WO2019068220A1 - 一种铅酸蓄电池极板用短纤维 - Google Patents

一种铅酸蓄电池极板用短纤维 Download PDF

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WO2019068220A1
WO2019068220A1 PCT/CN2017/105267 CN2017105267W WO2019068220A1 WO 2019068220 A1 WO2019068220 A1 WO 2019068220A1 CN 2017105267 W CN2017105267 W CN 2017105267W WO 2019068220 A1 WO2019068220 A1 WO 2019068220A1
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Prior art keywords
fiber
lead
electrode plate
short
acid battery
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PCT/CN2017/105267
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English (en)
French (fr)
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朱子毅
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朱子毅
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Priority to PCT/CN2017/105267 priority Critical patent/WO2019068220A1/zh
Publication of WO2019068220A1 publication Critical patent/WO2019068220A1/zh

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the present invention relates to the field of lead acid battery additives, and in particular to a short fiber for a lead-acid battery plate.
  • lead-acid batteries Since the invention of lead-acid batteries, they have always had an absolute advantage in chemical power sources. This is because of its low cost, easy availability of raw materials, sufficient reliability in use, high current discharge and a wide range of ambient temperatures. Lead-acid batteries are currently the world's most widely used, safe, and recyclable secondary energy source. At the same time, lead-acid battery technology has been developed over the years, and its breakthrough in energy, cycle life, high and low temperature adaptability, etc., short fiber as an important part of the battery plate, plays an important role in the battery. effect.
  • a short fiber having a length of l-4 mm and a short fiber as a skeleton of an active material is added to a lead paste for preparing a plate, and a three-dimensional network structure is formed in the electrode plate to enhance the mechanical strength of the electrode plate.
  • the lead paste is easily formed during the coating process, and the same layer prevents the cracking of the plates during the curing and drying process and reduces the powder removal of the plates during the assembly process.
  • the present invention provides a short fiber, which is added to a lead acid battery plate, which can greatly increase the strength of the electrode plate, and the effect is 3 times; the effective reduction of the floating powder is reduced by about 20%; Waste in the production process; about 25% reduction.
  • the specific technical solution of the present invention is as follows: Design a lead-acid battery plate (for) short fiber, comprising a plurality of organic fibers having a length of ⁇ 6 mm, wherein the single fiber fineness of the organic fiber is 0.1
  • Short fibers having a single fineness of 0.3 to 0.6 D are preferred.
  • short fibers having a single fineness of 0.35 to 0.5D;
  • short fibers having a single fineness of 0.35D
  • the above-mentioned lead-acid battery plate short fiber selected from one or more of polyester fiber or polypropylene fiber or polyacrylonitrile fiber;
  • the fine fiber has a fineness deviation rate of ⁇ 10%.
  • the beneficial effects of the present invention are as follows: By applying the invention, the strength of the electrode plate can be greatly improved, and the effect is 3 times; the effective reduction of the floating powder is reduced by about 20%; the waste in the production process is reduced; and the reduction is about 25%. Advantageous effects of the invention
  • the strength of the electrode plate can be greatly improved, and the effect is 3 times; the effective reduction of the floating powder is reduced by about 20%; the waste in the production process is reduced; and the reduction is about 25%.
  • Single fiber length unit mm (mm), single fiber fineness unit D (denier), denier is the weight in grams of 9000 meters of fiber at a given moisture regain. Denier is referred to as denier (D), such as 9000 meters of fiber weight
  • 1 gram is 1 denier, when the density of the fiber is constant, the larger the denier, the thicker the fiber.
  • the positive electrode plate is connected to the positive electrode of the power source
  • the negative electrode plate is connected to the negative electrode plate of the power source
  • the lead paste material on the positive electrode plate is electrochemically converted into Pb02.
