WO2020010754A1 - Manufacturing process of low-temperature-resistant lead-acid battery - Google Patents

Manufacturing process of low-temperature-resistant lead-acid battery Download PDF

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WO2020010754A1
WO2020010754A1 PCT/CN2018/112132 CN2018112132W WO2020010754A1 WO 2020010754 A1 WO2020010754 A1 WO 2020010754A1 CN 2018112132 W CN2018112132 W CN 2018112132W WO 2020010754 A1 WO2020010754 A1 WO 2020010754A1
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temperature
battery
low
glass fiber
lead
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PCT/CN2018/112132
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French (fr)
Chinese (zh)
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郭志刚
赵海敏
李桂发
张峰博
崔海涛
刘玉
邓成智
李亚
宋文龙
施璐
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天能电池集团有限公司
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Publication of WO2020010754A1 publication Critical patent/WO2020010754A1/en

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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
    • H01M10/12—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Definitions

  • the present application relates to the technical field of lead storage battery preparation, for example, to a manufacturing process of a low-temperature-resistant lead storage battery.
  • Lead-acid batteries are currently one of the most widely used batteries, and their development has lasted more than 150 years since the 19th century. In the long evolutionary history of lead-acid batteries, lead-acid batteries suitable for different uses have emerged.
  • the internal battery formation method is basically used now, but the low-temperature performance of the battery shows obvious signs of decline compared with the past.
  • the low-temperature performance of the battery is poor, which will affect the battery in low-temperature environments
  • the use of the battery, especially energy storage and power batteries (generally no special measures for thermal insulation) the battery is used in a low temperature environment, once the low temperature performance of the battery is poor, it can not meet the needs of users, causing the battery to fail in advance, giving users And enterprises caused losses, especially in China's cold northern regions, there are widespread problems such as insufficient battery charging and short driving distance. Therefore, how to improve the low-temperature performance of the battery has become one of the technical problems that perplex battery manufacturers.
  • the new GB / T22199-2017 valve-regulated battery for electric power-assisted vehicles requires requirements for the energy density and low-temperature performance of the battery.
  • Energy density The energy density of batteries 12Ah and below should not be less than 36Wh / kg; 12Ah The energy density of the above batteries should not be lower than 38Wh / kg.
  • Low temperature performance For low temperature capacity Cd1 at -18 °C, it should be no less than 0.70C2 in the second cycle; for low temperature capacity Cd2 at -10 °C, it should not be less than 0.80C2 in the second cycle.
  • battery manufacturers and composite additive manufacturers mainly improve the low-temperature performance of batteries by improving the formulation of positive and negative lead pastes, such as the use of barium sulfate, carbon black, and organic additives to improve battery performance.
  • the formula is to ensure the battery A necessary condition for performance. Only a formula with good low temperature performance can make a battery with good low temperature performance.
  • patent document CN103779557A adds lignin, humic acid, semi-carbonized wood chips, acetylene black, and barium sulfate to the negative lead paste to improve the charge acceptance performance and increase the discharge capacity of the battery at low temperatures.
  • the purpose of this application is to make a lead storage battery with good low temperature performance, which can satisfy its use in a low temperature environment.
  • a manufacturing process of a low-temperature-resistant lead storage battery includes the following steps:
  • this application uses a cooled electrolytic solution to reduce the temperature of the battery after adding the acid to ensure that the temperature of the battery after the addition of the acid does not exceed 35 ° C.
  • the temperature of the battery formation process is further controlled to make the negative plate
  • the expansion agent in the medium is well absorbed in the negative electrode active material, which comprehensively improves the low temperature performance of the battery.
  • the temperature of the electrolyte is -15 ° C to -5 ° C, and may be -10 ° C.
  • the current density is controlled at 3.5 mA / cm 2 in the initial stage of the formation.
  • step (3) the conversion time is 60-75h.
  • the negative electrode lead paste of the negative electrode plate is composed of lead powder, a negative electrode additive, water, and a sulfuric acid solution having a density of 1.30 to 1.40 g / cm 3 , and the weight of the lead powder is 100 parts.
  • the composition of the negative electrode additive includes: 0.5 to 1.5 parts of barium sulfate, 0.1 to 0.5 parts of carbon black, and 0.1 to 0.2 parts of sodium lignosulfonate having a molecular weight greater than 1200; and the added amount of the sulfuric acid solution is 9 to 10 parts
  • the amount of water is 10-12 parts.
  • the acid content of the negative electrode lead paste of the present application is increased by 10-20%.
  • the electrolyte is a sulfuric acid solution with a density of 1.20-1.30 g / cm 3 .
  • the AGM separator is formed by stacking a first glass fiber membrane and a second glass fiber membrane having a median pore diameter larger than that of the first glass fiber membrane, and the thickness of the second glass fiber membrane is 1% of the thickness of the AGM separator. / 3 ⁇ 1/2, during assembly, the second glass fiber membrane is bonded to the negative plate.
  • the pore size of the negative plate is larger than that of the positive plate, the ability of the negative plate to compete for acid is lower than that of the positive plate during low-temperature discharge. In this way, the one with the larger pore diameter faces the negative plate, which facilitates the diffusion of the acid amount in the separator to the negative plate and ensures the negative plate Supply of sulfuric acid during low-temperature discharge.
  • the pore size of the glass fiber membrane can be adjusted by the proportion of the fibers.
