WO2021129793A1 - Method for manufacturing long-life lead-acid battery negative electrode by using trace amount of graphene oxide flakes - Google Patents
Method for manufacturing long-life lead-acid battery negative electrode by using trace amount of graphene oxide flakes Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 9
- 229920005610 lignin Polymers 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 abstract description 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000019635 sulfation Effects 0.000 description 5
- 238000005670 sulfation reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910000370 mercury sulfate Inorganic materials 0.000 description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
A method for manufacturing a long-life lead-acid battery negative electrode by using a trace amount of graphene oxide flakes. A graphene oxide flake dispersion agent is prepared by a modified Hummer's method and used as an additive for a negative electrode plate of a lead-acid battery. On the basis of a conventional formula, a trace amount of graphene oxide flakes is added in a liquid form to a lead paste, so as to induce growth of large-sized porous lead rods during a formation process. The lead rods are one-dimensional structures with good electrical conductivity, and the lead rods are cross-linked inside the lead paste to form a three-dimensional porous network, which is conducive to diffusion of sulfuric acid, accelerates the occurrence of electrochemical reactions, promotes mutual conversion between lead and lead sulfate, and extends the service life of the battery. The obtained lead-acid battery has good cycle performance in a high-rate partial charge state, without affecting hydrogen evolution of the battery, and is particularly suitable for use in the field of power batteries.
Description
本申请要求于2019年12月26日提交中国专利局、申请号为201911361858.X、发明名称为“利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on December 26, 2019, the application number is 201911361858.X, and the invention title is "Method for manufacturing long-life lead-acid battery negative electrodes using trace graphene oxide sheets" , Its entire content is incorporated into this application by reference.
本发明涉及一种铅酸电池负极的制备方法，特别是涉及一种氧化石墨烯作为负极添加剂构造高倍率部分荷电状态长寿命铅酸电池的方法，应用于铅酸电池电化学储能技术领域。The invention relates to a method for preparing a lead-acid battery negative electrode, in particular to a method for using graphene oxide as a negative electrode additive to construct a high-rate partially charged state long-life lead-acid battery, which is applied to the technical field of electrochemical energy storage of lead-acid batteries .
当前，尽管市场上出现了很多种新型的电池，但是铅酸蓄电池由于安全性高、价格低廉、再循环能力强等优点仍占据很大的市场，目前铅酸蓄电池在混合动力汽车领域也得到了广泛的应用。在混合动力汽车中，当铅酸蓄电池以高倍率部分荷电状态运行时，电池负极板会发生严重的硫酸盐化。At present, despite the emergence of many new types of batteries on the market, lead-acid batteries still occupy a large market due to their high safety, low price, and strong recyclability. At present, lead-acid batteries are also found in the field of hybrid vehicles. Wide range of applications. In hybrid electric vehicles, when the lead-acid battery is operated in a high-rate partially charged state, the negative plate of the battery will undergo severe sulfation.
碳基材料具有较大的比表面积，导电性好，可提供双电层电容，被广泛应用到电化学领域。研究表明在铅酸电池负极板中添加碳材料能够有效地抑制负极板的硫酸盐化，提高电池的荷电接收能力和循环寿命。Carbon-based materials have a large specific surface area, good electrical conductivity, can provide electric double layer capacitance, and are widely used in the electrochemical field. Studies have shown that adding carbon materials to the negative plate of a lead-acid battery can effectively inhibit the sulfation of the negative plate and improve the battery's charge acceptance and cycle life.
石墨烯具有比表面积高、电子导电性优异、化学稳定性高和柔韧性好等特性，加入负极活性物质中，可形成连续的导电性网络。但是石墨烯和其他碳材料有以下缺点：价格昂贵，不利于大规模产业化；促进极板析氢，破坏铅膏内部结构，造成电池失水。这些不足都限制了石墨烯材料在铅酸蓄电池中应用，成为亟待解决的技术问题。Graphene has the characteristics of high specific surface area, excellent electronic conductivity, high chemical stability and good flexibility. When added to the negative electrode active material, it can form a continuous conductive network. However, graphene and other carbon materials have the following disadvantages: they are expensive, which is not conducive to large-scale industrialization; they promote the hydrogen evolution of the electrode plates, destroy the internal structure of the lead paste, and cause the battery to lose water. These deficiencies have restricted the application of graphene materials in lead-acid batteries, which has become an urgent technical problem to be solved.