  • Primary activity The substance, the lead material on the negative electrode plate is converted into an active substance mainly composed of spongy lead.
  • Drop test Each of the examples and the comparative plate were taken separately, numbered, and the weight was weighed. Let the plates parallel to the clean concrete floor, at 1 meter height, allow the plates to fall freely. The drop test was repeated until the plate had a large area of ointment and the experiment was stopped. The weight change before and after the recording was recorded, and the weight change was recorded 3 times, 6 times, and 9 times, and the experimental results were measured.
  • 1-1, 1-2, 1-3 are polyester fibers, 1-4 are polypropylene fibers, and 1-5 are polyacrylonitrile fibers, and the added mass is 0.1% of the total mass of the lead paste.
  • the single fiber length is 3mm and the single fiber fineness is 1.5D. The measurement results are as follows
  • 3-1,3-2, 3-3 is a polyester fiber
  • 3-4 is a polypropylene fiber
  • 3-5 is a polyacrylonitrile fiber
  • the added mass is 0.1% of the total mass of the lead paste.
  • the length of the single fiber is 3mm, and the single fiber fineness is 1.0 D.
  • the measurement results are as follows:
  • 4-1,4-2, 4-3 is a polyester fiber
  • 4-4 is a polypropylene fiber
  • 4-5 is a polyacrylonitrile fiber
  • the added mass is 0.1% of the total mass of the lead paste.
  • the single fiber has a length of 3 mm and a single fiber fineness of 0.8 D. The measurement results are as follows
  • 5-1, 5-2, 5-3 in the short fiber table is a polyester fiber
  • 5-4 is a polypropylene fiber
  • 5-5 is a polyacrylonitrile fiber
  • the added mass is 0.1% of the total mass of the lead paste.
  • the single fiber has a length of 3 mm and a single fiber fineness of 0.7 D. The measurement results are as follows
  • 6-1, 6-2, 6-3 are polyester fibers, 6-4 is polypropylene fiber, and 6-5 is polyacrylonitrile fiber, and the added mass is 0.1% of the total mass of the lead paste.
  • the single fiber length is 3mm and the single fiber fineness is 0.5D. The measurement results are as follows
  • 7-1, 7-2, 7-3 are polyester fibers, 7-4 is polypropylene fiber, and 7-5 is polyacrylonitrile fiber, and the added mass is 0.1% of the total mass of the lead paste.
  • the single fiber has a length of 3 mm and a single fiber fineness of 0.35 D. The measurement results are as follows
  • 8-1, 8-2, 8-3 are polyester fibers, 8-4 is polypropylene fiber, and 8-5 is polyacrylonitrile fiber, and the added mass is 0.1% of the total mass of the lead paste.
  • the length of the single fiber is 3mm, and the single fiber fineness is 0.15 D.
  • the strength of the plates is also related to the ratio of addition of the short fibers. For this reason, we tested the strength of the plates for different addition ratios of the short fibers.
  • Example 6 Optionally, 10 negative electrode plates were randomly numbered, and the single fiber fineness was selected to be 0.35 D, and the length was 2-3 mm, and the addition ratio was 0.15% of the total mass of the lead paste. The results are as follows: quiet
  • Example 7 Optional 5 negative electrode plates were randomly numbered, and the single fiber fineness was selected to be 0.35D, the length was 2-3 mm, and the addition ratio was 0.2% of the total mass of the lead paste. The results are as follows:
  • Example 7 The index of Example 7 was significantly better than the comparative example.
  • Example 8 Optional 10 positive electrode plates, random number, single fiber fineness selection 0. 5D, length 2-3mm addition ratio is 0.08% of the total mass of the lead paste. The results are as follows:
  • Example 9 Optional 10 positive electrode plates, random number, single fiber fineness selection 0. 5D, length 2-3mm, the addition ratio is 0.05% of the total mass of the lead paste. The results are as follows:
  • a beneficial effect can be obtained in the region where the addition ratio is 0.05-0.2.
  • the plate of the lead-acid battery was dissected and the short fibers were separated, and it was found that the fibers were basically unchanged.
  • the fineness of the short fibers in the plates of the lead-acid battery can be obtained, and the weight ratio of the short fibers and the active material of the plates can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

一种铅酸蓄电池极板用短纤维，包括多根长度为≤6mm的有机纤维，所述的有机纤维单纤细度为0.15-0.8D。应用所述短纤维，提高了极板的强度，降低生产过程中的废损，增加活性物质的机械强度，防止脱落，从而提高循环性能；同时减少浮粉产生，还可以提高正极板的孔率，提高初容量。

