CN114122532B - Horizontal lead-acid storage battery and preparation method thereof - Google Patents
Horizontal lead-acid storage battery and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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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
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- 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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- 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
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Abstract
The invention discloses a preparation method of a horizontal lead-acid storage battery, which relates to the technical field of the horizontal lead-acid storage battery, and comprises the following steps: s1, lead-coated wire drawing or casting plate; s2, weaving a net or punching the net; s3, vacuum mixing paste: vacuum stirring the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water to obtain positive lead plaster; wherein the red lead mixture consists of red lead and lead monoxide; vacuum stirring lead monoxide, sulfuric acid, a binder, sodium sulfate, a negative expansion agent and pure water to prepare negative lead plaster; s4, coating a plate; s5, pickling; s6, drying; s7, assembling; s8, cast welding; s9, sealing; s10, acid filling in vacuum; s11, forming; s12, wax filling. The horizontal lead-acid storage battery prepared by the preparation method provided by the invention has long service life, high shock resistance, high current property and ultralow temperature resistance.
Description
Technical Field
The invention relates to the technical field of horizontal lead-acid storage batteries, in particular to a horizontal lead-acid storage battery and a preparation method thereof.
Background
The horizontal lead-acid storage battery is a lead-acid storage battery with a novel structure, and has the advantages of low cost, high specific energy, high power and quick charge of the traditional sealed lead-acid storage battery.
However, the horizontal lead-acid battery on the market has poor vibration resistance and low temperature resistance. And the existing preparation method of the horizontal lead-acid storage battery is difficult to produce.
At present, no preparation method for the horizontal lead-acid storage battery is available, and the horizontal lead-acid storage battery with long service life, high shock resistance, high current and ultralow temperature resistance can be prepared.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of the horizontal lead-acid storage battery, and the horizontal lead-acid storage battery prepared by the preparation method provided by the invention has long service life, high shock resistance, high current property and ultralow temperature resistance.
The preparation method comprises the following steps:
s1, lead-coated wire drawing: heating the lead column to a semi-liquid state, extruding by adopting a die, immediately cooling, solidifying and winding on a spool to obtain a lead wire;
or cast sheet: melting metallic lead and a metallic additive to obtain molten metal, cooling and pulling out the molten metal to form a metal plate strip, and rolling to obtain a casting plate coil;
s2, weaving a mesh: braiding lead wires into a grid, serging the grid by using a hot melt wire, cutting the grid into strips, and rolling the strips on a winding drum;
or punching: stamping the cast plate coil stock through a high-speed continuous punch press to prepare a net belt, ultrasonically cleaning the net belt, and rolling the net belt on a winding drum;
s3, vacuum mixing paste: vacuum stirring the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water to obtain positive lead plaster; wherein the red lead mixture consists of red lead and lead monoxide; vacuum stirring lead monoxide, sulfuric acid, a binder, sodium sulfate, a negative expansion agent and pure water to prepare negative lead plaster;
s4, plate coating: respectively coating positive lead plaster and negative lead plaster on the left side and the right side of the mesh belt, and rolling and cutting to obtain a bipolar plate coated with the lead plaster;
s5, pickling: pickling the bipolar plate coated with the lead paste at a constant speed through a pickling tank filled with dilute sulfuric acid, so that the surface of the polar plate rapidly reacts to generate a lead sulfate layer, and a wet polar plate is prepared;
s6, drying: drying the wet polar plate in a drying device to obtain a dry polar plate;
s7, assembling: stacking the dry polar plate and the AGM diaphragm on a pressure frame by using a mechanical arm, compressing, and then adding a pressure cover plate to fix the battery core;
s8, cast welding: connecting terminal wires on terminal polar plates at the positive and negative ends of the stacked and compressed battery core with a terminal seat to perform welding casting to form a common terminal casting, and preparing the cast-welded battery core;
s9, sealing: filling the cast-welded battery core into a battery box, sealing the battery box by using a terminal clamp spring or a terminal nut and an O-shaped ring, and heat-sealing the battery box and a cover together by using a heat-sealing machine to prepare an assembled heat-sealed battery;
s10, acid filling in vacuum: under the vacuum condition, evacuating air in the assembled and heat-sealed battery, injecting sulfuric acid into the battery through negative pressure difference, and sucking sulfuric acid by an AGM diaphragm in the battery to prepare an acid-filled battery;
s11, formation: the battery after acid filling is subjected to formation to activate the battery, so that an activated battery is prepared;
s12, wax filling: and filling the molten paraffin into the gaps in the activated battery from bottom to top, and washing to obtain the horizontal lead-acid storage battery.