发明内容Summary of the invention
为了解决现有技术问题，本发明的目的在于克服已有技术存在的不足，提供一种利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，将痕量的氧化石墨烯片以液体形式添加到传统配方的负极板铅膏中，可提高铅酸电池的循环性能，但并不会对电池析氢造成影响。本发明在传统配方的基础上，添加痕量氧化石墨烯片的负极板组装的电池比传统配方组装的 电池性能提高了1.4倍。在高倍率部分荷电状态下，本发明方法有效缓解了负极板硫酸盐化，为铅酸电池的制备方法提供了新的可能性。In order to solve the problems of the prior art, the purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for manufacturing the negative electrode of a long-life lead-acid battery by using trace graphene oxide flakes. The form added to the negative plate lead paste of the traditional formula can improve the cycle performance of the lead-acid battery, but it will not affect the hydrogen evolution of the battery. On the basis of the traditional formula, the performance of the battery assembled with the negative electrode plate added with trace graphene oxide sheets is 1.4 times higher than that of the battery assembled with the traditional formula. In the high-rate partially charged state, the method of the present invention effectively alleviates the sulfation of the negative electrode plate, and provides a new possibility for the preparation method of the lead-acid battery.
为达到上述发明创造目的，本发明采用如下技术方案：In order to achieve the above-mentioned invention and creation objectives, the present invention adopts the following technical solutions:
一种利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，包括以下步骤：A method for manufacturing the negative electrode of a long-life lead-acid battery by using trace graphene oxide sheets, including the following steps:
a.利用改性Hummer'法制备氧化石墨烯片分散液原液；a. Preparation of graphene oxide sheet dispersion stock solution by modified Hummer' method;
b.制备铅膏：b. Preparation of lead paste:
将炭黑、木素、硫酸钡混合均匀，得到混合粉料；Mix carbon black, lignin, and barium sulfate uniformly to obtain a mixed powder;
然后向混合粉料中加入铅粉，进行搅拌混合，得到原料混合物；Then add lead powder to the mixed powder, stir and mix to obtain a raw material mixture;
再将在所述步骤a中制备的氧化石墨烯片分散液原液滴加到去离子水中，得到均一的氧化石墨烯片分散液；然后，将所述氧化石墨烯片分散液一次性加入到上述原料混合物中，搅拌均匀，再滴加质量百分比浓度不高于70％的稀硫酸，进行酸混，得到铅膏，备用；所述铅膏中，氧化石墨烯片的添加量不超过2ppm；Then, the original solution of the graphene oxide flake dispersion prepared in step a is added dropwise to deionized water to obtain a uniform graphene oxide flake dispersion; then, the graphene oxide flake dispersion is added to the above-mentioned one at a time In the raw material mixture, stir evenly, and then dropwise add dilute sulfuric acid with a mass percentage concentration of not higher than 70% to perform acid mixing to obtain a lead paste for use; in the lead paste, the addition amount of graphene oxide flakes does not exceed 2 ppm;
c.制备铅酸电池负极：c. Preparation of the negative electrode of the lead-acid battery:
将在所述步骤b中制得的铅膏涂覆于铅酸电池的负极板板栅，控制固化温度为50～70℃，湿度为50～95％，得到铅酸电池负极板。The lead paste prepared in the step b is coated on the negative grid of the lead-acid battery, and the curing temperature is controlled to be 50-70° C. and the humidity is 50-95% to obtain the negative plate of the lead-acid battery.
作为本发明优选的技术方案，在所述步骤a中，所述氧化石墨烯片分散液原液中氧化石墨烯片的固含量不高于5mg/mL。As a preferred technical solution of the present invention, in the step a, the solid content of the graphene oxide flakes in the graphene oxide flake dispersion stock solution is not higher than 5 mg/mL.
作为本发明优选的技术方案，在所述步骤b中，所述炭黑、硫酸钡、木素与铅粉的质量比分别为：0.2％、0.8％、0.2％。As a preferred technical solution of the present invention, in the step b, the mass ratios of the carbon black, barium sulfate, lignin and lead powder are respectively: 0.2%, 0.8%, and 0.2%.
作为本发明优选的技术方案，在所述步骤b中，氧化石墨烯片分散液中的去离子水与铅粉的质量比不高于12％，稀硫酸的密度不大于1.4g/cm
3，稀硫酸与铅粉的质量比不大于4.8％。
As a preferred technical solution of the present invention, in the step b, the mass ratio of deionized water to lead powder in the graphene oxide sheet dispersion is not higher than 12%, and the density of dilute sulfuric acid is not more than 1.4g/cm 3 , The mass ratio of dilute sulfuric acid to lead powder is not more than 4.8%.
作为本发明优选的技术方案，在所述步骤c中，将铅膏涂覆到板栅上后采用分步固化工艺进行固化，固化时间至少为96h。As a preferred technical solution of the present invention, in the step c, the lead paste is applied to the grid and then cured by a step-by-step curing process, and the curing time is at least 96 hours.