Description

发明名称：一种铅酸蓄电池极板用短纤维
技术领域
[0001] 本发明涉及铅酸电池添加剂领域， 具体涉及一种铅酸蓄电池极板用短纤维。
背景技术
[0002] 铅酸蓄电池自发明后， 在化学电源中一直占有绝对优势。 这是因为其价格低廉 、 原材料易于获得， 使用上有充分的可靠性， 适用于大电流放电及广泛的环境 温度范围等优点。 铅酸蓄电池是目前世界上应用范围最为广泛， 安全性能， 可 回收性最高的二次能源。 与此同吋， 铅酸蓄电池技术经过多年发展， 其比能量 、 循环寿命、 高低温适应性等问题已有所突破， 短纤维作为蓄电池极板中重要 的组成部分， 在电池中发挥着举足轻重的作用。
技术问题
[0003] 在制备极板的铅膏中加入了一般长度为 l-4mm短纤维， 短纤维作为活性物质粘 结的骨架， 在极板中构成三维网状结构， 增强了极板的机械强度。 加入短纤维 后， 在涂板过程中铅膏容易成型， 同吋也在一定程度上防止了固化干燥过程中 极板的幵裂和减少了装配过程中极板的脱粉。
问题的解决方案
技术解决方案
[0004] 为了解决上述技术问题， 本发明提供了一种短纤维， 添加入铅酸电池极板， 可 以大幅提高极板强度， 效果为原来 3倍； 有效减少浮粉， 约降低 20%左右； 降低 生产过程中废损； 约降低 25%左右。
[0005] 为了实现上述目的， 本发明具体的技术方案如下： 设计一种铅酸蓄电池极板 （ 用） 短纤维， 包括多根长度为≤6mm的有机纤维， 所述的有机纤维单纤细度为 0.1
5-0.8D。
[0006] 优选单纤细度为 0.3-0.6D的短纤维；
[0007] 进一步优选单纤细度为 0.35-0.5D的短纤维；
[0008] 进一步优选单纤细度为 0.35D的短纤维； [0009] 上述的铅酸蓄电池极板用短纤维， 选自聚酯纤维或聚丙烯纤维或聚丙烯腈纤维 中的一种或一种以上的混合；
[0010] 上述短纤维的细度偏差率≤10%。
[0011] 本发明的有益效果在于： 应用本发明， 可以大幅提高极板强度， 效果为原来 3 倍； 有效减少浮粉， 约降低 20%左右； 降低生产过程中废损； 约降低 25%左右。 发明的有益效果
有益效果
[0012] 应用本发明， 可以大幅提高极板强度， 效果为原来 3倍； 有效减少浮粉， 约降 低 20%左右； 降低生产过程中废损； 约降低 25%左右。
[0013] 。
对附图的简要说明
附图说明
[0014] 在此处键入附图说明描述段落。
实施该发明的最佳实施例
本发明的最佳实施方式
[0015] 为使本发明实现的技术手段、 技术特征、 达成目的与功效易于明白了解， 下面 结合实施例对本发明作进一步说明：
[0016] 单纤长度单位 mm (毫米） ， 单纤细度单位 D (旦尼尔） ， 旦尼尔是在公定回 潮率下， 9000米长的纤维的重量克数。 旦尼尔简称旦 （D) ， 如 9000米的纤维重
1克为 1旦， 当纤维的密度一定吋， 旦数越大， 纤维越粗。
[0017] 极板的制备过程如下：
[0018] (1) 把铅粉和短纤维放在混合器中， 加入硫酸和水通过不断的搅拌从而形成 适合涂板的铅膏；
[0019] (2) 把合好的铅膏压在板栅上面进行涂板；
[0020] (3) 固化干燥； 制成正负极板。
[0021] (4) 在稀硫酸的电解液中， 把正极板与电源的正极相连， 负极板与电源的负 极板相连， 用电化学的方法使正极板上的铅膏物质转化成为以 Pb02为主的活性 物质， 负极板上铅膏物质转化为以海绵状铅为主的活性物质。
[0022] 跌落试验： 分别取各实施例和对比例极板， 编好编号， 称取重量。 让极板平行 于干净水泥地面， 在 1米高度， 使极板自由落下。 重复跌落试验直至极板出现大 面积缺膏吋， 实验停止。 记录前后重量变化， 记录跌落 3次， 6次， 9次的重量 变化， 测得实验结果。
[0023] 浮粉测试： 取实施例和对比例极板， 编好编号， 称重； 用毛刷轻轻在极板表 面从极耳方向向下刷 5遍， 称重。 浮粉率 =重量差值 /极板初始重量 * 100%。
[0024] 第 1组对比例：
[0025] 短纤维表中 1-1,1-2,1-3为聚酯纤维， 1-4为聚丙烯纤维 ,1-5为聚丙烯腈纤维,添加 质量为铅膏总质量的 0.1%， 单纤长度为 3mm， 单纤细度为 1.5 D。 测量结果如下
[] [表 1]
Figure imgf000004_0001
[0026] 第 2组对比例：
[0027] 短纤维表中 2-1,2-2,2-3为聚酯纤维， 2-4为聚丙烯纤维 ,2-5为聚丙烯腈纤维， 添 下：
[表 2]
Figure imgf000005_0001
[0028]
[0029] 第 3组对比例：
[0030] 短纤维表中 3-1,3-2,3-3为聚酯纤维， 3-4为聚丙烯纤维 ,3-5为聚丙烯腈纤维， 添 加质量为铅膏总质量的 0.1%， 单纤长度为 3mm， 单纤细度为 1.0 D。 测量结果如 下：
[] [表 3]
Figure imgf000006_0001
[0031]
[0032] 第 1组实施例：
[0033] 短纤维表中 4-1,4-2,4-3为聚酯纤维， 4-4为聚丙烯纤维 ,4-5为聚丙烯腈纤维,添加 质量为铅膏总质量的 0.1%， 单纤长度为 3mm， 单纤细度为 0.8 D。 测量结果如下
