CN1149208A - Antimony-lead accumulator and manufacture thereof - Google Patents
Antimony-lead accumulator and manufacture thereof Download PDFInfo
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- CN1149208A CN1149208A CN95112498A CN95112498A CN1149208A CN 1149208 A CN1149208 A CN 1149208A CN 95112498 A CN95112498 A CN 95112498A CN 95112498 A CN95112498 A CN 95112498A CN 1149208 A CN1149208 A CN 1149208A
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- antimony
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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
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Abstract
An acid Sb-Pb accumulator as an improvement on acid Pb accumulator is composed of positive and negative electrode plates, diaphragm, electrolyte and container, and features that its negative electrode plate contains antimony and its positive one contains lead. The negative electrode plate is made up through coating the mixture of antimony oxide (or antimony) powder, copper powder and distilled water (or diluted sulfuric acid with concentration less than 20%) along with copper wire net on silver plated copper (or red copper) plate, solidifying and drying in air. Its advantages include no self discharge, high capacity and unit output power, good sealing, high utilization rate of Sb and long service life.
Description
The invention relates to a semi-lead storage battery, in particular to an antimony-lead acid storage battery with a positive plate containing lead and a negative plate containing antimony and a manufacturing method thereof.
The existing alkaline storage batteries (such as iron-nickel storage batteries and cadmium-nickel storage batteries) have lower capacity, higher internal resistance and higher price; lead-acid batteries have the disadvantages of difficult capacity improvement, prominent self-discharge problem and the like.
The invention aims to provide an antimony-lead acid storage battery with larger capacity, no self-discharge and low cost and a manufacturing method thereof.
The solution of the invention is an improvement on the prior lead-acid storage battery technology. The structure of the accumulator mainly comprises a positive plate, a negative plate, a diaphragm, an electrolyte and a container, and is characterized in that the negative plate contains an active material antimony.
The invention relates to a method for manufacturing a negative plate of an antimony-lead acid storage battery, which is to coat antimony oxide powder (Sb) on a silver-plated copper sheet (or a red copper sheet)2O3) [ or antimony powder (Sb)]The copper powder (Cu) is mixed with pure distilled water (or dilute sulfuric acid with concentration less than 20%) until it is free-flowing and does not drip by hand pressure, then the copper wire mesh is pressed on them, after solidification and air-drying, the negative plate is obtained, and the active material antimony content on the negative plate must meet the requirements of complete reaction of active material lead dioxide on the positive plate and dilute sulfuric acid.
The positive plate of the antimony-lead acid storage battery of the invention is just the same as the positive plate of the existing lead-acid storage battery, namely lead dioxide. The diaphragm is made of imbibing porous superfine glass fiber felt or acid-proof semi-permeable membrane or asbestos felt, and the positive plate is tightly wrapped by the diaphragm to separate the positive plate from the negative plate and prevent short circuitbetween the positive plate and the negative plate. The electrolyte is prepared from purified distilled water and purified concentrated sulfuric acid, the concentration of the dilute sulfuric acid is between 10% and 70%, and the optimal concentration is between 25% and 50%. The electrolyte plays a role in the antimony-lead acid storage battery, namely, the electrolyte can react with active substances in the positive and negative plates during discharge on one hand and can conduct electricity on the other hand. The container is generally made of a material resistant to sulfuric acid, such as hard rubber, plastic, glass, or the like.