本发明提供了上述制备方法制备得到的铅酸电池负极，包括铅酸电池负极板板栅和涂覆于所述铅酸电极板板栅表面的铅膏；制备所述铅膏的原料包括氧化石墨烯片、炭黑、木素、硫酸钡、铅酚和稀硫酸，所述氧化石墨烯片在铅膏中的添加量不超过2ppm。The present invention provides a lead-acid battery negative electrode prepared by the above preparation method, comprising a lead-acid battery negative electrode grid and a lead paste coated on the surface of the lead-acid electrode grid; the raw material for preparing the lead paste includes graphite oxide The addition amount of the graphene oxide flakes in the lead paste does not exceed 2 ppm.
本发明提供了上述铅酸电池负极在动力电池中的应用。The present invention provides the application of the above-mentioned lead-acid battery negative electrode in a power battery.
本发明提供了一种铅酸电池，负极为上述技术方案所述的铅酸电池负极。The present invention provides a lead-acid battery, and the negative electrode is the lead-acid battery negative electrode described in the above technical scheme.
本发明与现有技术相比较，具有如下显而易见的突出实质性特点和显著优点：Compared with the prior art, the present invention has the following obvious prominent substantive features and significant advantages:
1.本发明方法利用痕量氧化石墨烯片构造长寿命铅酸电池的方法操作简单，成本低廉，不需要特殊的设备，便于生产化；本发明采用痕量氧化石墨烯片，可以诱导化成过程中大尺寸、多孔铅棒的生长，提高导电性，增大极板的孔隙率，有利于硫酸的扩散，促进电化学反应的发生。痕量氧化石墨烯片用作铅酸电池负极板添加剂，所得到的铅酸电池具有良好的循环性能，特别适用于动力电池领域；1. The method of the present invention uses traces of graphene oxide flakes to construct long-life lead-acid batteries. The method has simple operation, low cost, does not require special equipment, and is convenient for production; the present invention uses traces of graphene oxide flakes, which can induce the formation process The growth of medium and large size, porous lead rods improves conductivity and increases the porosity of the electrode plates, which is beneficial to the diffusion of sulfuric acid and promotes the occurrence of electrochemical reactions. Trace graphene oxide flakes are used as additives for the negative plate of lead-acid batteries, and the resulting lead-acid batteries have good cycle performance, which is especially suitable for the field of power batteries;
2.本发明方法简单易行，产出率高，重复性好，适合推广使用。2. The method of the present invention is simple and easy to implement, has high output rate, good repeatability, and is suitable for popularization and use.
图1为本发明实施例一方法制备的氧化石墨烯片的TEM图；FIG. 1 is a TEM image of a graphene oxide sheet prepared by a method in Example 1 of the present invention;
图2为本发明实施例一方法制备的负极板化成后的SEM图；2 is an SEM image of the negative electrode plate prepared by the method of Example 1 of the present invention after formation;
图3为本发明实施例一方法制备的负极板和对比例制备的负极板CV测试图；FIG. 3 is a CV test diagram of the negative electrode plate prepared by the method according to the first embodiment of the present invention and the negative electrode plate prepared by the comparative example;
图4为本发明实施例一方法制备的负极板和对比例制备的负极板组装成电池后在高倍率部分荷电状态下循环测试图；4 is a cycle test diagram of the negative electrode plate prepared by the method of Example 1 of the present invention and the negative electrode plate prepared by the comparative example after being assembled into a battery under a high-rate partial charge state;
图5为对比例方法制备的负极板组装电池后在高倍率部分荷电状态下失效后的SEM图；Figure 5 is an SEM image of a negative electrode plate prepared by a comparative method after assembling a battery in a high-rate partially charged state after failure;
图6为本发明实施例一方法制备的负极板组装成电池后在高倍率部分荷电状态下失效后的SEM图。FIG. 6 is an SEM image of the negative electrode plate prepared by the method according to the first embodiment of the present invention after being assembled into a battery after failure in a high-rate partial charge state.
以下结合具体的实施例子对上述方案做进一步说明，本发明的优选实施例详述如下：The above scheme is further described below in conjunction with specific implementation examples. The preferred embodiments of the present invention are described in detail as follows:
在本发明中，所述氧化石墨烯片分散液原液为氧化石墨烯片分散在水中得到的分散液，氧化石墨烯片分散液原液中氧化石墨烯片的固含量指的是氧化石墨烯片分散在水中的固含量。In the present invention, the graphene oxide flake dispersion stock solution is a dispersion obtained by dispersing graphene oxide flakes in water, and the solid content of the graphene oxide flakes in the graphene oxide flake dispersion stock solution refers to the graphene oxide flake dispersion The solid content in water.