[]
[表 4]
Figure imgf000007_0001
[0034]
[0035] 第 2组实施例：
[0036] 短纤维表中 5-1,5-2,5-3为聚酯纤维， 5-4为聚丙烯纤维 ,5-5为聚丙烯腈纤维,添加 质量为铅膏总质量的 0.1%， 单纤长度为 3mm， 单纤细度为 0.7 D。 测量结果如下
[]
[表 5]
Figure imgf000008_0001
[0037]
[0038] 第 3组实施例：
[0039] 短纤维表中 6-1,6-2,6-3为聚酯纤维， 6-4为聚丙烯纤维 ,6-5为聚丙烯腈纤维,添加 质量为铅膏总质量的 0.1%， 单纤长度为 3mm， 单纤细度为 0.5 D。 测量结果如下
[]
[表 6]
Figure imgf000009_0001
[0040]
[0041] 第 4组实施例：
[0042] 短纤维表中 7-1,7-2,7-3为聚酯纤维， 7-4为聚丙烯纤维 ,7-5为聚丙烯腈纤维,添加 质量为铅膏总质量的 0.1%， 单纤长度为 3mm， 单纤细度为 0.35 D。 测量结果如下
[]
[表 7]
Figure imgf000010_0001
[0043]
[0044] 第 5组实施例：
[0045] 短纤维表中 8-1,8-2,8-3为聚酯纤维， 8-4为聚丙烯纤维 ,8-5为聚丙烯腈纤维,添加 质量为铅膏总质量的 0.1%， 单纤长度为 3mm， 单纤细度为 0.15 D。 测量结果如下
[]
幽
Figure imgf000011_0001
[0046]
[0047] 上述结果清楚的表明， 5组实施例的掉粉率和各次质损率大大优于 3个对比例的 技术指标。
[0048] 极板的强度也和短纤维的添加比例有关系， 为此我们对在短纤维相同细度下， 不同的添加比例进行极板强度的测试。
[0049] 实施例 6:任选 10块负极生极板，随机编号,其单纤细度选择 0.35D,长度 2-3mm， 添 加比例为占铅膏总质量的 0.15%。 结果如下： 幽
Figure imgf000012_0001
该实施例的对比例： 任选 10块负极生极板，随机编号,其单纤细度选择 1.5D,长度 2 -3mm, 添加比例为占铅膏总质量的 0.15%。 结果如下：
[表 10]
Figure imgf000013_0001
[0051] 实施例 6的指标明显优于对比例。
[0052] 实施例 7:任选 5块负极熟极板，随机编号,其单纤细度选择 0.35D,长度 2-3mm， 添 加比例为占铅膏总质量的 0.2%。 结果如下：
[]
[表 11]
Figure imgf000014_0001
[0053] 该实施例的对比例： 任选 5块负极熟极板，随机编号,其单纤细度选择 0.35D,长度 2
-3mm, 添加比例为占铅膏总质量的 0.2%。 结果如下：
[] [表 12]
Figure imgf000014_0002
[0054] 实施例 7的指标明显优于对比例。
[0055] 实施例 8: 任选 10块正极熟极板，随机编号,其单纤细度选择 0. 5D,长度 2-3mm 添加比例为占铅膏总质量的 0.08%。 结果如下：
[] [表 13]
Figure imgf000015_0001
该实施例的对比例： 任选 10块正极熟极板，随机编号,其单纤细度选择 1.5D,长度 2 -3mm, 添加比例为占铅膏总质量的 0.08%。 结果如下：
[表 14]
Figure imgf000016_0001
[0057] 实施例 8的指标明显优于对比例。
[0058] 实施例 9: 任选 10块正极生极板，随机编号,其单纤细度选择 0. 5D,长度 2-3mm， 添加比例为占铅膏总质量的 0.05%。 结果如下：
[]
[表 15]
Figure imgf000017_0001
该实施例的对比例： 任选 10块正极生极板，随机编号,其单纤细度选择 1. 5D,长度 2-3mm， 添加比例为占铅膏总质量的 0.05%。 结果如下：
[表 16]
Figure imgf000018_0001
[0060] 实施例 9的指标明显优于对比例。
[0061] 在添加比例为 0.05-0.2的区域内可以取得有益效果。
[0062] 按照中国专利 201110229425.6公幵的方法将铅酸蓄电池的极板解剖检验， 分离 出其中的短纤维来后， 可以发现， 纤维基本无变化。 通过相关设备测量其直径 ， 与材质相同的商品纤维长丝进行直径比对， 可以得出铅酸蓄电池的极板中短 纤维的细度， 并可以获得短纤维和极板活性物质的重量比例。
[0063] 尽管发明人已经对本发明的技术方案做了较为详细的阐述和列举， 应当理 解， 对于本领域的一般技术人员而言， 根据本发明所揭示的内容， 对上述实施 例做出修改和 /或改变或者采用等同的替代方案是显而易见的， 其都不能脱离本 发明要求保护的范围， 本发明中的保护范围以限定在权利要求书中的权利要求 为准。 本发明的实施方式
[0064] 在此处键入本发明的实施方式描述段落。
工业实用性
[0065] 在此处键入工业实用性描述段落。
序列表自由内容
[0066] 在此处键入序列表自由内容描述段落。

