CN1183651A - Lead-acid accumulator contg. modifier and its preparing method - Google Patents

Abstract

A lead-acid accumulator containing new modifier features that the electrolyte, electrode plate or isolating body of said lead-acid accumulator contain tea polyphenols or its derivative (0.01-5%), which can improve the performance of lead-acid accumulator and regenerate the failed sulfurizing and active substances.

Description

Lead-acid storage battery containing novel improver and preparation method thereof

The invention relates to using tea polyphenols (Tea Polyphenols) and tea polyphenol derivatives as lead-acid battery improvers and a preparation method for lead-acid batteries containing the improvers. Specifically, the present invention provides that the principle of improving the electrochemical reaction with tea polyphenols and derivatives thereof is: Lead-antimony, lead-calcium, lead-separator alloy, lead powder, lead oxide, lead sulfate, humic acid, carbon black, sulphate, baking glue and other compositions as electrodes, lead sulfate, sulfuric acid aqueous solution as electrolyte An improvement agent for performance indicators such as service life, energy density (capacity per unit mass), fast charge, fast discharge, and over-discharge adaptability of acid storage batteries, and a method for preparing lead-acid storage batteries containing the improvement agent.

Lead-acid battery is currently the world's largest secondary battery in terms of capacity. Widely used in various transportation vehicles, electric power, telecommunication systems and other industries. Although the lead-acid battery has a history of more than one hundred years, it still occupies the largest proportion in the secondary battery because of its low price and mature technology. However, lead-acid batteries have low energy density, only 40 watt-hours per kilogram of mass, and their working life largely depends on the number, degree, and intensity of charge and discharge, and they have fatal weaknesses such as acid and lead pollution to the environment. It needs to be fully improved and perfected. The present invention adopts the method of adding tea polyphenols or tea polyphenol derivatives to the lead-acid storage battery, which directly improves performance indicators such as the energy density, working life, fast charge, fast discharge and over-discharge adaptability of the lead-acid storage battery; , lead pollution and the amount of non-ferrous metals and other materials consumed by lead-acid batteries.

Currently widely used lead-acid batteries are composed of shells, lead positive and negative plate groups, separators, sulfuric acid electrolyte, bus bars, connecting bars and other parts. The sulfuric acid electrolyte is diluted with (GB4554-84) qualified concentrated acid with pure water; the positive and negative plates are made of red lead (Pb ₃ O ₄ ) lead monoxide (PbO) lead powder (Pb) and a small amount of sulfuric acid Barium (BaSO ₄ ), baked glue, carbon black, benzine, humic acid, etc. are mixed and pasted and applied to the mesh grid made of lead-antimony, lead-calcium, lead-cadmium alloy, etc., and formed with sulfuric acid electrolyte Made; the separator is made of loose and porous sheet-shaped profiles made of inert materials such as rubber, wood chips, and plastics; the connecting strips and bus bars are all lead-antimony alloys. The shell is made of inert materials such as plastic and glass. 〖1〗〖2〗〖4〗There is no precedent for using tea polyphenols in lead-acid batteries.

In the present invention, 0.01%-5% of tea polyphenol or its modified derivatives are added to any or all components such as lead-acid battery electrolyte, pole plate, or spacer, so as to improve the unit mass capacity of lead-acid battery and prolong the service life. Life, blocking internal self-discharge, improving fast charge, fast discharge and over-discharge adaptability and other purposes. Compared with conventional lead-acid batteries, constant current charging, potential-time curve (accompanying drawing 1A), constant current discharging, potential time curve (accompanying drawing 1B), all have obvious improvement.

After adding tea polyphenols or modified derivatives prepared from tea polyphenols to lead-acid batteries that have failed, vulcanized, and capacity decreased, there is an obvious regeneration effect.

母核上含二个以上羟基的一系列被称之为茶多酚的提取物。茶多酚衍生物指的是以该提取物为原料，经物理方法、化学方法改性制备的产物。物理改性指将茶多酚干品、茶多酚溶液、酸溶液电解、热处理、电磁辐射、光辐射等不改变茶多酚基本化学性质、化学结构的处理。化学改性指用硫酸、双氧水、铅化合物处理茶多酚的方法。这些方法实质是将铅酸蓄电池内的物理、化学变化向外转移，仍属本发明的一种表现形式。The tea polyphenols described in the present invention refer to those that can be accepted by the tea science circle, and are extracted from the leaves, stems, flowers, and fruits of Camellia plants, and have the following core structure:

A series of extracts called tea polyphenols containing more than two hydroxyl groups on the mother nucleus. Tea polyphenol derivatives refer to the products prepared by using the extract as raw material and modified by physical and chemical methods. Physical modification refers to the treatment of dry tea polyphenols, tea polyphenol solution, acid solution electrolysis, heat treatment, electromagnetic radiation, light radiation, etc. without changing the basic chemical properties and chemical structure of tea polyphenols. Chemical modification refers to the method of treating tea polyphenols with sulfuric acid, hydrogen peroxide, and lead compounds. The essence of these methods is to transfer the physical and chemical changes in the lead-acid battery to the outside, and still belongs to a form of expression of the present invention.