Preferably, in the step S1, the heating in the lead-coated wire drawing is performed to 110+/-15 ℃, the extrusion pressure is 28+/-5 MPa, and the winding speed is 200+/-10 mm/S; in the step S1, the melting temperature in the casting plate is 400-480 ℃, the cooling is realized by adopting a cooling rolling cylinder, and the thickness of the metal plate strip is 0.5-1.5mm.
Preferably, in step S1, the lead column is made of high tin-lead with tin content of 1.2%;
the metal additives are calcium, tin, aluminum and silver, and the mass of the calcium, the tin, the aluminum and the silver is respectively 0.04% -0.07%, 0.14% -1.2%, 0.03% -0.05% and 0.01% -0.012% of the mass of the metallic lead.
Preferably, in the step S3, the sulfuric acid is sulfuric acid with a specific gravity of 1.4 at 25 ℃, the binder is teflon, and the red lead mixture is prepared from the following components in percentage by mass: 3 red lead and lead monoxide;
the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water are prepared from the following components in parts by weight: 4.01:0.41:0.65:13.1;
the weight part ratio of the lead monoxide, the sulfuric acid, the adhesive, the sodium sulfate, the negative expansion agent and the pure water is 83.33:3.50:0.42:0.67:0.83:11.25;
the vacuum is 90-115mpa.
Preferably, in step S5, the specific gravity of the dilute sulfuric acid at 25 ℃ is 1.200±0.002, the temperature of the dilute sulfuric acid is 27±1 ℃, and the pickling time is 60±2 seconds.
Preferably, in step S6, the drying temperature is 55-60 ℃ and the drying time is 6h.
Preferably, in step S7, the compressed air pressure is 0.5-0.7MPa.
Preferably, in step S10, the specific gravity of the sulfuric acid at 25 ℃ is 1.220+/-0.002, the temperature of the sulfuric acid is 22-26 ℃, and the vacuum condition is that the vacuum pressure is 90-94kPa.
Preferably, in step S11, the temperature of the paraffin wax is 93-103 ℃.
Another object of the present invention is to protect the horizontal lead-acid battery produced by the above-mentioned production method.
The beneficial effects of the invention are as follows:
(1) The horizontal lead-acid storage battery prepared by the preparation method provided by the invention has long service life which is up to 400 weeks and is 50-100% longer than the service life of the traditional lead-acid storage battery.
(2) The horizontal lead-acid storage battery prepared by the preparation method provided by the invention has high vibration resistance, can reach the vibration resistance performance of 10g, and is far higher than 5g twice of the national standard vibration resistance standard of 30M/S2 in GB/T5008-2013 5.11.4.
(3) The horizontal lead-acid storage battery prepared by the preparation method provided by the invention has high current performance, can achieve 10C discharge multiplying power and 3C charge multiplying power, and is far higher than the traditional lead-acid storage battery in high current capacity, and the maximum 5C discharge multiplying power and 0.5C charge multiplying power.
(4) The horizontal lead-acid storage battery prepared by the preparation method provided by the invention has ultralow temperature performance, the discharge capacity at-18 ℃ can reach 80%, and the horizontal lead-acid storage battery can be charged and discharged at low temperature.
Detailed Description
Embodiments of the technical scheme of the present invention will be described in detail below. The following examples are only for more clearly illustrating the technical aspects of the present invention, and thus are merely examples, and are not intended to limit the scope of the present invention.
It is noted that unless otherwise indicated, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
Example 1
The embodiment provides a preparation method of a horizontal lead-acid storage battery, which is used for preparing a 12V 85Ah horizontal lead-acid storage battery.