实施例一：Example one:
在本实施例中，一种利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，包括以下步骤：In this embodiment, a method for manufacturing a long-life lead-acid battery negative electrode using trace amounts of graphene oxide sheets includes the following steps:
a.利用改性Hummer'法制备氧化石墨烯片分散液原液，所述氧化石墨烯片分散液原液中的氧化石墨烯片的固含量为5mg/mL；所制备的氧化石墨烯片参见图1；a. Using the modified Hummer' method to prepare the graphene oxide flake dispersion stock solution, the solid content of the graphene oxide flakes in the graphene oxide flake dispersion stock solution is 5 mg/mL; the prepared graphene oxide flakes are shown in Figure 1 ；
b.制备铅膏：b. Preparation of lead paste:
按照炭黑、硫酸钡、木素分别与铅粉的质量比进行计算，将炭黑0.2％、挪威木素0.2％、硫酸钡0.8％混合均匀，得到混合粉料；Calculate according to the mass ratios of carbon black, barium sulfate, and lignin to lead powder, and mix carbon black 0.2%, norwegian lignin 0.2%, and barium sulfate 0.8% to obtain a mixed powder;
然后向混合粉料中加入铅粉，进行搅拌混合，得到原料混合物；Then add lead powder to the mixed powder, stir and mix to obtain a raw material mixture;
再将在所述步骤a中制备的氧化石墨烯片分散液原液滴加到去离子水中，得到均一的氧化石墨烯片分散液，控制氧化石墨烯片分散液中的去离子水与铅粉的质量比为12％；然后，将氧化石墨烯片分散液一次性加入到上述原料混合物中，进行搅拌均匀，再滴加稀硫酸，进行酸混，得到铅膏，备用；所述稀硫酸的密度为1.4g/cm
3，稀硫酸与铅粉质量比为4.8％；在得到铅膏中，氧化石墨烯片的添加量为2ppm；
Then, the original solution of the graphene oxide flake dispersion prepared in step a is added dropwise to deionized water to obtain a uniform graphene oxide flake dispersion, and the deionized water and lead powder in the graphene oxide flake dispersion are controlled. The mass ratio is 12%; then, the graphene oxide flake dispersion is added to the above-mentioned raw material mixture at one time, and the mixture is stirred uniformly, and then dilute sulfuric acid is added dropwise for acid mixing to obtain a lead paste for use; the density of the dilute sulfuric acid 1.4g/cm 3 , the mass ratio of dilute sulfuric acid to lead powder is 4.8%; in the lead paste, the amount of graphene oxide flakes added is 2ppm;
c.制备铅酸电池负极：c. Preparation of lead-acid battery negative electrode:
将在所述步骤b中制得的铅膏涂覆于铅酸电池的负极板板栅，控制固化温度为50～70℃，湿度为50～95％，固化时间为96h，从而制得铅酸电池负极板。图2为本实施例加入2ppm氧化石墨烯片的负极板化成后的SEM图。The lead paste prepared in the step b is coated on the negative grid of the lead-acid battery, and the curing temperature is controlled to be 50-70°C, the humidity is 50-95%, and the curing time is 96h, so as to prepare the lead-acid battery. Battery negative plate. Figure 2 is an SEM image of a negative electrode plate formed with 2ppm graphene oxide sheets added in this embodiment.
实验测试分析：Experimental test analysis:
将本实施例制备的铅酸电池负极板做工作电极，商业铅酸电池正极作对电极，汞/硫酸亚汞电极作参比电极构成三电极体系，对制备的铅酸电池负极进行电化学表征。环伏安测试的电位窗口为0到-1.5V。将负极板和商业正极板组装电池，模拟高倍率部分荷电状态进行测试。The lead-acid battery negative plate prepared in this example was used as the working electrode, the commercial lead-acid battery positive electrode was used as the counter electrode, and the mercury/mercurous sulfate electrode was used as the reference electrode to form a three-electrode system, and the prepared lead-acid battery negative electrode was electrochemically characterized. The potential window of the ring voltammetry test is 0 to -1.5V. Assemble the battery with the negative plate and the commercial positive plate, and simulate the high-rate partial state of charge for testing.