Claims

权利要求书
[权利要求 1] 一种铅酸蓄电池极板用短纤维， 包括多根长度为≤6mm的有机纤维， 其特征在于， 所述的有机纤维单纤细度为 0.15-0.8D,所述的有机纤维 为聚酯纤维或聚丙烯纤维或聚丙烯腈纤维中的一种或一种以上的混合
PCT/CN2017/105267 2017-10-05 2017-10-05 一种铅酸蓄电池极板用短纤维 WO2019068220A1 (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017446A (en) * 1989-10-24 1991-05-21 Globe-Union Inc. Electrodes containing conductive metal oxides
CN1276919A (zh) * 1997-09-02 2000-12-13 Kvg技术股份有限公司 玻璃纤维隔板以及包括该隔板的电池
US20040180265A1 (en) * 2001-09-21 2004-09-16 Nippon Sheet Glass Co., Ltd. Separator for valve regulated lead acid battery and valve regulated lead acid battery
CN1707841A (zh) * 2004-06-04 2005-12-14 三樱工业株式会社 碱性电池、集电材料、电极、及电极的制造方法
CN101310049A (zh) * 2005-11-14 2008-11-19 日本合成化学工业株式会社 乙烯-乙烯醇类共聚物纤维

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017446A (en) * 1989-10-24 1991-05-21 Globe-Union Inc. Electrodes containing conductive metal oxides
CN1276919A (zh) * 1997-09-02 2000-12-13 Kvg技术股份有限公司 玻璃纤维隔板以及包括该隔板的电池
US20040180265A1 (en) * 2001-09-21 2004-09-16 Nippon Sheet Glass Co., Ltd. Separator for valve regulated lead acid battery and valve regulated lead acid battery
CN1707841A (zh) * 2004-06-04 2005-12-14 三樱工业株式会社 碱性电池、集电材料、电极、及电极的制造方法
CN101310049A (zh) * 2005-11-14 2008-11-19 日本合成化学工业株式会社 乙烯-乙烯醇类共聚物纤维

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