The preparation method comprises the following steps:
s1, lead-coated wire drawing: heating the lead column to a semi-liquid state, extruding by adopting a die, immediately cooling, solidifying and winding on a spool to obtain a lead wire;
s2, weaving a mesh: braiding lead wires into a grid, serging the grid by using a hot melt wire, cutting the grid into strips, and rolling the strips on a winding drum;
s3, vacuum mixing paste: vacuum stirring the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water to obtain positive lead plaster; wherein the red lead mixture consists of red lead and lead monoxide; vacuum stirring lead monoxide, sulfuric acid, a binder, sodium sulfate, a negative expansion agent and pure water to prepare negative lead plaster;
s4, plate coating: respectively coating positive lead plaster and negative lead plaster on the left side and the right side of the mesh belt, and rolling and cutting to obtain a bipolar plate coated with the lead plaster;
s5, pickling: pickling the bipolar plate coated with the lead paste at a constant speed through a pickling tank filled with dilute sulfuric acid, so that the surface of the polar plate rapidly reacts to generate a lead sulfate layer, and a wet polar plate is prepared;
s6, drying: drying the wet polar plate in a drying device to obtain a dry polar plate;
s7, assembling: stacking the dry polar plate and the AGM diaphragm on a pressure frame by using a mechanical arm, compressing, and then adding a pressure cover plate to fix the battery core;
s8, cast welding: connecting terminal wires on terminal polar plates at the positive and negative ends of the stacked and compressed battery core with a terminal seat to perform welding casting to form a common terminal casting, and preparing the cast-welded battery core;
s9, sealing: filling the cast-welded battery core into a battery box, sealing the battery box by using a terminal clamp spring or a terminal nut and an O-shaped ring, and heat-sealing the battery box and a cover together by using a heat-sealing machine to prepare an assembled heat-sealed battery;
s10, acid filling in vacuum: under the vacuum condition, evacuating air in the assembled and heat-sealed battery, injecting sulfuric acid into the battery through negative pressure difference, and sucking sulfuric acid by an AGM diaphragm in the battery to prepare an acid-filled battery;
s11, formation: the battery after acid filling is subjected to formation to activate the battery, so that an activated battery is prepared;
s12, wax filling: and filling the molten paraffin into the gaps in the activated battery from bottom to top, and washing to obtain the horizontal lead-acid storage battery.
In the step S1, the heating is to 110 ℃, the extrusion pressure is 28MPa, and the winding speed is 200mm/S.
In the step S1, the lead column is made of high tin-lead with tin content of 1.2%.
In the step S3, the sulfuric acid is sulfuric acid with specific gravity of 1.4 at 25 ℃, the adhesive is Teflon, and the red lead mixture comprises the following components in percentage by mass: 3 red lead and lead monoxide;
the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water are prepared from the following components in parts by weight: 4.01:0.41:0.65:13.1;
the weight part ratio of the lead monoxide, the sulfuric acid, the adhesive, the sodium sulfate, the negative expansion agent and the pure water is 83.33:3.50:0.42:0.67:0.83:11.25;
the vacuum is 102.5mpa.
In step S5, the specific gravity of the dilute sulfuric acid at 25 ℃ is 1.200, the temperature of the dilute sulfuric acid is 27 ℃, and the pickling time is 60 seconds.
In step S6, the drying temperature is 57 ℃ and the drying time is 6 hours.
In step S7, the compressed air pressure is 0.6MPa.
In step S10, the specific gravity of sulfuric acid at 25 ℃ is 1.220, the temperature of sulfuric acid is 24 ℃, and the vacuum condition is a vacuum pressure of 92kPa.
In step S11, the temperature of the paraffin wax is 98 ℃.
Example 2
Example 2 differs from example 1 in that:
in the step S1, heating to 95 ℃ in the lead-coated wire drawing, wherein the extrusion pressure is 23MPa, and the winding speed is 190mm/S;
in the step S1, the lead column is made of high tin-lead with tin content of 1.2%.
In the step S3, the sulfuric acid is sulfuric acid with specific gravity of 1.4 at 25 ℃, the adhesive is Teflon, and the red lead mixture comprises the following components in percentage by mass: 3 red lead and lead monoxide;
the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water are prepared from the following components in parts by weight: 4.01:0.41:0.65:13.1;
the weight part ratio of the lead monoxide, the sulfuric acid, the adhesive, the sodium sulfate, the negative expansion agent and the pure water is 83.33:3.50:0.42:0.67:0.83:11.25;
the vacuum is 90mpa.
In step S5, the specific gravity of the dilute sulfuric acid at 25 ℃ is 1.198, the temperature of the dilute sulfuric acid is 26 ℃, and the pickling time is 58 seconds.
In step S6, the drying temperature is 55 ℃ and the drying time is 6 hours.
In step S7, the compressed air pressure is 0.5MPa.
In step S10, the specific gravity of sulfuric acid at 25 ℃ is 1.218, the temperature of sulfuric acid is 22 ℃, and the vacuum condition is vacuum pressure of 90kPa.
In step S11, the temperature of the paraffin wax is 93 ℃.