  • the median pore size of the first glass fiber membrane is less than 4 ⁇ m, and the median pore size of the second glass fiber membrane is 5 to 6 ⁇ m.
  • the assembly pressure of the pole group is controlled at 60-80 kPa.
  • This application uses a pre-cooled electrolyte to reduce the temperature rise of the battery after adding acid, to ensure that the temperature of the battery after the acid is added is below 35 ° C, and subsequently uses a low-current formation process to further control the temperature of the battery formation process Avoid the precipitation of organic expansion agent due to the high temperature of acid addition, and avoid the increase of colloidal particles of organic expansion agent, ensure that the expansion agent in the negative plate is well adsorbed in the negative active material, and improve the low temperature performance of the battery.
  • the charging and discharging machine used in the embodiment is a Jinfan charging and discharging machine.
  • the existing equipment is used to assemble, acidify, and form the battery. After the formation, the low-temperature performance test of the battery is performed using the existing charger and low-temperature box.
  • Negative lead paste formula 100 kg of lead powder, 1.0 kg of barium sulfate, 0.2 kg of carbon black, 0.15 kg of high-temperature-resistant sodium lignosulfonate, 9.0 kg of sulfuric acid solution with a density of 1.40 g / cm 3 , and 12 kg of water.
  • the high-temperature-resistant sodium lignosulfonate is obtained by sieving a commercially available sodium lignosulfonate product on the market to obtain a sodium lignosulfonate having a molecular weight greater than 1200.
  • the finished product of sodium lignosulfonate that was not sieved was used as control 1, and the others were the same as those in this example.
  • the lead paste is made, and a 20-cell grid is used for coating and curing to obtain a negative electrode plate.
  • a single-layer AGM separator (median pore size: 4 ⁇ m) was used for battery assembly with the positive electrode plate and the negative electrode plate prepared in step 1. The comparison was made with the formula 1 as the comparison sample, and the battery number was 1. number.
  • a sulfuric acid solution having a density of 1.25 g / cm 3 was added to the battery No. 1 and a sulfuric acid solution having a density of 1.245 g / cm 3 was added to the battery No. 2.
  • the temperature of the sulfuric acid solution was 25 ° C.
  • Battery formation was performed with a current density of 5 mA / cm 2 , and the formation time was 48 h.
  • the temperature of the cryostat is controlled at -18 ° C. After being left for 12 hours, it is discharged with a current of 10A to a discharge time of 10.5 volts.
  • the measured experimental results are shown in Table 1:
  • Negative lead paste formula 100 kg of lead powder, 1.0 kg of barium sulfate, 0.2 kg of carbon black, 0.15 kg of high-temperature-resistant sodium lignosulfonate, 10 kg of sulfuric acid solution with a density of 1.40 g / cm 3 , and 11.4 kg of water.
  • the addition amount of the sulfuric acid solution in the negative electrode lead paste formulation was 9.0 kg as the control 2, and the others were the same as in this embodiment.
  • the lead paste is made, and a 20-cell grid is used for coating and curing to obtain a negative electrode plate.
  • a single-layer AGM separator (median pore size: 4 ⁇ m) was used for battery assembly with the positive electrode plate and the negative electrode plate prepared in step 1. The comparison was made with the formula 2 as the comparison sample, the battery number was 3, and the battery number of the formula in this example was 4 number.
  • the formation was performed using a current density of 4 mA / cm 2 , and the formation time was 60 h.
  • the temperature of the cryostat is controlled at -18 ° C. After being left for 12 hours, it is discharged with a current of 10A to a discharge time of 10.5 volts.
  • the measured experimental results are shown in Table 2:
  • Negative lead paste formula 100 kg of lead powder, 1.0 kg of barium sulfate, 0.2 kg of carbon black, 0.18 kg of high temperature sodium lignosulfonate, 10.0 kg of sulfuric acid solution with a density of 1.40 g / cm 3 , and 11.4 kg of water.
  • the added amount of the sulfuric acid solution in the negative electrode lead paste formulation was 9.0 kg as the control 3, and the others were the same as in this embodiment.
  • the lead paste is made, and a 20-cell grid is used for coating and curing to obtain a negative electrode plate.
  • a single-layer AGM separator (median pore size: 4 ⁇ m) was used to assemble the battery with the positive plate and the negative plate prepared in Comparative Example 3. As a comparison, the battery was numbered 5.
  • a two-layer AGM separator is used.
  • One layer has a median pore size of 6.0 ⁇ m and a thickness of 1/3 of the total thickness of the separator.
  • the other layer is a common AGM separator with a median pore size of 4.0 ⁇ m. 2/3 of the total thickness.
  • the side with the large aperture faces the negative electrode plate prepared in this embodiment, and the 6-DZM-20 battery is assembled, and the battery number is 6.
  • the battery 5 and the battery 6 were respectively added with a sulfuric acid solution having a density of 1.24 g / cm 3 , and the temperature of the electrolyte was controlled at -10 ° C.
  • the formation was performed at a current density of 3.5 mA / cm 2 , and the formation time was 68.5 h.
  • the battery 5 and the battery 6 are first discharged at a two-hour rate at room temperature, and then the following tests are performed without charging:
  • the temperature of the cryostat is controlled at -18 ° C. After being left for 12 hours, it is discharged with a current of 10A to a discharge time of 10.5 volts.
