CN109755563A - A kind of lead-acid accumulator negative pole lead paste and preparation method thereof - Google Patents
A kind of lead-acid accumulator negative pole lead paste and preparation method thereof Download PDFInfo
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- CN109755563A CN109755563A CN201811608995.4A CN201811608995A CN109755563A CN 109755563 A CN109755563 A CN 109755563A CN 201811608995 A CN201811608995 A CN 201811608995A CN 109755563 A CN109755563 A CN 109755563A
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- lead
- acid
- negative pole
- copper fiber
- acid accumulator
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of lead-acid accumulator negative pole lead pastes and preparation method thereof, belong to battery technology field.The lead-acid accumulator negative pole lead paste, component include lead powder, barium sulfate, humic acid, sulfuric acid and water, further include the modification copper fiber that surface is coated with lead or metal.Modified copper fiber has excellent electric conductivity and electro-chemical activity and mechanical performance, it is good with active material compatibility in lead-acid battery cathode lead plaster to be added to, there is big contact area with active material, improve the dispersibility of active material, conductive network can be constructed, improve the utilization rate of active material and the high-power performance of lead-acid battery, and the mechanical strength of pole plate can be improved, increase battery cycle life, test result shows, specific capacity promotes 10~60%, and specific energy improves 25~70%, and cycle life is obviously prolonged under high magnification partial state of charge.
Description
Technical field
The present invention relates to battery technology fields, and in particular to a kind of lead-acid accumulator negative pole lead paste and preparation method thereof.
Background technique
Lead-acid battery is mainly made of lead and its oxide, and electrolyte is sulfuric acid solution.Under state-of-charge, anode mainly at
It is divided into brown lead oxide, cathode main component is lead；Under discharge condition, the main component of positive and negative anodes is lead sulfate, is with density
The sulfuric acid solution of 1.28~1.32g/mL (concentration is 27%~37%) is referred to as lead-acid accumulator (also known as " lead as electrolyte
Battery ").Lead-acid accumulator is that power peak regulation, the operation of raising system are steady in the research emphasis of electric system application field at present
The stored energy applications such as qualitative and raising power supply quality.This requires battery to meet, and energy density is high, high temperature performance is excellent, safety
The application characteristics such as get well, have extended cycle life, can be quickly charged and discharged.
Conventional lead-acid battery safety and high temperature performance is excellent, and improves the specific energy of lead-acid battery, can quickly fill
Discharge performance and the service life for extending lead-acid battery become the three big focuses of attention that limitation lead-acid battery is applied in energy storage field.
Application publication number is that the patent document of CN 108832080A discloses a kind of lead-acid accumulator negative pole lead paste.This is negative
Pole lead plaster is made of major ingredient and auxiliary material two parts, and each component is as follows by weight ratio: major ingredient: tribasic lead sulfate (3BS) 40-
50, lead powder 50-60；Auxiliary material: deionized water 15-20, acetylene black 0.1-1, sodium sulphate 0.1-0.5, conductive fiber 0.1-0.25, wood
Plain 0.1-0.5, humic acid 0.1-0.5, barium sulfate 0.5-2 are prepared by the way that above-mentioned each component to be uniformly mixed.It is negative using this
Pole lead plaster can improve the chemical property of lead-acid accumulator, extend the service life of battery.
Application publication number is that CN 103413946A discloses a kind of formula of lead-acid storage battery negative pole diachylon, each component weight
Percentage are as follows: lead powder 70-90%, sulfuric acid 3-15%, water 5-20%, staple fiber 0.05-2%, sodium polyaspartate 0.1-
20%, carbon nanotubes 0.1-10%.Anode active material particles are refined using sodium polyaspartate in the invention, improve cathode
Capacity and charge acceptance reduce cathode overpotential of hydrogen evolution and reduce cathode hydrogen-separating quantity；It is improved by addition conductive nano carbon pipe
Electric conductivity between negative electrode active material reduces internal resistance, improves negative electrode charging acceptance capacity, reduces negative electrode active material and shrinks, improves
Battery.