对比例：Comparative ratio:
在本实施例中，一种制备铅酸电池负极的方法，包括以下步骤：In this embodiment, a method for preparing the negative electrode of a lead-acid battery includes the following steps:
(1)制备铅膏：(1) Preparation of lead paste:
按照炭黑、硫酸钡、木素分别与铅粉的质量比进行计算，将炭黑0.2％、挪威木素0.2％、硫酸钡0.8％混合均匀，得到混合粉料；Calculate according to the mass ratio of carbon black, barium sulfate, lignin and lead powder respectively, and mix carbon black 0.2%, norwegian lignin 0.2%, and barium sulfate 0.8% to obtain a mixed powder;
然后向混合粉料中加入铅粉，搅拌混合，得到原料混合物；将去离子水一次性加入到混合铅粉中，控制去离子水与铅粉的质量比为12％；搅拌均匀；最后，滴加稀硫酸，混合均匀，备用；所述稀硫酸的密度为1.4g/cm
3，稀硫酸与铅粉的质量比为4.8％；
Then add lead powder to the mixed powder, stir and mix to obtain a raw material mixture; add deionized water to the mixed lead powder at one time, control the mass ratio of deionized water to lead powder to 12%; stir evenly; finally, drip Add dilute sulfuric acid, mix well, and reserve; the density of the dilute sulfuric acid is 1.4g/cm 3 , and the mass ratio of dilute sulfuric acid to lead powder is 4.8%;
(2)制备铅酸电池负极：(2) Preparation of negative electrode of lead-acid battery:
将所述步骤(1)中制得的铅膏涂覆于铅酸电池的负极板板栅，控制固化温度为50～70℃，湿度为50～95％，固化时间为96h，从而制得铅酸电池负极板。The lead paste prepared in the step (1) is coated on the negative grid of a lead-acid battery, and the curing temperature is controlled to be 50-70°C, the humidity is 50-95%, and the curing time is 96h, thereby preparing lead Negative plate of acid battery.
实验测试分析：Experimental test analysis:
以本对比例制备的铅酸电池负极板作工作电极，商业铅酸电池正极板作对电极，汞/硫酸亚汞电极作参比电极构成三电极体系，对制备的铅酸电池负极进行电化学表征。循环伏安测试的电位窗口为0到-1.5V。将负极板和商业正极板组装电池(一负两正)，模拟高倍率部分荷电状态进行测试。The lead-acid battery negative plate prepared in this comparative example was used as the working electrode, the commercial lead-acid battery positive plate was used as the counter electrode, and the mercury/mercurous sulfate electrode was used as the reference electrode to form a three-electrode system. The prepared lead-acid battery negative electrode was electrochemically characterized . The potential window of the cyclic voltammetry test is 0 to -1.5V. The negative plate and the commercial positive plate are assembled into the battery (one negative and two positive), and the high-rate partial state of charge is simulated for testing.
参见图3和图4，图3为本发明实施例一方法制备的负极板和对比例制备的负极板CV测试图。图4为本发明实施例一方法制备的负极板和对比例制备的负极板组装成电池后在高倍率部分荷电状态下循环测试图。本发明实施例一方法在对比例配方的基础上，添加痕量氧化石墨烯片的负极板组装的电池比传统配方组装的电池性能提高了1.4倍。并且，对比例铅膏配方组装的电池在经历两次循环后电池失效，而添加痕量的氧化石墨烯片的负极板组装的电池在第四圈循环时仍能达到6301圈。在高倍率部分荷电状态下，本发明有效缓解了负极板硫酸盐化，为铅酸电池的制备方法提供了新的可能性。Referring to FIGS. 3 and 4, FIG. 3 is a CV test diagram of the negative electrode plate prepared by the method of Example 1 of the present invention and the negative electrode plate prepared by the comparative example. 4 is a cycle test diagram of the negative electrode plate prepared by the method of Example 1 of the present invention and the negative electrode plate prepared by the comparative example after being assembled into a battery under a high-rate partial charge state. Based on the formula of the comparative example, in the method of the first embodiment of the present invention, the performance of the battery assembled with the negative electrode plate added with trace graphene oxide sheet is 1.4 times higher than that of the battery assembled with the traditional formula. In addition, the battery assembled with the lead paste formulation of the comparative example failed after two cycles, while the battery assembled with the negative electrode plate with trace amount of graphene oxide sheet could still reach 6301 cycles at the fourth cycle. In the high-rate partially charged state, the invention effectively alleviates the sulfation of the negative plate, and provides a new possibility for the preparation method of the lead-acid battery.
参见图5和图6。图5为对比例方法制备的负极板组装电池后在高倍率部分荷电状态下失效后的SEM图。图6为本发明实施例一方法制备的负极板组装成电池后在高倍率部分荷电状态下失效后的SEM图。See Figure 5 and Figure 6. Fig. 5 is an SEM image of the negative electrode plate prepared by the method of the comparative example after the battery fails after being assembled in the high-rate partial charge state. FIG. 6 is an SEM image of the negative electrode plate prepared by the method according to the first embodiment of the present invention after being assembled into a battery after failure in a high-rate partial charge state.