  • the measured experimental results are shown in Table 3:

Abstract

The present invention relates to the technical field of lead-acid battery preparation, and disclosed is a manufacturing process of a low-temperature-resistant lead-acid battery. The manufacturing process comprises: (1) preparing positive and negative electrode plates, assembling the positive and negative electrode plates with an AGM separator to form a pole group, and putting the pole group into a battery box to prepare a finished battery; (2) adding an electrolyte having a temperature of -25°C-0°C to the battery box of the finished battery; and (3) forming the electrolyte-added finished battery by using a current having density of 2-4 mA/cm2, and preparing the low-temperature-resistant lead-acid battery.

Description

一种耐低温铅蓄电池的制作工艺Manufacturing process of low temperature resistant lead storage battery 技术领域Technical field
本申请涉及铅蓄电池制备技术领域，例如涉及一种耐低温铅蓄电池的制作工艺。The present application relates to the technical field of lead storage battery preparation, for example, to a manufacturing process of a low-temperature-resistant lead storage battery.
背景技术Background technique
铅酸电池是目前使用范围最广泛的电池之一，其发展从19世纪至今已历时150余年。在漫长的铅酸电池进化史中，涌现出了适用于不同用途的铅酸蓄电池。Lead-acid batteries are currently one of the most widely used batteries, and their development has lasted more than 150 years since the 19th century. In the long evolutionary history of lead-acid batteries, lead-acid batteries suitable for different uses have emerged.
由于环保的要求、企业成本和工艺优化的需要，现在基本上采用电池内化成方式，但是电池的低温性能与过去相比出现明显的下滑的迹象，电池的低温性能差，会影响电池在低温环境下的使用，特别是储能和动力电池(一般没有保温的特殊措施)，电池在低温的环境中使用，一旦电池的低温性能变差，就满足不了用户的需求，造成电池提前失效，给用户和企业造成损失，特别是在我国寒冷的北方地区普遍存在电动助力车的电池充不足电和行驶路程短等问题。因此，如何提升电池的低温性能成为困惑电池厂家的技术难题之一。Due to environmental protection requirements, corporate costs and the need for process optimization, the internal battery formation method is basically used now, but the low-temperature performance of the battery shows obvious signs of decline compared with the past. The low-temperature performance of the battery is poor, which will affect the battery in low-temperature environments The use of the battery, especially energy storage and power batteries (generally no special measures for thermal insulation), the battery is used in a low temperature environment, once the low temperature performance of the battery is poor, it can not meet the needs of users, causing the battery to fail in advance, giving users And enterprises caused losses, especially in China's cold northern regions, there are widespread problems such as insufficient battery charging and short driving distance. Therefore, how to improve the low-temperature performance of the battery has become one of the technical problems that perplex battery manufacturers.
新的国标中GB/T22199-2017的电动助力车用阀控式蓄电池，对电池的能量密度和低温性能都提出了要求，能量密度：12Ah及以下蓄电池的能量密度应不低于36Wh/kg；12Ah以上蓄电池的能量密度应不低于38Wh/kg。低温性能：对-18℃低温容量Cd1在二次循环内应不低于0.70C2；-10℃低温容量Cd2在二次循环内应不低于0.80C2。The new GB / T22199-2017 valve-regulated battery for electric power-assisted vehicles requires requirements for the energy density and low-temperature performance of the battery. Energy density: The energy density of batteries 12Ah and below should not be less than 36Wh / kg; 12Ah The energy density of the above batteries should not be lower than 38Wh / kg. Low temperature performance: For low temperature capacity Cd1 at -18 ℃, it should be no less than 0.70C2 in the second cycle; for low temperature capacity Cd2 at -10 ℃, it should not be less than 0.80C2 in the second cycle.
电池的低温性能是采用塑料隔板代替木隔板后再引起了人们的重视，采用塑料隔板后，电池的低温性能降低，研究结果发现，在木质隔板中含有木质素类的物质，木质素类的物质是提高电池低温性能的重要因素，此后经过多年的实验改进，开发出了可以提高低温性能的添加剂包括木质素、木素磺酸钠、腐殖酸和吲哚林、栲胶、合成揉剂等有机添加剂。The low-temperature performance of batteries has attracted people's attention after the use of plastic separators instead of wooden separators. After using plastic separators, the low-temperature performance of batteries decreases. The results of the study found that lignin-containing substances, Pigments are an important factor to improve the low-temperature performance of batteries. After years of experimental improvements, additives that can improve the low-temperature performance have been developed including lignin, sodium lignosulfonate, humic acid and indolin, extractives, Organic additives such as synthetic kneading agents.
目前电池生产厂家和复合添加剂的生产厂家主要是通过改进正负极 铅膏配方来改善电池的低温性能，如通过硫酸钡、炭黑和有机添加剂的联合使用来提高电池的性能，配方是保证电池性能必要条件，只有低温性能好的配方才有可能制作出低温性能好的电池。如专利文献CN103779557A通过在负极铅膏中添加木素、腐植酸、半炭化木屑、乙炔黑、硫酸钡来提升电池低温时的充电接受性能和增加放电容量。At present, battery manufacturers and composite additive manufacturers mainly improve the low-temperature performance of batteries by improving the formulation of positive and negative lead pastes, such as the use of barium sulfate, carbon black, and organic additives to improve battery performance. The formula is to ensure the battery A necessary condition for performance. Only a formula with good low temperature performance can make a battery with good low temperature performance. For example, patent document CN103779557A adds lignin, humic acid, semi-carbonized wood chips, acetylene black, and barium sulfate to the negative lead paste to improve the charge acceptance performance and increase the discharge capacity of the battery at low temperatures.