Currently, the use for how improving the specific energy of lead-acid battery, can be quickly charged and discharged performance and extending lead-acid battery
Service life is still the Main way of battery research.
Summary of the invention
The purpose of the present invention is to provide a kind of lead-acid accumulator negative pole lead pastes, living with good electric conductivity and electrochemistry
The modification copper fiber of property is added in lead-acid accumulator negative pole lead paste, to promote the comprehensive performance of lead-acid accumulator.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of lead-acid accumulator negative pole lead paste, component include lead powder, barium sulfate, humic acid, sulfuric acid and water, further include table
Face is coated with the modification copper fiber of lead or metal.
The present invention is studies have shown that lead plating copper fiber not only has lead-sulfuric acid Reversible redox reaction, but also has excellent
Good electric conductivity reduces the sulfation phenomenon of lead-acid battery cathode in big multiplying power pulse charge and discharge process, extends plumbic acid
Cycle life of the battery under HRPSoC operating condition, the negative electrode material suitable for electric car and energy storage lead-acid battery.
Preferably, the surface be coated with the diameter of the modification copper fiber of lead or metal be 15~55 μm, length be 1~
3mm, surface coating is with a thickness of 5~25 μm.Of length no more than 5mm of modified copper fiber, length is more than 5mm easily because of curing and drying mistake
Pole plate internal stress changes and damaged exposing section in journey；Preferably, surface coating is with a thickness of not less than 10 μm, it is ensured that mixing paste mistake
Local excessive acid destroys fiber coating in journey.
The surface is coated with the preparation method of the modification copper fiber of lead or metal, comprising the following steps: will be pretreated
Copper fiber, which is placed in plating solution, carries out chemical plating；The plating solution composition includes: Pb2+0.001~0.01mol/L, Sn2+0~
0.08mol/L, EDTA 25mol/L, sodium citrate 0.01mol/L, the TiCl that mass percent concentration is 15%3Solution 25mL/
L uses Na2CO3Adjusting plating solution PH is 7；Slicker solder ion total weight ratio is 1:2.8~4.5 in copper fiber quality and plating solution；Describedization
The reaction temperature for learning plating is 40~60 DEG C, and the reaction time is 30~120min.
Preferably, plating process 300~500W of ultrasonic power, 60~500r/min of revolving speed mechanical agitation under
It carries out.Ultrasound is introduced during plating and mechanical agitation energy improves the dispersibility of copper fiber, and copper fiber surface can uniform plating
Lead or pb-sn alloy plating.
Preferably, it is surface in terms of 100 parts that the lead-acid accumulator negative pole lead paste component, which includes: by lead powder parts by weight,
It is coated with lead or 1~15 part of the modification copper fiber of metal, 0.1~2.5 part of barium sulfate, 0.1~2.5 part of humic acid, sulfuric acid 4~10
Part, 5~20 parts of water.
Further preferably, it is 3~13 parts that surface, which is coated with the additive amount of the modification copper fiber of lead or metal,.
Further preferably, it is 5~10 parts that surface, which is coated with the additive amount of the modification copper fiber of lead or metal,.
More preferably, the lead-acid accumulator negative pole lead paste component are as follows: by lead powder parts by weight be 100 parts in terms of, surface plating
There are lead or 5 parts of the modification copper fiber of metal, 0.5 part of barium sulfate, 1 part of humic acid, 8 parts of sulfuric acid, 16 parts of water.
The present invention also provides the methods for preparing the lead-acid accumulator negative pole lead paste, comprising the following steps:
Surface is coated with lead or the modification copper fiber of metal is first mixed with part lead powder after immersion 1-2s in 5% sulfuric acid solution
It closes, stirs evenly, it is dry-mixed to add remaining lead powder, barium sulfate and humic acid, and then plus water-wet is mixed, is eventually adding sulfuric acid and institute is made
State lead-acid accumulator negative pole lead paste.