The antimony of negative plate in the antimony-lead acid accumulator can not replace the hydrogen in the dilute sulfuric acid, so it can not react with the dilute sulfuric acid in the electrolyte, and thus it can not self-discharge. When charging, as long as the voltage is controlled within the decomposition voltage of hydrogen and oxygen, no gas is generated, and sealing is possible. In addition, the concentration of dilute sulfuric acid in the electrolyte can be properly increased, the volume of the electrolyte is reduced, the electrolyte can be absorbed in the polar plate and the diaphragm, the polar plate can be additionally arranged, the capacity of the battery is relatively increased, and the liquid can not flow. Therefore, the antimony-lead acid storage battery of the invention, which is improved on the basis of the lead-acid storage battery, can be stored for a long time after charging because of no self-discharge, has longer relative discharge service time and service life than the lead-acid storage battery, and simultaneously has the advantages of larger capacity and sealing performance compared with the lead-acid storage battery. In addition, because the antimony sulfate is dissolved in water, the passivation phenomenon of the negative plate is weakened, the output power per unit volume is large, the utilization rate of the active substance negative electrode antimony is improved, materials are saved relatively, and the manufacturing cost is reduced.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
FIG. 1 is a schematic structural view of an antimony lead acid battery of the present invention assembled using an NP4-6 type can container;
FIG. 2 is a schematic diagram of the electromotive force generation process of the antimony lead acid secondary battery according to the present invention;
FIG. 3 is a schematic diagram of the chemical reaction of the antimony lead acid battery of the present invention during discharging;
FIG. 4 is a schematic diagram of the chemical reaction of the antimony lead acid battery according to the present invention during charging;
FIG. 5 is a schematic view of the inside of the antimony-lead acid storage battery according to the present invention after charging;
fig. 6 is a block diagram showing a process flow of assembling the antimony lead acid secondary battery of the present invention using an NP4-6 type can.
See fig. 1. The structure of the antimony-lead acid storage battery mainly comprises a positive plate 1, a negative plate 2, a diaphragm 3, an electrolyte 4 and a container 5, and is characterized in that the negative plate 2 contains an active substance antimony.
See fig. 2. The positive plate of the antimony-lead acid accumulator is lead dioxide (PbO)2) The negative plate is antimony (Sb), which are two different active species and therefore react with dilute sulfuric acid (H)2SO4) The results of the chemical action performed are also different.
The lead dioxide of the positive plate has a small amount of lead dioxide molecules permeating into the electrolyte under the action of water molecules in the electrolyte, and divalent oxygen ions (O) in the lead dioxide molecules2) Hydration to convert the lead dioxide molecule into a transitional and dissociable substance [ Pb (OH)]4]Namely:
and tetravalent lead ion (Pb)4+) If the electron beam is still left on the electrode plate, electrons are lacked on the electrode plate, and the electrode plate shows positive electricity.
Although the antimony (Sb) of the negative electrode plate does not react with dilute sulfuric acid and water in the electrolyte, the dilute sulfuric acid in the electrolyte is lack of electron electropositivity on the lead dioxide plate of the positive electrode plate(H2SO4) Is ionized into hydrogen positive ions (H)+) And sulfate ion (SO)4 2-) Under the action of positive electricity of the positive plate, the hydrogen positive ions and sulfate negative ions in the electrolyte become orderly arranged, and the periphery near the positive plate is filled with a large amount of sulfate ions (SO) with negative charges4 2-) And a small amount of negatively charged hydroxyl ions (OH)-) The negative electrode plate is surrounded by a large number of positively charged hydrogen ions (H)+) Under the action of electrostatic attraction, the surface of the negative electrode plate is negatively charged, and therefore the negative electrode plate exhibits negative charge with respect to the positive electrode plate.
As a result, when the load is not applied, the positive electrode plate and the negative electrode plate exhibit positive and negative polarities due to chemical and electrostatic attraction, and a certain potential difference (electromotive force) is generated between the two electrodes.
See fig. 3. When a load (such as a lamp) is connected to an external circuit, electrons on the negative plate enter the positive plate through the load to form a current I under the action of a potential difference (electromotive force) between the positive plate and the negative plate of the antimony-lead acid storage battery. At the same time, a chemical reaction takes place inside the battery.