本发明实施例一方法利用痕量氧化石墨烯片构造长寿命铅酸电池的方法，解决铅酸蓄电池在高倍率部分荷电状态下循环寿命低的问题，在传统的铅膏配方的基础上，以液体的形式添加痕量的氧化石墨烯片，即可极大地提高铅酸蓄电池的循环性能，并且不会对电池析氢造成影响。该方法 操作简单、成本低廉、工艺成熟，具有良好的应用前景。The method of the first embodiment of the present invention uses trace amounts of graphene oxide sheets to construct long-life lead-acid batteries, which solves the problem of low cycle life of lead-acid batteries under high-rate partially charged states. On the basis of traditional lead paste formulations, Adding trace amounts of graphene oxide flakes in liquid form can greatly improve the cycle performance of lead-acid batteries without affecting the hydrogen evolution of the battery. The method is simple in operation, low in cost, mature in technology, and has good application prospects.
实施例二：Embodiment two:
本实施例与实施例一基本相同，特别之处在于：This embodiment is basically the same as the first embodiment, and the special features are:
在本实施例中，在所述步骤b中制备铅膏时，将铅膏涂覆到板栅上采用分步固化工艺进行固化，更好地实现铅酸电池负极板的均匀固化，得到高质量的铅酸电池负极板。共进行了两种电池的对比，所以只有实施例一和对比例两种工艺，所有的工艺固化程序相同。In this embodiment, when the lead paste is prepared in the step b, the lead paste is applied to the grid and cured by a step-by-step curing process, which better realizes the uniform curing of the negative plate of the lead-acid battery and obtains high quality Negative plate of lead-acid battery. A total of two types of batteries were compared, so there are only two processes in Example 1 and Comparative Example, and the curing procedures of all processes are the same.
本发明上述实施例方法利用痕量氧化石墨烯片构造长寿命铅酸电池的方法，在负极板中添加适量的氧化石墨烯片能够有效地抑制负极板的硫酸盐化，提高电池在高倍率部分荷电状态下的循环寿命，但并未对析氢造成影响。石墨烯作为一种碳材料，具有优异的性能，能提高铅酸电池在高倍率部分荷电状态下的循环能力。由于石墨烯和其他碳材料会存在以下问题：The above-mentioned embodiment method of the present invention uses trace amounts of graphene oxide sheets to construct long-life lead-acid batteries. Adding an appropriate amount of graphene oxide sheets to the negative plate can effectively inhibit the sulfation of the negative plate and improve the high-rate part of the battery. The cycle life under the charged state, but did not affect the hydrogen evolution. As a carbon material, graphene has excellent performance and can improve the cycle capacity of lead-acid batteries under high-rate partially charged states. As graphene and other carbon materials have the following problems:
(1)价格昂贵，不利于大规模产业化。(1) The price is expensive, which is not conducive to large-scale industrialization.
(2)碳材料促进极板析氢，破坏铅膏内部的结构，造成电池失水。传统的和膏方法是将石墨烯和其他膨胀剂与铅粉物理混合，再加入水和稀硫酸进行调配。本发明在传统配方的基础上，将痕量的氧化石墨烯片分散在适量的水中，再将氧化石墨烯片分散液和稀硫酸加入混合物中调配铅膏。本发明采用痕量氧化石墨烯片，可以诱导化成过程中多孔铅棒的生长。这是由于：(2) The carbon material promotes the hydrogen evolution of the electrode plate, destroys the internal structure of the lead paste, and causes the battery to lose water. The traditional paste method is to physically mix graphene and other expansion agents with lead powder, and then add water and dilute sulfuric acid to mix. Based on the traditional formula, the present invention disperses trace amounts of graphene oxide flakes in an appropriate amount of water, and then adds graphene oxide flake dispersion and dilute sulfuric acid into the mixture to prepare a lead paste. The invention adopts trace amount of graphene oxide flakes, which can induce the growth of porous lead rods in the formation process. This is because:
(1)铅棒是一维结构，具有良好的导电性；(1) The lead rod is a one-dimensional structure with good conductivity;
(2)大尺寸的铅棒相互交联形成三维多孔网络，有利于硫酸的扩散，促进铅和硫酸铅的相互转化；(2) Large-size lead rods are cross-linked to form a three-dimensional porous network, which is conducive to the diffusion of sulfuric acid and promotes the mutual conversion of lead and lead sulfate;
(3)铅棒上的多孔结构，有利于储存电解液，加速铅和硫酸铅电化学反应的发生。(3) The porous structure on the lead rod is good for storing electrolyte and accelerating the electrochemical reaction between lead and lead sulfate.