The unique feature of the present invention is that all components such as lead-acid accumulator electrolyte, spacer, polar plate or any component in the work exist in ), to regenerate the lead-acid battery with sulfide or active material partial or complete failure, neutralize the electrolyte, separator or plate to pH ≈ 7, and use GB8313-87 to detect the concentration of tea with a concentration of 0.01%-5% Phenol or its derivatives.

The present invention is based on the improvement mechanism of lead-acid animal battery:

1. The energy density of the lead-acid battery is directly proportional to the ratio of the mass of the active material of the plate to the total mass of the plate; it is positively correlated with the active material and the amount of sulfuric acid in the sulfuric acid electrolyte. Increasing the proportion of active material in the total mass of the plate can increase the energy density. The active material limit components of lead-acid batteries are mainly composed of lead dioxide PbO2 and fluffy lead powder. The main difference between the positive and negative plates is that the positive plate contains more lead dioxide, and the negative plate contains more PbO and Pb. , the positive reaction during charging and discharging is: The positive electrode has an active substance, PbO _2, and there is an additional reaction during the charging process: The lead dioxide (PbO ₂ ) in the active material of the positive electrode will be gradually consumed during the charge and discharge cycle. After adding tea polyphenols or their derivatives, tea polyphenols or their derivatives can oxidize PbO to PbO ₂ , thereby maintaining or increasing the ratio of positive active materials, increasing energy density, improving performance, and prolonging life

2. The long-term application practice of lead-acid batteries shows that the life of lead-acid batteries depends on the quality and consumption of positive plates. The consumption of positive plates is much larger than that of negative plates. Tea polyphenols and their derivatives promote PbO ₂ Deposit on the positive plate to reduce the consumption of the positive plate, thereby prolonging the service life of the lead-acid battery.

3. The energy density, fast charge, fast discharge, and over-discharge adaptability of lead-acid batteries depend on the H ⁺ ion transfer conditions, and the micropore dredging conditions, improving the H ⁺ ion transfer, and the micropore dredging conditions can improve the performance indicators. More tea Phenol molecules with multiple active hydroxyl groups are effective H ⁺ carriers, and have good affinity and adhesion with lead ions, and can effectively transfer H ⁺ in sulfuric acid electrolyte, so that the micropores of the positive plate are sparse and the pores The internal H ₂ SO ₄ is quickly balanced with the electrolyte outside the hole, thereby improving related performance indicators. A large number of experiments and tests have proved that the effect is obvious.

The methods of adding tea polyphenols and its derivatives to lead-acid batteries are:

1. Dissolve directly in pure water or sulfuric acid electrolyte and add to the battery.

Embodiment 1: To the 6-Q-195 type lead-acid storage battery that needs to supplement 1000ml pure water, get the tea polyphenols with 50g tea polyphenols content ≥ 95% (produced by Tea Research Institute of Chinese Academy of Agricultural Sciences), dissolve in 1000ml pure Water, after mixing, add the required amount of liquid from the liquid hole to the battery.

Embodiment 2: For the 6-Q-165 type lead-acid storage battery that needs to be supplemented with 1000ml of sulfuric acid (d=1.10 G cm ^-3 ), get 20g of the same tea polyphenols as in Example 1, and dissolve it in 200ml of pure water Finally, the specific gravity was adjusted to 1.10G·cm ^-3 with concentrated sulfuric acid, and the solution was injected into the battery from the filling hole.

2. Directly add to the battery

Embodiment 3: Add the pure tea polyphenols from the liquid hole directly into lead-acid batteries that have been assembled, are being used, have not been used, or have been used with performance index decline, active material failure, etc. through the liquid hole.

3. Add it in the coating formula for preparing positive and negative plates, or in the chemical formation process and formula.

Example 4: Add 0.2% tea polyphenols or tea polyphenol derivatives to the positive electrode plate lead paste.

Add 0.5% tea polyphenols or tea polyphenol derivatives to the formula of the negative electrode plate.

Add tea polyphenol or its derivatives with a mass concentration of 0.2% of the chemical solution directly into the chemical solution, or directly add acid and water to dissolve the tea polyphenols or its derivatives with a mass percentage of 0.4% on the plate and apply it on the plate .

4. Preparation of spacers containing tea polyphenols or derivatives thereof.

Embodiment 5: Dissolve tea polyphenols or derivatives thereof in pure water or sulfuric acid with a mass concentration of 0.1-25% in water or sulfuric acid, immerse the spacer in the solution, and then dry or not dry; tea polyphenols can also be Make it into a thick paste, apply it directly on the separator, and assemble it into the battery.

The addition test to seven conventionally produced lead-acid accumulator products shows that: after adding tea polyphenols and tea polyphenol lead deposits, under the same service conditions and charge and discharge conditions, the lead-acid accumulator prepared by the utility model is the same as the Compared with other lead-acid batteries, it can increase the unit weight capacity by 27%; prolong the service life by 60%; can charge quickly at a rate of 10 hours for a long time without causing a sharp decline in service life; internal resistance decreases, and the terminal voltage is lower than 0.30 volts after over-discharge While not reducing the unit weight capacity and service life. After standing for 28 days, the capacity loss was 25% less than that of the control (type Q).