On the negative plate, each antimony atom (Sb) emits 3 electrons (3e) to form positive antimony ions (Sb)3+) Therefore, a plurality of surplus electrons appear on the negative plate, and the electrons continuously flow into the positive electrode through an external circuit under the action of the potential difference to form current. In the electrolyte, positive hydrogen ions (H) are present due to the ionization of sulfuric acid molecules+) And sulfate anion (SO)4 2-) Are present. At this time, the process of the present invention,positive hydrogen ions (H) due to the electrostatic action of opposite charges (ions)+) Move to the positive electrode, sulfate anion (SO)4 2-) Moving to the negative electrode, thus forming an ionic current inside the battery. When acid radical anion (SO)4 2-) Antimony positive ion (Sb) with negative electrode3+) When they meet each other, antimony sulfate [ Sb]is generated2(SO4)3]Molecules are attached to the negative electrode or dissolved in the electrolyte, i.e.:
at the positive electrode, electrons enter from an external circuit, and then are reacted with tetravalent lead positive ions (Pb)4+) Combined to a divalent lead positive ion (Pb)2+) And immediately reacts with acid radical ions (SO) near the positive electrode4 2-) Combined together to produce lead sulfate molecules (PbSO)4) Attached to the positive electrode. Simultaneously, hydrogen positive ion (H) moves to the positive electrode+) Then react with oxygen anion (O)2-) Combine to form water molecule H2O, namely: the overall chemical reaction at discharge is then:
since the discharge can not be known by measuring the specific gravity of sulfuric acid as in the case of a lead-acid battery, the discharge degree of the battery can only be known by measuring the voltage. When discharging, the discharge voltage is 1.2V, which indicates that the antimony-lead acid storage battery is completely discharged. Typically, 1.2 volts is the terminal voltage of an antimony lead acid battery.
See fig. 4 and 5. Charging is the reverse of discharging. During charging, a direct current power supply (a charger or a rectifier) is externally connected to the storage battery, so that active substances consumed by the positive and negative plates during discharging are reduced, and the externally-added electric energy is converted into chemical energy to be stored. Under the action of the charging power supply, the current 1 of the external circuit flows in from the positive plate of the storage battery and flows out through the electrolyte and the negative plate. Thus, the power source continuously takes electronsfrom the positive plate and transfers them to the negative electrode, which promotes lead sulfate (PbSO) on the positive plate4) Continuously advanceIs dissociated by the electrolyte; on the negative plate or by electrolysisAntimony sulfate [ Sb]in liquid2(SO4)3]Are constantly liberated in the electrolyte. The following chemical reactions thus take place inside the cell:
on the negative plate, trivalent antimony ions (Sb) are obtained as electrons are obtained3+) The electrons obtained are neutralized into antimony (Sb) because the ability to obtain electrons is stronger than that of hydrogen ions, and are attached to the negative plate in a solid state, that is:
the electrons lost from the positive electrode plate are divalent lead ions (Pb) in the electrolyte, which are located near the electrode plate and are in a free state2+) Two electrons are continuously emitted to supplement. When it becomes quadrivalent lead ion (Pb)4+) Then, the water is immediately mixed with hydroxyl ions [ (OH)-]Combine to form transitional and dissociable species and free hydrogen ions, and continue to be decomposed into lead dioxide (PbO)2) And water, i.e.:
H+move to the negative plate under the action of current and SO4 2-Moving towards the positive plate, the two ions combine into sulfuric acid due to electrostatic attraction:
the overall chemical reaction upon charging is then:
when charging, it can not detect whether the antimony-lead acid accumulator is charged by measuring the specific gravity of electrolyte like the lead-acid accumulator, but only by measuring the charging voltage. And when the charging voltage is stabilized at 1.8-1.85V, the charging is finished.
The negative electrode antimony of the antimony-lead acid storage battery is 0.24V relative to the hydrogen standard electrode potential in aqueous solution, and the standard oxidation-reduction potential of bivalent lead ions relative to quadrivalent lead ions is Po2+/Pb4+1.7 volts, i.e. the standard electromotive force of an antimony lead acid battery is 1.7-0.24 to 1.46 volts, but since in dilute sulfuric acid the electromotive force is increased to some extent, about 1.6 volts. Namely, the open-circuit voltage of the antimony-lead acid storage battery is 1.6 volts, and the working voltage of the antimony-lead acid storage battery can reach more than 1.5 volts; the stop voltage is 1.2V, the charging voltage is 1.7-1.9V, no hydrogen is generated in the range, and the charging can be stopped when the charging voltage is stabilized at 1.8-1.85V. The charging is completed by measuring the voltage range. The charging current generally adopts a charging rate of 15-16 hours. When the terminal voltage is 1.2V during discharging, the discharging is considered to be finished, and the discharging can be stopped.