发明内容Summary of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics detailed in this article. This summary is not intended to limit the scope of protection of the claims.
由于电池化成是一个复杂的过程，如果没有考虑到电池化成过程以及电池设计尤其是超细玻璃纤维隔板(AGM隔板)的设计对电池低温性能的影响，仅依靠铅膏配方改进是没有办法真正解决电池低温性能差的问题。Because battery formation is a complicated process, if the battery formation process and the design of the battery, especially the design of ultra-fine glass fiber separators (AGM separators), have not been considered, the battery low-temperature performance cannot be improved by relying only on the formulation of lead paste. Really solve the problem of poor low temperature performance of the battery.
本申请的目的在于制作一种低温性能好的铅蓄电池，满足其在低温环境下使用。The purpose of this application is to make a lead storage battery with good low temperature performance, which can satisfy its use in a low temperature environment.
为实现上述目的，本申请采用如下技术方案：In order to achieve the above purpose, this application uses the following technical solutions:
一种耐低温铅蓄电池的制作工艺，包括以下步骤：A manufacturing process of a low-temperature-resistant lead storage battery includes the following steps:
(1)制备正、负极板，并与AGM隔板组装成极群，入电池盒制得成品电池；(1) Prepare positive and negative plates, assemble them with AGM separator to form a pole group, and put them into a battery box to make a finished battery;
(2)往成品电池的电池盒内加入温度为-25℃～0℃的电解液；(2) Add an electrolyte having a temperature of -25 ° C to 0 ° C into the battery case of the finished battery;
(3)采用电流密度为2～4mA/cm 2对加电解液后的成品电池进行化成，制得所述的耐低温铅蓄电池。 (3) using a current density of 2 to 4 mA / cm 2 to chemically convert the finished battery after adding the electrolyte to obtain the low-temperature-resistant lead storage battery.
由于加酸后电池温度徒增，过高的温度会使负极膨胀剂在硫酸中胶体粒子直径增加，增加负极板孔径，远远大于AGM隔板的中值孔径，这样造成AGM隔板向负极供酸困难，降低电池的低温性能。因此，本申请采用冷却过的电解液，降低加酸后电池的温度，确保加酸后的电池温度不超过35℃，再结合小电流的化成工艺，进一步控制电池化成过程的温度，使负极板中的膨胀剂很好地吸附在负极活性物质中，综合提升电池的低温性能。Due to the excessive increase in battery temperature after the addition of acid, excessively high temperatures will increase the diameter of the colloidal particles of the negative electrode expansion agent in sulfuric acid and increase the diameter of the negative electrode plate, which is much larger than the median diameter of the AGM separator. Difficult acid, reduce the low temperature performance of the battery. Therefore, this application uses a cooled electrolytic solution to reduce the temperature of the battery after adding the acid to ensure that the temperature of the battery after the addition of the acid does not exceed 35 ° C. In combination with the low-current formation process, the temperature of the battery formation process is further controlled to make the negative plate The expansion agent in the medium is well absorbed in the negative electrode active material, which comprehensively improves the low temperature performance of the battery.
可选地，所述电解液的温度为-15℃～-5℃，可以为-10℃。Optionally, the temperature of the electrolyte is -15 ° C to -5 ° C, and may be -10 ° C.
采用适度的电流，控制电池化成过程的温度。如过高的电流密度将会使电池的温度升高，木素磺酸钠形成大的胶粒，增加负极板的孔径，降低 电池的性能。过小的电流会使化成时间延长，不能满足生产的要求。可选地，步骤(3)中，化成初期，电流密度控制在3.5mA/cm 2。 Use a moderate current to control the temperature of the battery formation process. If the current density is too high, the temperature of the battery will rise, and sodium lignosulfonate will form large colloidal particles, which will increase the pore size of the negative plate and reduce the performance of the battery. Too small current will lengthen the formation time and cannot meet the production requirements. Optionally, in the step (3), the current density is controlled at 3.5 mA / cm 2 in the initial stage of the formation.
可选地，步骤(3)中，化成时间为60-75h。Optionally, in step (3), the conversion time is 60-75h.
本申请还可以通过优化负极铅膏的配方，提高电池的低温性能。可选地，步骤(1)中，所述负极板的负极铅膏由铅粉、负极添加剂、水和密度为1.30～1.40g/cm 3的硫酸溶液组成，以铅粉的重量份为100份计，所述负极添加剂的组成包括：硫酸钡0.5～1.5份、炭黑0.1～0.5份、分子量大于1200的木素磺酸钠0.1～0.2份；所述硫酸溶液的添加量为9～10份，水的用量为10～12份。 The application can also improve the low-temperature performance of the battery by optimizing the formula of the negative electrode lead paste. Optionally, in step (1), the negative electrode lead paste of the negative electrode plate is composed of lead powder, a negative electrode additive, water, and a sulfuric acid solution having a density of 1.30 to 1.40 g / cm 3 , and the weight of the lead powder is 100 parts. In total, the composition of the negative electrode additive includes: 0.5 to 1.5 parts of barium sulfate, 0.1 to 0.5 parts of carbon black, and 0.1 to 0.2 parts of sodium lignosulfonate having a molecular weight greater than 1200; and the added amount of the sulfuric acid solution is 9 to 10 parts The amount of water is 10-12 parts.