There are three situations in realizing the best solution of the present invention:

1. For conventionally produced lead-acid batteries, when filling the electrolyte for the first time ^, directly add 0.45%-1.60% (weight percent of the electrolyte) of tea polyphenols or Its derivatives are then put into use directly or after initial charge and discharge treatment according to the original technical requirements.

2. For lead-acid batteries that have not been added with tea polyphenols, add 0.3%-1.6% tea polyphenols or their modified derivatives of the total electrolyte weight percentage when replenishing pure water or electrolyte. For the battery that needs to replace the electrolyte in use, it can be carried out according to the addition method 1 of the new battery.

3. For lead-acid batteries with severe vulcanization and active material failure, tea polyphenols or their modified derivatives can be directly dissolved in pure water, added to lead-acid batteries, charged at a rate of 5-10 hours, and discharged twice. After charging, pour out the electrolyte, and then add it as a new lead-acid battery.

The invention can be implemented on various lead-acid storage batteries, and can also directly produce lead-acid storage batteries containing tea polyphenol or derivatives thereof. [1] Guo Jiang, "Lead Storage Battery and Charging Equipment", Sichuan People's Publishing House, 1980 [2] High-efficiency Yue, etc., Internal resistance and its changing behavior of sealed lead storage battery, Power Technology, 1992.5, 13-16 [3] Zhang Hao, etc. , Research on wet-charged lead-acid batteries, Battery, 1989(2), 13-17[4]GB5008.2-91

Claims (8)

1. A lead-acid accumulator containing new modifier is composed of casing, lead positive and negative electrode plate groups, separator, sulfuric acid electrolyte, bus bar and connecting bar, and features that the electrolyte, electrode plate or separator contains tea polyphenol or its physically and chemically modified derivative in 0.01-5 wt%.

2. The method for preparing lead-acid battery containing new improver as described in claim 1, wherein the tea polyphenol or its physically and chemically modified derivative with concentration of 0.01% -5% by weight of the battery is added in the process of preparing the lead-acid battery.

3. The tea polyphenol according to claim 1 or 2, which is acceptable in the field of tea science, and is obtained by extracting the plant leaves or other organs such as young stems and flowers of the genus camellia (Camell-ia) with a mother nucleus structure:a series of polyphenols containing more than two hydroxyl groups.

4. The physical modification of claim 1 or 2 refers to heating, freezing, electrolyzing, treating with electric field, magnetic field, electromagnetic radiation, light radiation, etc. the modification does not completely change the tea polyphenol composition structure or the basic properties of the modified lead-acid storage battery.

5. The chemical modification of claim 1 and 2 refers to the treatment of tea polyphenol with sulfuric acid, hydrogen peroxide, aqueous solution of sulfuric acid, lead, calcium, barium, antimony, cadmium and other compounds or the further introduction of hydroxyl, and is characterized in that the chemical change in the lead-acid storage battery is only transferred to the outside of the battery, and the invention still belongs to the scope of the invention.

6. The tea polyphenol modifier of claim 1 and 2 is added to achieve the following purposes:

(1) in order to improve the unit mass capacity of the lead-acid storage battery, the adaptability of quick charge, quick discharge and over discharge, the performance indexes of prolonging the service life and the like;

(2) partially or fully deactivating the active material, and regenerating a partially or fully sulfurized lead-acid battery;

(3) internal standard anti-counterfeiting;

(1) any or all of the objects of (1) to (3), wherein the objects are achieved by adding tea polyphenol or a physically and chemically modified derivative of tea polyphenol.

7. The method for adding the modifying agent of the invention according to claim 2 comprises:

(1) the modifier is directly added into a used, in-use or unused lead-acid storage battery or a semi-finished product, a component or a raw material for the lead-acid storage battery;

(2) dissolving the modifier in pure water, sulfuric acid solution or other solution capable of being used by lead-acid storage batteries, and adding the solution into the lead-acid storage batteries;

(3) the modifier is coated on a separator, an electrode plate or other components and assembled into a lead-acid storage battery;

(4) adding into the polar plate forming liquid or polar plate, or adding into the polar plate forming liquid or coating on the polar plate or the separator.

And the method of any or all of the preceding claims (1) to (4) is added in combination, wherein the tea polyphenol can be detected by a conventional tea polyphenol measuring method such as GB8313-87 when the electrolyte, the polar plate or the separator is neutralized to pH 7.0.

7. The lead-acid battery of claim 1 or 2, wherein the electrochemical reaction principle is that, using a combination of lead antimony, lead calcium, lead cadmium alloy, lead powder, lead oxide, lead sulfate, sulfuric acid, etc. as electrodes, using lead sulfate, dilute sulfuric acid as electrolyte, or using a dilute sulfuric acid-containing solution that can be used by other lead-acid batteries as electrolyte:

various lead-acid batteries.

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