Example 3
Example 3 differs from example 1 in that:
in the step S1, heating is carried out in the lead-coated wire drawing to 125 ℃, the extrusion pressure is 33MPa, and the winding speed is 210mm/S;
in the step S1, the lead column is made of high tin-lead with tin content of 1.2%.
In the step S3, the sulfuric acid is sulfuric acid with specific gravity of 1.4 at 25 ℃, the adhesive is Teflon, and the red lead mixture comprises the following components in percentage by mass: 3 red lead and lead monoxide;
the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water are prepared from the following components in parts by weight: 4.01:0.41:0.65:13.1;
the weight part ratio of the lead monoxide, the sulfuric acid, the adhesive, the sodium sulfate, the negative expansion agent and the pure water is 83.33:3.50:0.42:0.67:0.83:11.25;
the vacuum is 115mpa.
In step S5, the specific gravity of the dilute sulfuric acid at 25 ℃ is 1.202, the temperature of the dilute sulfuric acid is 28 ℃, and the pickling time is 62 seconds.
In step S6, the drying temperature is 60 ℃ and the drying time is 6 hours.
In step S7, the compressed air pressure is 0.7MPa.
In step S10, the specific gravity of sulfuric acid at 25 ℃ is 1.222, the temperature of sulfuric acid is 26 ℃, and the vacuum condition is a vacuum pressure of 94kPa.
In step S11, the temperature of the paraffin wax is 103 ℃.
Example 4
Example 4 differs from example 1 in that:
the preparation method comprises the following steps:
s1, casting a plate: melting metallic lead and a metallic additive to obtain molten metal, cooling and pulling out the molten metal to form a metal plate strip, and rolling to obtain a casting plate coil;
s2, punching: stamping the cast plate coil stock through a high-speed continuous punch press to prepare a net belt, ultrasonically cleaning the net belt, and rolling the net belt on a winding drum;
in the step S1, the melting temperature in the casting plate is 440 ℃, the cooling is realized by adopting a cooling rolling cylinder, and the thickness of the metal plate belt is 1mm.
In the step S1, the metal additives are calcium, tin, aluminum and silver, and the mass of the calcium, the tin, the aluminum and the silver are respectively 0.05 percent, 0.67 percent, 0.04 percent and 0.011 percent of the mass of the metallic lead.
Test examples
Test of the Performance of the 12V 85Ah level lead acid storage battery prepared in example 1
1. Cycle life
The test method comprises the following steps: discharge was checked at a discharge rate of 3 hours (80% dod) every 10 weeks at a rate of 3 hours until the capacity dropped to 80% of the rated capacity to end-of-life.
TABLE 1
| Examples | |
| Charging time/h | 4.5 |
| Mass specific energy Wh.kg for 3 hours -1 | 37.5 |
| Cycle life/week | 430 |
2. High current performance
The test method comprises the following steps: GB/T31486-2015
Test results: specific power is 700W/kg, maximum discharge multiplying power can reach more than 30C, and charging multiplying power is more than 10C.
3. Shock resistance
The test method comprises the following steps: GB/T18332.1-2001
Test results: no sharp change of current and abnormal voltage, no damage of shell and no leakage of electrolyte.
