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

Lead-acid accumulator contg. modifier and its preparing method Download PDF

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Publication number
CN1183651A
CN1183651A CN95118086A CN95118086A CN1183651A CN 1183651 A CN1183651 A CN 1183651A CN 95118086 A CN95118086 A CN 95118086A CN 95118086 A CN95118086 A CN 95118086A CN 1183651 A CN1183651 A CN 1183651A
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lead
acid
tea polyphenol
storage battery
battery
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肖纯
张凯农
王华夫
李名君
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SOUTHWEST AGRICULTURAL UNIVERSITY
Tea Research Institute Chinese Academy of Agricultural Sciences
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SOUTHWEST AGRICULTURAL UNIVERSITY
Tea Research Institute Chinese Academy of Agricultural Sciences
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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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 modifier and preparation method thereof
The invention relates to a lead-acid battery modifier prepared from Tea polyphenol (Tea Polyphenols) and Tea polyphenol derivatives and a preparation method of a lead-acid battery containing the modifier. Specifically, the invention provides the principle of improving the electrochemical reaction by using the tea polyphenol and the derivatives thereof as raw materials: the lead-acid accumulator using lead-antimony, lead-calcium, lead-isolating alloy, lead powder, lead oxide, lead sulfate, humic acid, carbon black, lignin and baking glue as electrode and aqueous solution of lead sulfate and sulfuric acid as electrolyte has long service life, high energy density, fast charge, fast discharge and over-discharge adaptability and other performance indexes.
Lead-acid batteries are the largest secondary batteries currently consumed in the world as measured by capacity. The method is widely applied to industries such as various transportation tools, electric power systems, telecommunication systems and the like. Although lead-acid storage batteries have been used for hundreds of years, the best proportion of secondary batteries is still achieved by the mature technology at low cost. However, the lead-acid storage battery has the defects that the energy density is low, the mass per kilogram is only 40 watts, the working life depends on the charging and discharging times, degree and strength to a great extent, and the lead-acid storage battery has the fatal defects of acid and lead pollution to the environment. Needs to be improved and perfected comprehensively. The invention adopts the method of adding tea polyphenol or tea polyphenol derivatives into the lead-acid storage battery, directly improves the performance indexes of the lead-acid storage battery, such as energy density, working life, quick charge, quick discharge, overdischarge adaptability and the like: indirectly reduces the amount of nonferrous metal and other materials consumed by acid, lead pollution and lead-acid storage batteries.
The lead-acid accumulator widely used at present is composed of casing, positive and negative lead plates, separator, sulfuric acid electrolyte, bus bar and connecting bar. The sulfuric acid electrolyte is prepared by diluting qualified concentrated flowing acid (GB4554-84) with pure water; the positive and negative electrode plates are made of PlumbumPreparatium (Pb)3O4) Lead monoxide (PbO) lead powder (Pb) and a small amount of barium sulfate (BaSO)4) Mixing baking glue, carbon black, sodium benzoate, humic acid and the like, pasting the mixture on a reticular grid made of lead-antimony, lead-calcium, lead-cadmium alloy and the like, and forming the reticular grid with sulfuric acid electrolyte to obtain the composite material; the separator is made into loose porous sheet-shaped section bars by inert materials such as rubber, wood chips, plastics and the like; the connecting bar, the bus bar and the like are all lead-antimony alloy. The shell is made of inert materials such as plastic, glass and the like. As a method of using tea polyphenols in lead-acid storage batteries, 1(s) (2) (as a method of using tea polyphenols in lead-acid storage batteries) has been known.
The invention adds 0.01-5% of tea polyphenol or modified derivative thereof into any or all components of lead-acid storage battery electrolyte, polar plate or separator, and the like, thereby achieving the purposes of improving the unit mass capacity of the lead-acid storage battery, prolonging the service life, blocking internal self-discharge, improving the adaptability of quick charge, quick discharge and over-discharge, and the like. Compared with the conventional lead-acid storage battery, the constant-current charging, potential-time curve (figure 1A), constant-current discharging and potential-time curve (figure 1B) are all obviously improved.
The lead-acid storage battery with the regeneration agent has obvious regeneration effect after the lead-acid storage battery loses efficacy, is vulcanized and has reduced capacity and is added with tea polyphenol or modified derivatives prepared by taking the tea polyphenol as raw materials.