See fig. 6. The manufacturing process of the antimony-lead acid storage battery is further explained by taking a trial test sample as an example. In this example, a small-sized sealed lead-acid battery NP4-6 type case manufactured by the Japanese soup shallow corporation was used as a container for the battery of the present invention, which had dimensions of 70mm in length, 47mm in width and 105.5mm in height and contained only one of the cells; the lead dioxide positive plate is used as the positive plate of the storage battery; the diaphragm of the accumulator is used as the diaphragm of the accumulator (only a single layer is needed); silver-plated copper sheets (or red copper sheets) with the same size as the negative plates are used, and the thickness is about 0.2 mm; weaving a copper wire mesh (namely a single-layer copper mesh) by using copper wires; the copper powder and antimony oxide powder are mixed with pure distilled water (or dilute sulfuric acid with concentration less than 20%) according to the ratio of 1: 5 or 1: 6 until they do not flow freely and do not drop by hand pressure. The mixture and a copper net are applied on a copper sheet and compressed, the thickness is not more than 1.2 mm, and the mixture is used as a negative plate of the antimony-lead acid storage battery after solidification and air drying. Then, arranging three positive plates, four negative plates and a diaphragm according to each grid, paying attention to the fact that short circuit cannot occur between the positive plates and the negative plates, putting the positive plates and the negative plates into the single grid together, and adding dilute sulfuric acid with the concentration of 40% -50% on the basis that no free flowing liquid exists in the single grid. The discharge is carried out for about 35 hours by charging with 0.3 to 0.5 ampere current, and 3 small bulbs of 1.5 volts and 0.2 ampere are used for carrying out single-cell discharge, and the discharge can be continuously carried out for more than 14 hours. The voltage at the starting end is more than 1.5 volts, andthe voltage at the ending end is 1.2 volts. Repeated charging and discharging for several times, and if the dilute sulfuric acid is not enough, the solution can be added. The capacity of the lead-acid battery can reach more than 7.56Ah, the energy is more than 11W, each cubic liter is more than 100W, and both the capacity and the energy exceed the single-cell capacity and the energy of the NP4-6 type lead-acid battery.
Claims (3)
1. The acid Sb-Pb accumulator consists of mainly positive plate, negative plate, diaphragm, electrolyte and container, and features that the negative plate contains active Sb.
2. A process for preparing the acidic Sb-Pb accumulator features that the lead dioxide plate is used as positive electrode plate, the porous superfine glass fibre felt or acid-proof semi-permeable film or asbestos felt as diaphragm, the electrolyte is prepared from distilled water and concentrated sulfuric acid, the concentration of diluted sulfuric acid is 10-78%, and the container is made of hard rubber, plastics and glass2O3) [ or antimony powder (Sb)]The copper powder (Cu) is mixed with pure distilled water (or dilute sulfuric acid with concentration less than 20%) until it is free-flowing and does not drip by hand pressure, then the copper wire mesh is pressed on them, after solidification and air-drying, the negative plate is obtained, and the active material antimony content on the negative plate must meet the requirements of complete reaction of active material lead dioxide on the positive plate and dilute sulfuric acid.
3. The method of claim 2, wherein the dilute sulfuric acid has a concentration of between 25% and 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112498A CN1149208A (en) | 1995-10-24 | 1995-10-24 | Antimony-lead accumulator and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112498A CN1149208A (en) | 1995-10-24 | 1995-10-24 | Antimony-lead accumulator and manufacture thereof |
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| CN1149208A true CN1149208A (en) | 1997-05-07 |
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| CN95112498A Pending CN1149208A (en) | 1995-10-24 | 1995-10-24 | Antimony-lead accumulator and manufacture thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248547B (en) * | 2005-08-01 | 2010-05-19 | 托马斯·约翰·迈耶 | An electrode and a method for forming an electrode |
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1995
- 1995-10-24 CN CN95112498A patent/CN1149208A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248547B (en) * | 2005-08-01 | 2010-05-19 | 托马斯·约翰·迈耶 | An electrode and a method for forming an electrode |
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