4. Ultra low temperature resistance
The test method comprises the following steps: GB/T18332.1-2001
Test results: the discharge capacity at the temperature of 18 ℃ below zero can reach 80% of rated value, and the discharge time at 3C is 3 minutes and is 3 times of that of the standard;
the discharge capacity at-40 ℃ can reach 53% of rated value, and the discharge time at 0.3 ℃ is 80min.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (8)
1. A preparation method of a horizontal lead-acid storage battery is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, lead-coated wire drawing: heating the lead column to a semi-liquid state, extruding by adopting a die, immediately cooling, solidifying and winding on a spool to obtain a lead wire;
or cast sheet: melting metallic lead and a metallic additive to obtain molten metal, cooling and pulling out the molten metal to form a metal plate strip, and rolling to obtain a casting plate coil;
s2, weaving a mesh: braiding lead wires into a grid, serging the grid by using a hot melt wire, cutting the grid into strips, and rolling the strips on a winding drum;
or punching: stamping the cast plate coil stock through a high-speed continuous punch press to prepare a net belt, ultrasonically cleaning the net belt, and rolling the net belt on a winding drum;
s3, vacuum mixing paste: vacuum stirring the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water to obtain positive lead plaster; wherein the red lead mixture consists of red lead and lead monoxide; vacuum stirring lead monoxide, sulfuric acid, a binder, sodium sulfate, a negative expansion agent and pure water to prepare negative lead plaster;
s4, plate coating: respectively coating positive lead plaster and negative lead plaster on the left side and the right side of the mesh belt, and rolling and cutting to obtain a bipolar plate coated with the lead plaster;
s5, pickling: pickling the bipolar plate coated with the lead paste at a constant speed through a pickling tank filled with dilute sulfuric acid, so that the surface of the polar plate rapidly reacts to generate a lead sulfate layer, and a wet polar plate is prepared;
s6, drying: drying the wet polar plate in a drying device to obtain a dry polar plate;
s7, assembling: stacking the dry polar plate and the AGM diaphragm on a pressure frame by using a mechanical arm, compressing, and then adding a pressure cover plate to fix the battery core;
s8, cast welding: connecting terminal wires on terminal polar plates at the positive and negative ends of the stacked and compressed battery core with a terminal seat to perform welding casting to form a common terminal casting, and preparing the cast-welded battery core;
s9, sealing: filling the cast-welded battery core into a battery box, sealing the battery box by using a terminal clamp spring or a terminal nut and an O-shaped ring, and heat-sealing the battery box and a cover together by using a heat-sealing machine to prepare an assembled heat-sealed battery;
s10, acid filling in vacuum: under the vacuum condition, evacuating air in the assembled and heat-sealed battery, injecting sulfuric acid into the battery through negative pressure difference, and sucking sulfuric acid by an AGM diaphragm in the battery to prepare an acid-filled battery;
s11, formation: the battery after acid filling is subjected to formation to activate the battery, so that an activated battery is prepared;
s12, wax filling: filling the molten paraffin into the gaps in the activated battery from bottom to top, and washing to obtain the horizontal lead-acid storage battery;
in the step S1, the lead column is made of high tin-lead with tin content of 1.2%; the metal additives are calcium, tin, aluminum and silver, and the mass of the calcium, the tin, the aluminum and the silver is respectively 0.04% -0.07%, 0.14% -1.2%, 0.03% -0.05% and 0.01% -0.012% of the mass of the metallic lead;
in the step S3, the sulfuric acid is sulfuric acid with the specific gravity of 1.4, the adhesive is Teflon, and the red lead mixture comprises the following components in percentage by mass: 3 red lead and lead monoxide; the red lead mixture, sulfuric acid, adhesive, sodium sulfate and pure water are prepared from the following components in parts by weight: 4.01:0.41:0.65:13.1; the weight part ratio of the lead monoxide, the sulfuric acid, the adhesive, the sodium sulfate, the negative expansion agent and the pure water is 83.33:3.50:0.42:0.67:0.83:11.25; the vacuum is 90-115mpa.
2. The method for manufacturing a horizontal lead-acid battery according to claim 1, wherein: in the step S1, heating is carried out in the lead-coated wire drawing to 110+/-15 ℃, the extrusion pressure is 28+/-5 MPa, and the winding speed is 200+/-10 mm/S; in the step S1, the melting temperature in the casting plate is 400-480 ℃, the cooling is realized by adopting a cooling rolling cylinder, and the thickness of the metal plate strip is 0.5-1.5mm.
3. The method for manufacturing a horizontal lead-acid battery according to claim 1, wherein: in the step S5, the specific gravity of the dilute sulfuric acid at 25 ℃ is 1.200+/-0.002, the temperature of the dilute sulfuric acid is 27+/-1 ℃, and the pickling time is 60+/-2 seconds.
4. The method for manufacturing a horizontal lead-acid battery according to claim 1, wherein: in the step S6, the drying temperature is 55-60 ℃ and the drying time is 6 hours.
5. The method for manufacturing a horizontal lead-acid battery according to claim 1, wherein: in the step S7, the pressure of the compressed air is 0.5-0.7MPa.
6. The method for manufacturing a horizontal lead-acid battery according to claim 1, wherein: in the step S10, the specific gravity of the sulfuric acid at 25 ℃ is 1.220+/-0.002, the temperature of the sulfuric acid is 22-26 ℃, and the vacuum condition is that the vacuum pressure is 90-94kPa.
7. The method for manufacturing a horizontal lead-acid battery according to claim 1, wherein: in the step S11, the temperature of the paraffin wax is 93-103 ℃.
8. A horizontal lead-acid battery made by the method of any one of claims 1-7.
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