本申请在有机膨胀剂的筛选研究中得出：相较于小分子量的木素磺酸钠，分子量在1200以上的木素磺酸钠不容易从负极活性物质中脱附，因此，本申请选用大分子量的木素磺酸钠，并适度增加其添加量，保证其在在负极板中的有效剂量。In the screening study of organic bulking agents, the present application concluded that, compared with sodium lignosulfonate with a small molecular weight, sodium lignosulfonate with a molecular weight of 1200 or more is not easy to desorb from the negative electrode active material. Therefore, this application uses Large molecular weight sodium lignosulfonate, and increase its amount to ensure its effective dose in the negative plate.
相对于现有的负极铅膏配方，本申请的负极铅膏的含酸量增加了10～20％。Compared with the existing negative electrode lead paste formula, the acid content of the negative electrode lead paste of the present application is increased by 10-20%.
由于负极板含酸量提高，采用的电解液的比重可适度降低，以降低加酸后的温升，所述的电解液为密度为1.20-1.30g/cm 3的硫酸溶液。 Due to the increase in the acid content of the negative electrode plate, the specific gravity of the electrolyte used can be moderately reduced to reduce the temperature rise after the acid is added. The electrolyte is a sulfuric acid solution with a density of 1.20-1.30 g / cm 3 .
可选地，所述的AGM隔板由第一玻璃纤维膜和孔径中值大于第一玻璃纤维膜的第二玻璃纤维膜叠加而成，第二玻璃纤维膜的厚度为AGM隔板厚度的1/3～1/2，组装时，第二玻璃纤维膜贴合负极板。Optionally, the AGM separator is formed by stacking a first glass fiber membrane and a second glass fiber membrane having a median pore diameter larger than that of the first glass fiber membrane, and the thickness of the second glass fiber membrane is 1% of the thickness of the AGM separator. / 3 ～ 1/2, during assembly, the second glass fiber membrane is bonded to the negative plate.
由于负极板的孔径比正极板大，在低温放电时，负极板争夺酸的能力比正极板差，这样采用孔径大的一方朝向负极板，利于隔板中的酸量向负极扩散，保障负极板低温放电时硫酸的供应。玻璃纤维膜的孔径大小可以通过纤维的配比来调整。Because the pore size of the negative plate is larger than that of the positive plate, the ability of the negative plate to compete for acid is lower than that of the positive plate during low-temperature discharge. In this way, the one with the larger pore diameter faces the negative plate, which facilitates the diffusion of the acid amount in the separator to the negative plate and ensures the negative plate Supply of sulfuric acid during low-temperature discharge. The pore size of the glass fiber membrane can be adjusted by the proportion of the fibers.
可选地，所述的第一玻璃纤维膜的孔径中值小于4μm，第二玻璃纤维膜的孔径中值为5～6μm。Optionally, the median pore size of the first glass fiber membrane is less than 4 μm, and the median pore size of the second glass fiber membrane is 5 to 6 μm.
为了保持隔板和正负极板的接触，所述极群的装配压力控制在60～80kPa。In order to maintain the contact between the separator and the positive and negative plates, the assembly pressure of the pole group is controlled at 60-80 kPa.
本申请具备的有益效果：The beneficial effects of this application:
(1)本申请采用预先冷却的电解液，降低了加酸后电池的温升，保证电池加酸后的温度在35℃以下，后续采用小电流的化成工艺，进一步控制 电池化成过程的温度，避免因为加酸温度过高造成有机膨胀剂的析出，同时避免了有机膨胀剂胶体颗粒的增加，保证负极板中的膨胀剂很好地吸附在负极活性物质中，提升电池的低温性能。(1) This application uses a pre-cooled electrolyte to reduce the temperature rise of the battery after adding acid, to ensure that the temperature of the battery after the acid is added is below 35 ° C, and subsequently uses a low-current formation process to further control the temperature of the battery formation process Avoid the precipitation of organic expansion agent due to the high temperature of acid addition, and avoid the increase of colloidal particles of organic expansion agent, ensure that the expansion agent in the negative plate is well adsorbed in the negative active material, and improve the low temperature performance of the battery.
(2)采用本申请的制作工艺制作的铅蓄电池的低温性能提高了30％以上，具有极好的推广价值。(2) The low-temperature performance of the lead-acid battery produced by the manufacturing process of the present application is improved by more than 30%, and has excellent promotion value.
在阅读并理解了详细描述后，可以明白其他方面。After reading and understanding the detailed description, you can understand other aspects.
具体实施方式detailed description
下面结合实施例对本申请作进一步说明，但下述实施例仅仅为本申请的优选实施例，并非全部。The following further describes the present application with reference to the embodiments, but the following embodiments are merely preferred embodiments of the present application, but not all of them.
实施例中采用的充放电机为金帆充放电机。本申请方法采用现有的设备对电池进行组装、加酸、化成，化成后用现有的充电机和低温箱进行电池的低温性能测试。The charging and discharging machine used in the embodiment is a Jinfan charging and discharging machine. In the method of the present application, the existing equipment is used to assemble, acidify, and form the battery. After the formation, the low-temperature performance test of the battery is performed using the existing charger and low-temperature box.