The tea polyphenol of the invention is accepted by the tea science world, is extracted from leaves, stems or flowers and fruits of Camellia (Camellia) plants, and has the following mother nucleus structure:
Figure A9511808600051
a series of extracts called tea polyphenols containing more than two hydroxyl groups on the mother nucleus. The tea polyphenol derivative is a product prepared by taking the extract as a raw material and modifying the extract by a physical method and a chemical method. The physical modification refers to the treatment of electrolyzing, thermally treating, electromagnetically radiating, and light radiating tea polyphenol product, tea polyphenol solution, acid solution, etc. without changing the basic chemical property and structure of tea polyphenol. The chemical modification refers to a method for treating tea polyphenol by using sulfuric acid, hydrogen peroxide and lead compounds. The methods are used for transferring physical and chemical changes in the lead-acid storage battery outwards, and still belong to one expression form of the invention.
The invention is characterized in that the electrolyte, the separator, the polar plate and other all components or any components of the lead-acid storage battery in operation can improve the performance (unit mass capacity, adaptability of sexual charging, quick discharging and over discharging and service life), lead-acid storage batteries with partial or total failure of vulcanized and active substances can be regenerated, and the tea polyphenol or the derivatives thereof with the concentration of 0.01-5% can be detected by GB8313-87 when the electrolyte, the separator or the polar plate is neutralized to the pH value of about 7.
The improvement mechanism of the lead-acid storage battery is based on the following steps:
1. the energy density of the lead-acid storage battery is in direct proportion to the proportion of the mass of the active material of the pole plate in the total mass of the pole plate; is positivelycorrelated with the active substance and the sulfuric acid content in the sulfuric acid electrolyte. Increasing the proportion of active material in the total mass of the plate increases the energy density. The active material limiting component of the lead-acid storage battery mainly comprises lead dioxide PbO2 and velvet lead powder, the main difference of the positive plate and the negative plate is that the positive plate contains more lead dioxide, the negative plate contains more PbO and Pb, and the positive reaction in the charging and discharging process is as follows: positive electrode with active material PbO2There is an additional reaction during charging: lead dioxide (PbO) in positive electrode active material2) Will be gradually consumed in the charge and discharge cycles. After tea polyphenol or derivatives thereof are added, the tea polyphenol or derivatives thereof can oxidize PbO into PbO2Thereby maintaining or improving the proportion of the positive active material, increasing the energy density, improving the performance and prolonging the service life
2. The long-term lead-acid storage battery application practice shows that the service life of the lead-acid storage battery depends on the quality and consumption of a positive electrode plate, the consumption of the positive electrode plate is far larger than that of a negative electrode plate, and the tea polyphenol and derivatives thereof promote PbO in the charging and discharging processes2And the deposition is carried out on the positive plate, so that the consumption of the positive plate is reduced, and the service life of the lead-acid storage battery is prolonged.
3. The energy density, quick charge, quick discharge and over discharge adaptability of the lead-acid storage battery depend on H+Ion transfer conditions, micropore dredging conditions, improvement of H+The performance index can be improved under the conditions of ion transfer and micropore dredging, and the tea polyphenol molecule with a plurality of active hydroxyl groups is effective H+The carrier has good affinity and adhesion with lead ions, and can effectively transfer H in sulfuric acid electrolyte+The micropores of the positive plate are thinned and have H in the holes2SO4Rapidly equilibrate with the electrolyte outside the pores, thereby improving the relevant performance index. A large number of experiments and experiments prove that the effect is obvious.
The method for adding the tea polyphenol and the derivatives thereof into the lead-acid storage battery comprises the following steps:
1. directly dissolved in pure water or sulfuric acid electrolyte and added into a storage battery.
Example 1: for a 6-Q-195 type lead-acid storage battery which needs to be supplemented with 1000ml of pure water, 50g of tea polyphenol with the tea polyphenol content of more than or equal to 95% (produced by tea research institute of Chinese academy of agricultural sciences) is dissolved in 1000ml of pure water, and the mixture is uniformly mixed and added into the battery according to the amount of each lattice liquid to be supplemented.