When with cathode lead plaster processed, first impregnated in sulfuric acid solution before adding modified copper fiber, it is then quickly mixed with lead powder
It closes, it is therefore an objective to form the composite protection film of lead sulfate or stannous sulfate or above two sulfate outside copper fiber coating, prevent
Only local acid concentration height destroys fiber coating during mixing paste.Other subsequent processes are the same as conventional mixing paste.
The present invention also provides a kind of lead-acid accumulator, including negative plate, the negative plate is by the lead-acid accumulator
Cathode lead plaster is made through coated plate, solidification.
It is that the present invention has the utility model has the advantages that
The copper fiber of surface lead plating or terne metal has excellent electric conductivity and electro-chemical activity and mechanical performance, addition
It is good with active material compatibility into lead-acid battery cathode lead plaster, there is big contact area with active material, improves active matter
The dispersibility of matter can construct conductive network, improve the utilization rate of active material and the high-power performance of lead-acid battery, and
The mechanical strength of pole plate can be improved, battery cycle life is increased.
Modified copper fiber can be improved the dispersibility of active material and the electric conductivity of cathode lead plaster, make lead-acid battery in high power
Working performance is improved largely under rate partial state of charge, and test result shows that specific capacity promotes 10~60%, and specific energy mentions
High by 25~70%, cycle life is obviously prolonged under high magnification partial state of charge.
Detailed description of the invention
Fig. 1 is the high magnification partial state of charge loop test of simulated battery in embodiment.
Fig. 2 is that simulated battery is being large current discharge curve in embodiment.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the present invention is not limited thereto.
Embodiment 1
1, modified copper fiber the preparation method comprises the following steps: to take length be 1~3mm, the copper fiber 1.5g that diameter is 10~30 μm exists
Oil removing in the NaOH solution of 1mol/L, in the H of 1mol/L after being washed with deionized2SO4Solution in carry out roughening treatment, water
Chemical plating is carried out after washing, drying, plating process carries out under 300W ultrasound, 60r/min revolving speed mechanical stirring.
Plating solution composition are as follows: methane sulfonic acid lead 0.001mol/L, stannous methanesulfonate 0.05mol/L, EDTA25mol/L, lemon
Lemon acid sodium 0.01mol/L, TiCl3(15% solution) 25mL/L, total 600ml.Use Na2CO3Adjusting plating solution PH is 7, electroless plating reaction
Temperature is 50 DEG C, reaction time 60min.
2, cathode lead plaster is prepared
Cathode lead plaster formula: lead powder, modified copper fiber, barium sulfate, humic acid, sulfuric acid, water, with lead powder parts by weight for 100
Part meter, modified 5 parts of copper fiber, 0.5 part of barium sulfate, 1 part of humic acid, 8 parts of sulfuric acid, 16 parts of water.
Mixing paste technology: modified copper fiber addition pretreatment process is fast after impregnating 1-2s in 5% sulfuric acid solution in mixing paste
Speed is mixed with lead powder, is stirred evenly；Other steps are the same as conventional mixing paste technology.
3, the lead-acid battery cathode lead plaster comprising modified copper fiber is coated on negative electrode grid, is successively solidified and is melted into
Cathode is prepared, is anode with commercial positive plate, is 1.3g/cm with density using AGM separator paper as diaphragm3Sulfuric acid be electricity
Xie Zhi tests different multiplying with the plumbic acid simulated battery of two pieces of positive plates, one piece of negative plate " two positive one is negative " assembling 1.5Ah 2V
Lower specific capacity, specific power size, as a result shown in table 1；The discharge curve under cycle life and high current under its HRPSoC state
As depicted in figs. 1 and 2.
Table 1 adds Modified Cu fiber electrode compared with blank electrode performance
Note: blank lead-acid battery is not add modified copper fiber in lead plaster, other are the same as the modified copper fiber lead-acid battery of addition.