实施例1Example 1
1、制备负极极板1.Preparing the negative electrode plate
负极铅膏配方：铅粉100kg、硫酸钡1.0kg、炭黑0.2kg、耐高温木素磺酸钠0.15kg、密度为1.40g/cm 3的硫酸溶液9.0kg、水12kg。 Negative lead paste formula: 100 kg of lead powder, 1.0 kg of barium sulfate, 0.2 kg of carbon black, 0.15 kg of high-temperature-resistant sodium lignosulfonate, 9.0 kg of sulfuric acid solution with a density of 1.40 g / cm 3 , and 12 kg of water.
其中耐高温木素磺酸钠由市场上购买的木素磺酸钠成品进行筛分后获得的分子量大于1200的木素磺酸钠。The high-temperature-resistant sodium lignosulfonate is obtained by sieving a commercially available sodium lignosulfonate product on the market to obtain a sodium lignosulfonate having a molecular weight greater than 1200.
以未进行筛分的木素磺酸钠成品作为对照1，其他同本实施例。The finished product of sodium lignosulfonate that was not sieved was used as control 1, and the others were the same as those in this example.
再参照现有工艺进行铅膏的和制、用20电池板栅涂板、固化，制得负极极板。Then, referring to the existing process, the lead paste is made, and a 20-cell grid is used for coating and curing to obtain a negative electrode plate.
2、电池组装2.Battery assembly
采用单层的AGM隔板(中值孔径为4μm)与正极板、步骤1制备的负极板进行电池组装，对照1配方作为对比样，电池编号为1号，本实施例配方的电池编号为2号。A single-layer AGM separator (median pore size: 4 μm) was used for battery assembly with the positive electrode plate and the negative electrode plate prepared in step 1. The comparison was made with the formula 1 as the comparison sample, and the battery number was 1. number.
3、电池化成3. Battery formation
编号为1电池内加入密度为1.25g/cm 3的硫酸溶液，编号为2电池内加入密度为1.245g/cm 3的硫酸溶液。硫酸溶液的温度为25℃。 A sulfuric acid solution having a density of 1.25 g / cm 3 was added to the battery No. 1 and a sulfuric acid solution having a density of 1.245 g / cm 3 was added to the battery No. 2. The temperature of the sulfuric acid solution was 25 ° C.
电流密度为5mA/cm 2进行电池化成，化成时间为48h。 Battery formation was performed with a current density of 5 mA / cm 2 , and the formation time was 48 h.
4、电池低温检测4, battery low temperature detection
电池1和电池2在进行了一次常温两小时率放电后，再在不充电的情 况下进行如下测试：Battery 1 and Battery 2 were discharged at room temperature for two hours, and then the following tests were performed without charging:
低温箱的温度控制在-18℃，在放置12小时后，以10A的电流放电至10.5伏的放电时间。测得的实验结果如表1所示：The temperature of the cryostat is controlled at -18 ° C. After being left for 12 hours, it is discharged with a current of 10A to a discharge time of 10.5 volts. The measured experimental results are shown in Table 1:
表1：-18℃电池放电时间Table 1: Battery discharge time at -18 ℃
Figure PCTCN2018112132-appb-000001
Figure PCTCN2018112132-appb-000001
从表1的结果看出，经过改进后的木素磺酸钠电池的低温性能比不改进的木素磺酸钠的低温效果好，主要是分子量增加后，在电池化成过程中，更容易吸附在负极板上，促使电池低温性能提升。From the results in Table 1, it can be seen that the low-temperature performance of the improved sodium lignosulfonate battery is better than that of the unmodified sodium lignosulfonate. The main reason is that after the molecular weight increases, it is easier to adsorb during the battery formation process. On the negative plate, it promotes the low-temperature performance of the battery.
实施例2Example 2
1、制备负极极板1.Preparing the negative electrode plate
负极铅膏配方：铅粉100kg、硫酸钡1.0kg、炭黑0.2kg、耐高温木素磺酸钠0.15kg、密度为1.40g/cm 3的硫酸溶液10kg、水11.4kg。 Negative lead paste formula: 100 kg of lead powder, 1.0 kg of barium sulfate, 0.2 kg of carbon black, 0.15 kg of high-temperature-resistant sodium lignosulfonate, 10 kg of sulfuric acid solution with a density of 1.40 g / cm 3 , and 11.4 kg of water.
以负极铅膏配方中的硫酸溶液添加量为9.0kg作为对照2，其他同本实施例。The addition amount of the sulfuric acid solution in the negative electrode lead paste formulation was 9.0 kg as the control 2, and the others were the same as in this embodiment.
再参照现有工艺进行铅膏的和制、用20电池板栅涂板、固化，制得负极极板。Then, referring to the existing process, the lead paste is made, and a 20-cell grid is used for coating and curing to obtain a negative electrode plate.
2、电池组装2.Battery assembly
采用单层的AGM隔板(孔径中值为4μm)与正极板、步骤1制备的负极板进行电池组装，对照2配方作为对比样，电池编号为3号，本实施例配方的电池编号为4号。A single-layer AGM separator (median pore size: 4 μm) was used for battery assembly with the positive electrode plate and the negative electrode plate prepared in step 1. The comparison was made with the formula 2 as the comparison sample, the battery number was 3, and the battery number of the formula in this example was 4 number.
