxide lead powder;
putting the lead ingot into a ball mill, introducing air, and grinding for 9 hours at 200 ℃ to prepare the lead-lead oxide lead powder with the average particle size of 2.7 mu m.
Step 3, preparing lead-graphene composite negative electrode lead plaster;
adding 50 parts of the lead-lead oxide with the particle size of 2.7 mu m into a paste mixing machine, adding 1.4 parts of barium sulfate, 0.2 part of lignin, 0.1 part of humic acid and 0.1 part of conductive fiber, continuously adding 0.3 part of carbon black into the rest 50 parts of lead-lead oxide lead powder, dry-mixing for 10min, rapidly adding 12 parts of pure water with the conductivity of less than 2 mu s/cm after mixing, wet-mixing and stirring for 10min, slowly dropwise adding 10 parts of dilute sulfuric acid solution with the density of 1.4g/ml within 15min, and continuously mixing and stirring for 10min after sulfuric acid addition to obtain the high-performance lead-carbon black composite negative electrode lead paste.
The cycle life of the battery assembled by the negative plate prepared by the method of the present example and the conventional positive plate reaches 244 times.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the lead-graphene negative electrode lead plaster is characterized by comprising the following steps of:
step 1, preparing a lead graphene lead ingot;
uniformly stirring and mixing graphene and sodium hydroxide, then placing the graphene and sodium hydroxide and the metal lead in an atmosphere furnace, introducing protective gas for protection, heating to 600-800 ℃, performing ultrasonic vibration and mixing, and casting the mixed graphene and sodium hydroxide into lead ingots;
step 2, preparing lead-lead oxide-graphene lead powder;
cutting the lead graphene lead ingot cast in the step 1 into blocks, cutting the pure lead ingot into blocks, then putting the lead graphene lead ingot blocks and the pure lead ingot blocks into a ball mill together, introducing air and grinding to obtain lead-lead oxide-graphene lead powder;
step 3, preparing lead-graphene composite negative electrode lead plaster;
and (3) adding a part of the lead-lead oxide-graphene lead powder prepared in the step (2) into a paste mixing machine, adding barium sulfate, lignin, humic acid and conductive fibers, continuously adding the rest of the lead-lead oxide-graphene lead powder for dry mixing, adding pure water for wet mixing and stirring after mixing, slowly dropwise adding a dilute sulfuric acid solution, and continuously mixing and stirring after adding the dilute sulfuric acid solution, so as to obtain the high-performance lead-graphene composite negative electrode lead paste.
2. The method for preparing the lead-graphene negative electrode lead plaster according to claim 1, wherein in the step 1, 1-50 layers of graphene with the weight ratio of 5-10% and sodium hydroxide with the weight ratio of 1-5% are stirred and mixed uniformly, and then are placed in an atmosphere furnace together with 80-90% of metallic lead, and nitrogen or argon is introduced for protection.
3. The method for preparing lead-graphene negative electrode lead paste according to claim 2, wherein in the step 1, the ultrasonic vibration mixing frequency is 20-40hz, and the ultrasonic vibration mixing time is 0.5-1h.
4. The method for preparing lead-graphene anode lead plaster according to claim 1, wherein in the step 2, the input mass ratio of the lead graphene lead ingot cut pieces to the pure lead ingot cut pieces is 1:5-10.
5. The method for preparing lead-graphene negative electrode lead plaster according to claim 4, wherein in the step 2, the grinding temperature of the cut lead ingot of lead graphene and the cut lead ingot of pure lead is 180-200 ℃, the grinding time is 1-10h, and the grain size of the prepared lead-lead oxide-graphene lead powder is 1-5 μm.
6. The method for preparing lead-graphene negative electrode lead paste according to claim 5, wherein in the step 2, the oxidation degree of the lead-lead oxide-graphene lead powder is 70-80%.
7. The method for preparing lead-graphene negative electrode lead paste according to claim 6, wherein in the step 2, the lead-lead oxide-graphene lead powder is core-shell structured lead powder having an inner core, a middle shell structure and an outer shell structure; the core-shell structure lead powder takes lead as an inner core, a middle-layer shell structure is formed by wrapping lead oxide on the periphery of the lead inner core, and an outer-layer shell structure is formed by wrapping graphene on the periphery of the lead oxide.
8. The method for preparing lead-graphene negative electrode lead paste according to claim 1, wherein in the step 3, the amount of barium sulfate added is 0.8-1.5 parts, the amount of lignin added is 0.1-0.5 parts, the amount of humic acid added is 0.1-0.5 parts, and the amount of conductive fiber added is 0.01-0.06 parts, based on 100 parts of lead-lead oxide-graphene lead powder.
9. The method for preparing lead-graphene anode lead paste according to claim 8, wherein in the step 3, the dry mixing time is 5-10min; after the dry mixing is finished, 10-12 parts of pure water with the conductivity less than 2 mu s/cm is quickly added in 1-5min, wet mixing and stirring are carried out for 5-10min, and then 6-10 parts of dilute sulfuric acid solution with the density of 1.4g/ml is slowly added dropwise in 10-15 min.
10. A lead-graphene negative electrode lead plaster, which is characterized by being prepared by adopting the lead-graphene negative electrode lead plaster as claimed in claims 1 to 9 and a preparation method thereof.
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