Example 2: 1000ml of dilute sulfuric acid (d ═ 1.10. G. cm) are added to the used dilute sulfuric acid-3) A6-Q-165 type lead-acid battery was prepared by dissolving 20G of the same tea polyphenol as in example 1 in 200ml of pure water, and adjusting the specific gravity to 1.10 G.cm with concentrated sulfuric acid-3Then the solution is injected into the cell from the liquid adding hole.
2. Direct-charging accumulator
Example 3: the pure tea polyphenol product obtained in the same example 1 is directly added into a lead-acid storage battery which is assembled, is in use, is not used or has been used, has reduced performance indexes, invalid active substances and the like from a liquid hole.
3. The coating agent is added in the coating formula for preparing the positive and negative plates or the formation process and the formula.
Example 4: tea polyphenol or tea polyphenol derivatives with the mass percentage of 0.2 percent of lead powder are added into the positive pole plate lead plaster.
Tea polyphenol or tea polyphenol derivatives with the mass percent of 0.5 percent of lead powder are added into the formula of the negative electrode plate.
Directly adding tea polyphenol or its derivative with the mass concentration of 0.2% into the formed liquid, or directly adding tea polyphenol or its derivative with the mass percentage of 0.4% into acid and water, dissolving, and coating on the polar plate.
4. Preparing a barrier material comprising tea polyphenols or derivatives thereof.
Example 5: dissolving tea polyphenol or its derivative in pure water or dilute sulfuric acid with mass concentration of 0.1-25% in water or dilute sulfuric acid, immersing the spacer in the solution, and drying or not drying; or mixing tea polyphenols into thick paste, directly smearing on the separator, and assembling into battery.
The addition tests of seven conventionally produced lead-acid storage battery products show that: after the tea polyphenol and the lead precipitate of the tea polyphenol are added, the lead-acid storage battery prepared by the utility model can improve the unit weight capacity by 27 percent compared with other lead-acid storage batteries under the same use condition and charge-discharge condition; the service life is prolonged by 60 percent; the quick charging can be carried out at a rate of 10 hours for a long time without causing the rapid reduction of the service life; the internal resistance is reduced, and the unit weight capacity and the service life are not reduced when the internal resistance is overdischarged to the terminal voltage of less than 0.30V. The capacity loss after 28 days of standing was less than 25% of the control (form Q).
The best solution for implementing the present invention has three situations:
1. the lead-acid accumulator produced conventionally has specific weight of 1.20-1.35G.CM when it is first filled with electrolyte-3The electrolyte is directly added with 0.45-1.60 percent (by weight percentage) of tea polyphenol or derivatives thereof, and then is directly put into use or put into use after initial charge and discharge treatment according to the original technical requirements.
2. For the lead-acid storage battery which is not added with tea polyphenol, 0.3-1.6 percent of tea polyphenol or modified derivatives thereof in percentage by weight of the total electrolyte is added when pure water or the electrolyte is supplemented. The method 1 for adding new accumulator can be used for accumulator needing to be replaced in use.
3. The lead-acid accumulator with serious sulfurization and active matter failure can be prepared by dissolving tea polyphenol or its modified derivative in pure water, adding lead-acid accumulator, quickly charging at 5-10 hr, discharging twice, pouring out electrolyte after full charging, and adding new lead-acid accumulator.
The invention can be implemented on various lead-acid storage batteries and can also be used for directly producing the lead-acid storage battery containing tea polyphenol or derivatives thereof. [1]Guojiang, lead accumulator and charging equipment, Sichuan people's press, 1980[2]Kagao et al, internal resistance of sealed lead accumulator and its variation behavior, power supply technology, 1992.5, 13-16[3]zhanghao et al, research on wet charged lead-acid accumulator, 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.
CN95118086A 1995-11-11 1995-11-11 Lead-acid accumulator contg. modifier and its preparing method Pending CN1183651A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110034341A (en) * 2019-04-26 2019-07-19 张健 A kind of neutral electrolyte
CN114122532A (en) * 2021-11-19 2022-03-01 何幸华 Horizontal lead-acid storage battery and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110034341A (en) * 2019-04-26 2019-07-19 张健 A kind of neutral electrolyte
CN114122532A (en) * 2021-11-19 2022-03-01 何幸华 Horizontal lead-acid storage battery and preparation method thereof
CN114122532B (en) * 2021-11-19 2023-06-06 何幸华 Horizontal lead-acid storage battery and preparation method thereof

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