3、电池化成3. Battery formation
电池3中加入密度为1.25g/cm 3的硫酸溶液，电池4中加入密度为1.24g/cm 3的硫酸溶液，电解液的温度控制在-10℃。 3 was added to cell density of 1.25g / cm 3 sulfuric acid solution, a density of the battery 4 is added a solution of sulfuric acid 1.24g / cm 3, the temperature of the electrolytic solution controlled at -10 ℃.
采用4mA/cm 2的电流密度进行化成，化成时间为60h。 The formation was performed using a current density of 4 mA / cm 2 , and the formation time was 60 h.
4、电池低温检测4, battery low temperature detection
电池3和电池4首先进行了一次常温两小时率放电后，在不充电的情况下进行如下测试：Battery 3 and Battery 4 were first discharged at a two-hour rate at room temperature, and the following tests were performed without charging:
低温箱的温度控制在-18℃，在放置12小时后，以10A的电流放电至10.5伏的放电时间。测得实验结果如表2所示：The temperature of the cryostat is controlled at -18 ° C. After being left for 12 hours, it is discharged with a current of 10A to a discharge time of 10.5 volts. The measured experimental results are shown in Table 2:
表2：-18℃电池放电时间Table 2: Battery discharge time at -18 ℃
Figure PCTCN2018112132-appb-000002
Figure PCTCN2018112132-appb-000002
从表2结果可以看出，采用冷却的电解液，使加酸后电池温度明显降低，同时，采用较小的化成电流密度，电池化成过程中的温度也明显降低，保证加入的木素磺酸钠在负极板中的有效吸附，提高了电池的低温性能。From the results in Table 2, it can be seen that the temperature of the battery is significantly reduced after the acid is added using the cooled electrolyte, and at the same time, the smaller the formation current density is, the lower the temperature during the battery formation process is. The effective adsorption of sodium in the negative plate improves the low temperature performance of the battery.
实施例3Example 3
1、制备负极极板1.Preparing the negative electrode plate
负极铅膏配方：铅粉100kg、硫酸钡1.0kg、炭黑0.2kg、耐高温木素磺酸钠0.18kg、密度为1.40g/cm 3的硫酸溶液10.0kg、水11.4kg。 Negative lead paste formula: 100 kg of lead powder, 1.0 kg of barium sulfate, 0.2 kg of carbon black, 0.18 kg of high temperature sodium lignosulfonate, 10.0 kg of sulfuric acid solution with a density of 1.40 g / cm 3 , and 11.4 kg of water.
以负极铅膏配方中的硫酸溶液添加量为9.0kg作为对照3，其他同本实施例。The added amount of the sulfuric acid solution in the negative electrode lead paste formulation was 9.0 kg as the control 3, and the others were the same as in this embodiment.
再参照现有工艺进行铅膏的和制、用20电池板栅涂板、固化，制得负极极板。Then, referring to the existing process, the lead paste is made, and a 20-cell grid is used for coating and curing to obtain a negative electrode plate.
2、电池组装2.Battery assembly
采用单层的AGM隔板(孔径中值为4μm)与正极板、对照3制备的负极板进行电池组装，作为对比样，电池编号为5号。A single-layer AGM separator (median pore size: 4 μm) was used to assemble the battery with the positive plate and the negative plate prepared in Comparative Example 3. As a comparison, the battery was numbered 5.
采用双层的AGM隔板，其中一层的孔径中值为6.0μm，厚度为隔板总厚度的1/3，另一层为孔径中值为4.0μm的普通AGM隔板，厚度为隔板总厚度的2/3。孔径大的一侧朝向本实施例配方制备的负极板，进行6-DZM-20电池的组装，电池编号为6号。A two-layer AGM separator is used. One layer has a median pore size of 6.0 μm and a thickness of 1/3 of the total thickness of the separator. The other layer is a common AGM separator with a median pore size of 4.0 μm. 2/3 of the total thickness. The side with the large aperture faces the negative electrode plate prepared in this embodiment, and the 6-DZM-20 battery is assembled, and the battery number is 6.
3、电池化成3. Battery formation
电池5和电池6分别加入密度为1.24g/cm 3的硫酸溶液，电解液的温度控制在-10℃。 The battery 5 and the battery 6 were respectively added with a sulfuric acid solution having a density of 1.24 g / cm 3 , and the temperature of the electrolyte was controlled at -10 ° C.
采用3.5mA/cm 2的电流密度进行化成，化成的时间68.5h。 The formation was performed at a current density of 3.5 mA / cm 2 , and the formation time was 68.5 h.
4、电池低温检测4, battery low temperature detection
电池5和电池6先进行一次常温两小时率放电后，在不充电的情况下进行如下测试：The battery 5 and the battery 6 are first discharged at a two-hour rate at room temperature, and then the following tests are performed without charging:
低温箱的温度控制在-18℃，在放置12小时后，以10A的电流放电至10.5伏的放电时间。测得实验结果如表3所示：The temperature of the cryostat is controlled at -18 ° C. After being left for 12 hours, it is discharged with a current of 10A to a discharge time of 10.5 volts. The measured experimental results are shown in Table 3:
表3：-18℃电池放电时间Table 3: Battery discharge time at -18 ℃
Figure PCTCN2018112132-appb-000003
Figure PCTCN2018112132-appb-000003
从上面结果看出，采用耐高温的木素磺酸钠并适度提高负极配方中的酸量、采用冷却过的低温电解液(-10℃)电解液，使用双层的AGM隔板并使孔径大的一侧朝向负极板，采用小的电流充电，电池的低温性能会明显提高。It can be seen from the above results that the use of high-temperature-resistant sodium lignosulfonate and a moderate increase in the amount of acid in the negative electrode formulation, the use of a cooled low-temperature electrolyte (-10 ° C) electrolyte, the use of a double-layer AGM separator and the aperture The large side faces the negative plate, and charging with a small current will significantly improve the low temperature performance of the battery.