同时发现，在CV测试中，虽然加入氧化石墨烯片后，铅和硫酸铅的氧化还原峰有很大的增加，但在电压为-1.5V处由析氢产生的电流几乎没有变化。表明本发明方法能提高铅酸电池的性能，但并未对析氢造成影响。对负极板和一负两正的商业正极板组装电池的模拟高倍率部分荷电状态，实验表明，由传统铅膏配方组装的电池，第一次循环次数为21307圈，而 加入2ppm氧化石墨烯片后组装的电池循环了29971圈，循环性能提高了1.4倍。并且由传统铅膏配方组装的电池经历过2次循环后电池失效，而添加2ppm氧化石墨烯片的电池第四次循环仍能达6301圈。At the same time, it was found that in the CV test, although the redox peaks of lead and lead sulfate increased greatly after adding graphene oxide sheets, the current generated by hydrogen evolution at a voltage of -1.5V hardly changed. It shows that the method of the present invention can improve the performance of lead-acid batteries, but does not affect hydrogen evolution. The simulated high-rate partial charge state of the battery assembled with the negative plate and one negative and two positive commercial positive plates. Experiments show that the battery assembled from the traditional lead paste formula has a first cycle of 21,307 cycles, and 2ppm graphene oxide is added The battery assembled after the film cycled 29971 cycles, and the cycle performance was increased by 1.4 times. And the battery assembled from the traditional lead paste formula has gone through two cycles and the battery failed, while the battery with 2ppm graphene oxide flakes added can still reach 6301 cycles in the fourth cycle.
本发明上述实施例方法通过改性Hummer'法制备了氧化石墨烯片分散液，并用于铅酸电池负极板添加剂。在传统配方的基础上，将痕量氧化石墨烯片以液体形式加入到铅膏中，可以诱导化成过程中大尺寸、多孔铅棒的生长。铅棒是一维结构，具有良好的导电性，并且铅棒在铅膏内部互相交联形成的三维多孔网络，有利于硫酸的扩散，加速电化学反应的发生，促进铅和硫酸铅之间的相互转化，延长电池的使用寿命。本发明利用痕量氧化石墨烯片构造长寿命铅酸电池的方法操作简单，成本低廉，不需要特殊的设备，便于生产化。痕量氧化石墨烯片可以诱导化成过程中大尺寸、多孔铅棒的生长，提高导电性，增大极板的孔隙率，有利于硫酸的扩散，促进电化学反应的发生。用作铅酸电池负极板添加剂，所得到的铅酸电池具有良好的循环性能和荷电接收能力，特别适用于动力电池领域。The above-mentioned embodiment method of the present invention prepares the graphene oxide flake dispersion by the modified Hummer' method, and is used as an additive for the negative plate of a lead-acid battery. On the basis of the traditional formula, adding trace amounts of graphene oxide flakes to the lead paste in liquid form can induce the growth of large-sized, porous lead rods during the formation process. Lead rods have a one-dimensional structure with good electrical conductivity. The three-dimensional porous network formed by cross-linking the lead rods in the lead paste facilitates the diffusion of sulfuric acid, accelerates the occurrence of electrochemical reactions, and promotes the interaction between lead and lead sulfate. Transform each other to extend the service life of the battery. The method for constructing a long-life lead-acid battery by using trace graphene oxide sheets in the present invention is simple in operation, low in cost, does not require special equipment, and is convenient for production. Trace graphene oxide flakes can induce the growth of large-sized, porous lead rods during the formation process, improve conductivity, increase the porosity of the electrode plate, facilitate the diffusion of sulfuric acid, and promote the occurrence of electrochemical reactions. Used as an additive to the negative plate of a lead-acid battery, the resulting lead-acid battery has good cycle performance and charge receiving ability, and is particularly suitable for the field of power batteries.
上面对本发明实施例结合附图进行了说明，但本发明不限于上述实施例，还可以根据本发明的发明创造的目的做出多种变化，凡依据本发明技术方案的精神实质和原理下做的改变、修饰、替代、组合或简化，均应为等效的置换方式，只要符合本发明的发明目的，只要不背离本发明利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法的技术原理和发明构思，都属于本发明的保护范围。The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention. Any changes are made in accordance with the spirit and principle of the technical solution of the present invention. The changes, modifications, substitutions, combinations or simplifications should be equivalent replacement methods, as long as they meet the purpose of the present invention, as long as they do not deviate from the method of the present invention for manufacturing long-life lead-acid battery negative electrodes using trace graphene oxide sheets. Both the technical principle and the inventive concept belong to the protection scope of the present invention.
