CN111554884B - Deep-cycle long-life lead-acid storage battery and charging method - Google Patents

Deep-cycle long-life lead-acid storage battery and charging method Download PDF

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CN111554884B
CN111554884B CN202010202050.3A CN202010202050A CN111554884B CN 111554884 B CN111554884 B CN 111554884B CN 202010202050 A CN202010202050 A CN 202010202050A CN 111554884 B CN111554884 B CN 111554884B
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lead
battery
charging
plate
deep
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CN111554884A (en
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韩振
苑景春
陈加成
蒋岚
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Zhejiang Narada Power Source Co Ltd
Hangzhou Nandu Power Technology Co Ltd
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Zhejiang Narada Power Source Co Ltd
Hangzhou Nandu Power Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • H01M10/08Selection of materials as electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • H01M10/12Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • H01M10/12Construction or manufacture
    • H01M10/128Processes for forming or storing electrodes in the battery container
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • H01M10/446Initial charging measures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/14Electrodes for lead-acid accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463Separators, membranes or diaphragms characterised by their shape
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a deep-cycle long-life lead-acid storage battery and a charging method. The deep-cycle long-life lead-acid storage battery comprises a positive plate coated with lead paste and having an aspect ratio of (0.8-1.6):1, and a negative plate coated with lead paste and having an aspect ratio of (0.8-1.6):1, wherein the positive plate and the negative plate are separated by a separator, and the thickness of the separator ranges from 1.6mm to 1.8 mm. The charging method comprises two steps: when charging is started, constant current charging at 0.25-0.5C is adopted; then charging at constant voltage of 2.30V-2.35V/cell, and limiting charging time for 4h-8 h.