Claims (9)

  1. 一种耐低温铅蓄电池的制作工艺，其中，包括以下步骤：A manufacturing process of a low-temperature-resistant lead storage battery, which includes the following steps:
    (1)制备正、负极板，并与超细玻璃纤维隔板组装成极群，入电池盒制得成品电池；(1) Prepare positive and negative plates, assemble them with ultra-fine glass fiber separators, and put them into a battery box to make finished batteries;
    (2)往成品电池的电池盒内加入温度为-25℃～0℃的电解液；(2) Add an electrolyte having a temperature of -25 ° C to 0 ° C into the battery case of the finished battery;
    (3)采用电流密度为2～4mA/cm 2对加电解液后的成品电池进行化成，制得所述的耐低温铅蓄电池。 (3) using a current density of 2 to 4 mA / cm 2 to chemically convert the finished battery after adding the electrolyte to obtain the low-temperature-resistant lead storage battery.
  2. 如权利要求1所述的耐低温铅蓄电池的制作工艺，其中，步骤(1)中，所述负极板的负极铅膏由铅粉、负极添加剂、水和密度为1.30～1.40g/cm 3的硫酸溶液组成，以铅粉的重量份为100份计，所述负极添加剂的组成包括：硫酸钡0.5～1.5份、炭黑0.1～0.5份、分子量大于1200的木素磺酸钠0.1～0.2份；所述硫酸溶液的添加量为9～10份，水的用量为10～12份。 Low temperature fabrication process according to the lead storage battery as claimed in claim 1, wherein step (1), the negative electrode plate of a lead-lead oxide paste, a negative electrode additive, water and a density of 1.30 ~ 1.40g / cm 3 of The composition of the sulfuric acid solution is 100 parts by weight of lead powder. The composition of the negative electrode additive includes: 0.5 to 1.5 parts of barium sulfate, 0.1 to 0.5 parts of carbon black, and 0.1 to 0.2 parts of sodium lignosulfonate having a molecular weight greater than 1200. The added amount of the sulfuric acid solution is 9-10 parts, and the used amount of water is 10-12 parts.
  3. 如权利要求1所述的耐低温铅蓄电池的制作工艺，其中，所述的超细玻璃纤维隔板由第一玻璃纤维膜和孔径中值大于第一玻璃纤维膜的第二玻璃纤维膜叠加而成，第二玻璃纤维膜的厚度为超细玻璃纤维隔板厚度的1/3～1/2，组装时，第二玻璃纤维膜贴合负极板。The process for manufacturing a low-temperature lead-acid battery according to claim 1, wherein the ultra-fine glass fiber separator is formed by superposing a first glass fiber membrane and a second glass fiber membrane having a median pore size larger than the first glass fiber membrane. The thickness of the second glass fiber membrane is 1/3 to 1/2 of the thickness of the ultra-fine glass fiber separator. During assembly, the second glass fiber membrane is bonded to the negative plate.
  4. 如权利要求1所述的耐低温铅蓄电池的制作工艺，其中，所述电解液的温度为-15℃～-5℃。The manufacturing process of the low-temperature-resistant lead storage battery according to claim 1, wherein the temperature of the electrolytic solution is -15 ° C to -5 ° C.
  5. 如权利要求1所述的耐低温铅蓄电池的制作工艺，其中，步骤(3)中，化成初期，电流密度控制在3.5mA/cm 2。 The process for manufacturing a low-temperature lead-acid battery according to claim 1, wherein in the step (3), the current density is controlled at 3.5 mA / cm 2 at the initial stage of formation.
  6. 如权利要求1所述的耐低温铅蓄电池的制作工艺，其中，步骤(3)中，化成时间为60～75h。The process for manufacturing a low-temperature-resistant lead storage battery according to claim 1, wherein in the step (3), the formation time is 60 to 75 hours.
  7. 如权利要求1或2所述的耐低温铅蓄电池的制作工艺，其中，所述电解液为密度为1.20～1.30g/cm 3的硫酸溶液。 Production process or low temperature of the lead-acid battery as claimed in claim 1 or 2, wherein the electrolyte is a density of 1.20 ~ 1.30g / cm 3 sulfuric acid solution.
  8. 如权利要求3所述的耐低温铅蓄电池的制作工艺，其中，所述的第一玻璃纤维膜的孔径中值小于4μm，第二玻璃纤维膜的孔径中值为5～6μm。The process for manufacturing a low temperature resistant lead storage battery according to claim 3, wherein the median pore size of the first glass fiber membrane is less than 4 μm, and the median pore size of the second glass fiber membrane is 5 to 6 μm.
  9. 如权利要求1所述的耐低温铅蓄电池的制作工艺，其中，所述极群的装配压力为60～80kPa。The manufacturing process of the low-temperature-resistant lead storage battery according to claim 1, wherein an assembly pressure of the pole group is 60 to 80 kPa.
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