As can be seen from Table 1, after lead-acid battery cathode plate adds modified copper fiber, the performance of lead-acid battery has been obtained obviously
It is promoted, especially specific capacity and specific power are compared to blank battery and greatly improve under high current work.
Claims (10)
1. a kind of lead-acid accumulator negative pole lead paste, component includes lead powder, barium sulfate, humic acid, sulfuric acid and water, and feature exists
In further including the modification copper fiber that surface is coated with lead or metal.
2. lead-acid accumulator negative pole lead paste as described in claim 1, which is characterized in that the surface is coated with lead or metal
The diameter of modified copper fiber is 15~55 μm, length is 1~3mm, and surface coating is with a thickness of 5~25 μm.
3. lead-acid accumulator negative pole lead paste as described in claim 1, which is characterized in that the surface is coated with lead or metal
The preparation method of modified copper fiber, comprising the following steps: pretreated copper fiber is placed in plating solution and carries out chemical plating；The plating
Liquid composition includes: Pb2+0.001~0.01mol/L, Sn2+0~0.08mol/L, EDTA 25mol/L, sodium citrate 0.01mol/
L, the TiCl that mass percent concentration is 15%3Solution 25mL/L, uses Na2CO3Adjusting plating solution PH is 7；Copper fiber quality and plating solution
Middle slicker solder ion total weight ratio is 1:2.8~4.5；The reaction temperature of the chemical plating be 40~60 DEG C, the reaction time be 30~
120min。
4. lead-acid accumulator negative pole lead paste as claimed in claim 3, which is characterized in that plating process ultrasonic power 300~
500W, 60~500r/min of revolving speed mechanical agitation under carry out.
5. lead-acid accumulator negative pole lead paste according to any one of claims 1-4, which is characterized in that its component includes: with lead
Powder parts by weight are 100 parts of meters, and surface is coated with lead or 1~15 part of the modification copper fiber of metal, 0.1~2.5 part of barium sulfate, rotten plant
Sour 0.1~2.5 part, 4~10 parts of sulfuric acid, 5~20 parts of water.
6. lead-acid accumulator negative pole lead paste as claimed in claim 5, which is characterized in that surface is coated with the modification of lead or metal
The additive amount of copper fiber is 3~13 parts.
7. lead-acid accumulator negative pole lead paste as claimed in claim 6, which is characterized in that surface is coated with the modification of lead or metal
The additive amount of copper fiber is 5~10 parts.
8. lead-acid accumulator negative pole lead paste as claimed in claim 7, which is characterized in that its component are as follows: be with lead powder parts by weight
100 parts of meters, surface is coated with lead or 5 parts of the modification copper fiber of metal, 0.5 part of barium sulfate, 1 part of humic acid, 8 parts of sulfuric acid, water 16
Part.
9. such as the preparation method of the described in any item lead-acid accumulator negative pole lead pastes of claim 1-8 characterized by comprising
Surface is coated with lead or the modification copper fiber of metal first mixes after immersion 1-2s with part lead powder in 5% sulfuric acid solution, stirs
Uniformly, it is dry-mixed that remaining lead powder, barium sulfate and humic acid are added, then plus water-wet is mixed, is eventually adding sulfuric acid and the plumbic acid is made
Battery terminal negative lead plaster.
10. a kind of lead-acid accumulator, including negative plate, which is characterized in that the negative plate is by any one of such as claim 1-8 institute
The lead-acid accumulator negative pole lead paste stated is made through coated plate, solidification.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811608995.4A CN109755563B (en) | 2018-12-27 | 2018-12-27 | Lead-acid storage battery negative electrode lead paste and preparation method thereof |
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| CN201811608995.4A CN109755563B (en) | 2018-12-27 | 2018-12-27 | Lead-acid storage battery negative electrode lead paste and preparation method thereof |
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| CN109755563B CN109755563B (en) | 2020-09-29 |
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| CN112599787A (en) * | 2020-12-31 | 2021-04-02 | 国网河南省电力公司南阳供电公司 | Preparation method of lead-acid storage battery |
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