Claims (9)
- 一种利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，其特征在于，包括以下步骤：A method for manufacturing the negative electrode of a long-life lead-acid battery by using trace graphene oxide sheets, which is characterized in that it comprises the following steps:a.利用改性Hummer'法制备氧化石墨烯片分散液原液；a. Preparation of graphene oxide sheet dispersion stock solution by modified Hummer' method;b.制备铅膏：b. Preparation of lead paste:将炭黑、木素、硫酸钡混合均匀，得到混合粉料；Mix carbon black, lignin, and barium sulfate uniformly to obtain a mixed powder;然后向所述混合粉料中加入铅粉，进行搅拌混合，得到原料混合物；Then, lead powder is added to the mixed powder, and the mixture is stirred and mixed to obtain a raw material mixture;再将在所述步骤a中制备的氧化石墨烯片分散液原液滴加到去离子水中，得到均一的氧化石墨烯片分散液；然后，将所述氧化石墨烯片分散液一次性加入到上述原料混合物中，搅拌均匀，再滴加质量百分比浓度不高于70％的稀硫酸，进行酸混，得到铅膏，备用；所述铅膏中氧化石墨烯片的添加量不超过2ppm；Then, the original solution of the graphene oxide flake dispersion prepared in step a is added dropwise to deionized water to obtain a uniform graphene oxide flake dispersion; then, the graphene oxide flake dispersion is added to the above-mentioned one at a time In the raw material mixture, stir evenly, and then dropwise add dilute sulfuric acid with a mass percentage concentration of not higher than 70% to perform acid mixing to obtain a lead paste for use; the addition amount of graphene oxide flakes in the lead paste does not exceed 2 ppm;c.制备铅酸电池负极：c. Preparation of lead-acid battery negative electrode:将在所述步骤b中制得的铅膏涂覆于铅酸电池的负极板板栅，控制固化温度为50～70℃，湿度为50～95％，得到铅酸电池负极板。The lead paste prepared in the step b is coated on the negative grid of the lead-acid battery, and the curing temperature is controlled to be 50-70° C. and the humidity is 50-95% to obtain the negative plate of the lead-acid battery.
- 根据权利要求1所述利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，其特征在于：所述步骤a中，所述氧化石墨烯片分散液原液中的氧化石墨烯片的固含量不高于5mg/mL。The method for manufacturing a long-life lead-acid battery negative electrode using trace amounts of graphene oxide flakes according to claim 1, characterized in that: in step a, the solid graphene oxide flakes in the stock solution of the graphene oxide flake dispersion liquid The content is not higher than 5mg/mL.
- 根据权利要求1所述利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，其特征在于：所述步骤b中，所述炭黑、硫酸钡、木素与铅粉的质量比分别为：0.2％、0.8％、0.2％。The method for manufacturing a long-life lead-acid battery negative electrode using trace graphene oxide sheets according to claim 1, wherein in step b, the mass ratios of the carbon black, barium sulfate, lignin and lead powder are respectively It is: 0.2%, 0.8%, 0.2%.
- 根据权利要求1所述利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，其特征在于：所述步骤b中，氧化石墨烯片分散液中的去离子水与铅粉的质量比不高于12％。The method for manufacturing a long-life lead-acid battery negative electrode using trace amounts of graphene oxide flakes according to claim 1, wherein in step b, the mass ratio of deionized water to lead powder in the graphene oxide flake dispersion is Not higher than 12%.
- 根据权利要求1或4所述利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，其特征在于：所述步骤b中，稀硫酸的密度不大于1.4g/cm 3，稀硫酸与铅粉的质量比不大于4.8％。 The method for manufacturing a long-life lead-acid battery negative electrode using trace graphene oxide sheets according to claim 1 or 4, characterized in that: in step b, the density of dilute sulfuric acid is not more than 1.4g/cm 3 , and the dilute sulfuric acid is combined with The mass ratio of lead powder is not more than 4.8%.
- 根据权利要求1所述利用痕量氧化石墨烯片制造长寿命铅酸电池负极的方法，其特征在于：所述步骤c中，所述固化采用分步固化工艺进行，固化时间至少为96h。The method for manufacturing a long-life lead-acid battery negative electrode using trace graphene oxide sheets according to claim 1, wherein in step c, the curing is performed by a step-by-step curing process, and the curing time is at least 96 hours.
- 权利要求1～6任意一项所述方法制备得到的铅酸电池负极，包括铅酸电池负极板板栅和涂覆于所述铅酸电极板板栅表面的铅膏；制备所述铅膏的原料包括氧化石墨烯片、炭黑、木素、硫酸钡、铅粉和稀硫酸，所述氧化石墨烯片在铅膏中的添加量不超过2ppm。The lead-acid battery negative electrode prepared by the method of any one of claims 1 to 6, comprising a lead-acid battery negative grid and a lead paste coated on the surface of the lead-acid electrode grid; The raw materials include graphene oxide flakes, carbon black, lignin, barium sulfate, lead powder, and dilute sulfuric acid, and the addition amount of the graphene oxide flakes in the lead paste does not exceed 2 ppm.
- 权利要求7所述铅酸电池负极在动力电池中的应用。The application of the negative electrode of the lead-acid battery according to claim 7 in a power battery.
- 一种铅酸电池，其特征在于，负极为权利要求7所述的铅酸电池负极。A lead-acid battery, characterized in that the negative electrode is the lead-acid battery negative electrode according to claim 7.
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