Description

Deep-cycle long-life lead-acid storage battery and charging method
Technical Field
The invention relates to the technical field of batteries, in particular to a deep-cycle long-life lead-acid storage battery and a charging method.
Background
The lead-acid storage battery is the battery with the largest market share and the widest application range in chemical secondary batteries, and particularly in the application fields of starting, large-scale energy storage and the like, the lead-acid storage battery is difficult to replace by other novel batteries for a long time. The lead-acid storage battery has the advantages of low price, mature technology, excellent high and low temperature performance, stability, reliability, high safety, good resource reusability and the like, and has obvious market competitive advantage. Compared with other battery metal materials, the lead resource is rich, the lead reserve and the secondary lead ensure that the sustainable development of the lead-acid storage battery industry has a relatively long age, and the lead-acid storage battery is applied in large quantities and cannot cause the shortage of the lead resource in a long time.
However, lead-acid batteries have different cycle times depending on the depth of discharge, and generally, the lower the depth of discharge, the smaller the cycle times, and the number of deep cycles (full charge and discharge) of power batteries in the market is generally about 300. The structure of a lead-acid storage battery commonly available on the market is shown in figure 1. And at present, the lead-acid storage battery generally adopts a three-stage charging method, constant current charging is adopted at the beginning and the end of charging, and constant voltage charging (generally 2.45V/cell) is adopted as an intermediate step. When the current decays to a predetermined value, the second phase is switched to the third phase. Although this method can reduce the amount of exhaust gas, it requires ten or more hours for each full charge, which is not favorable for heat dissipation of the battery, nor is it in accordance with the requirement for rapid charging.
Disclosure of Invention
The invention aims to provide a deep-cycle long-life lead-acid storage battery and a charging method.
In order to solve the technical problem, the deep-cycle long-life lead-acid storage battery provided by the invention comprises a positive plate coated with lead paste and having an aspect ratio of (0.8-1.6):1 and a negative plate coated with lead paste and having an aspect ratio of (0.8-1.6):1, wherein the positive plate and the negative plate are separated by a separator, and the thickness of the separator ranges from 1.6mm to 1.8 mm.
Optionally, the aspect ratio of the positive plate is (0.9-1):1, and the aspect ratio of the negative plate is equal to that of the positive plate.
Optionally, the thickness of the separator ranges from 1.7mm to 1.75 mm.
Optionally, the ratio of the thickness of the lead paste on the positive plate to the thickness of the lead paste on the negative plate is 1.5-1.4.
Optionally, the deep-cycle long-life lead-acid storage battery also comprises a battery active acid density of (1.20-1.25) g/cm3The electrolyte of (1). Preferably, the cell activating acid density is 1.22-1.24g/cm3
Optionally, the positive plate and the negative plate in the deep-cycle long-life lead-acid storage battery are both horizontally arranged.
Optionally, the deep-cycle long-life lead-acid battery has a plurality of battery slots, the positive plate and the negative plate are distributed in each battery slot, and the height of each battery slot is smaller than the length and width of the positive plate.
Optionally, when n battery containers are arranged in the deep-cycle long-life lead-acid storage battery in the height direction of the battery containers, the height of each battery container is 1/n of the length of the positive plate.
Optionally, the positive plate is semicircular, and the shape of the negative plate is the same as that of the positive plate.
The invention also provides a charging method, which is used in the deep-cycle long-life lead-acid storage battery and comprises the following two steps:
when charging is started, constant current charging at 0.25-0.5C is adopted;
then charging at constant voltage of 2.30V-2.35V/cell, and limiting charging time for 4h-8 h.
In conclusion, the deep-cycle long-life lead-acid storage battery provided by the invention has the advantages that the thickness of the partition plate is increased by adjusting the length-width ratio of the polar plate, and the charging cycle life of the battery is greatly prolonged.
Furthermore, by reducing the acid adding density, the positive and negative plates are horizontally arranged, so that the charging cycle life of the battery can be further prolonged.
Moreover, the two-step charging method provided by the invention can greatly prolong the charging cycle life of the battery.
Drawings
FIG. 1 is a schematic diagram of a conventional lead-acid battery;
FIG. 2 is a schematic diagram of a deep cycle long life lead acid battery provided by an embodiment of the present invention;
FIG. 3 is a cycle life curve for a deep cycle long life lead acid battery provided by various embodiments of the present invention;
fig. 4 is a schematic diagram of the shape of the positive and negative electrode plates of a deep cycle long life lead acid battery of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The long life referred to in the present invention means that the number of deep cycles (complete charge and discharge) is 500 or more. All ranges in this disclosure are inclusive of the endpoints, and both above and below in this disclosure are inclusive of the instant numbers.
Please refer to fig. 1. The first and second comparative examples of the present invention each used an existing battery, with positive and negative plates both vertically disposed and both elongated, with aspect ratios of both positive and negative plates greater than 1.5. The activated acid density of the battery is more than 1.25g/cm3The thickness of the clapboard is less than 1.6 mm.
Specifically, the lead-acid battery of comparative example one employed a common charging method: the first step is as follows: charging at constant current of 0.15 ℃ until the voltage reaches 2.45V/single lattice rotation step; step two, 2.45V/single cell constant voltage charging, and turning to step when the current is reduced to 0.02C; the third step: 0.02C current, voltage 2.30V/cell, and charging is finished for 4 h.
The lead-acid battery of comparative example two employs a two-step charging method: the first step is as follows: charging at constant current of 0.30 ℃ until the voltage reaches 2.45V/single lattice rotation step; the second step is that: 2.45V/cell constant voltage charging (initial current is 0.30C), no matter what value the current drops to, the limit charging time 6h ends.
Referring to fig. 2, the positive plate and the negative plate of the long-life cycle lead-acid battery provided in the first embodiment to the fourth embodiment of the present invention are horizontally disposed. The positive and negative polar plates are all rectangular. However, the present invention is not limited to the horizontal arrangement of the positive and negative plates, and in other embodiments, the positive and negative plates may also be arranged vertically.
The deep-cycle long-life lead-acid storage battery provided by the invention is provided with six battery containers 3, the six battery containers 3 are arranged in two rows and three rows, the positive plates and the negative plates are distributed in the six battery containers 3, the height H of each battery container 3 is smaller than the length A and the width B of each positive plate, and in other embodiments, the height H of each battery container is preferably one third of the length A of each positive plate. The external positive and negative electrode ports 2 of the storage battery are arranged at the top of the storage battery.
Example one
The deep-circulation long-life lead-acid storage battery is characterized in that the length-width ratio of positive and negative electrode plates 1 of the battery is 0.90, the thickness of lead paste on a positive plate and the thickness of lead paste on a negative plate are 0.3mm and 0.2mm respectively, the positive plate and the negative plate are separated by a partition plate, the thickness of the partition plate is 1.75mm, and the deep-circulation long-life lead-acid storage battery also comprises a battery activated acid with the density of 1.22g/cm3The electrolyte of (1).
The lead-acid storage battery adopts a two-step charging method: the charging current of the battery is 0.3C, the voltage is 2.35V/cell, and the charging time is limited to 6 h.
The lead-acid storage battery prepared and used by the method has qualified initial performance, the charging time is shortened to 6 hours, the cycle life reaches more than 1000 times, and the specific experimental result is shown in figure 3.
Example two
The deep-circulation long-life lead-acid storage battery is characterized in that the length-width ratio of positive and negative electrode plates 1 of the battery is 1.6, the thickness of lead paste on a positive plate and the thickness of lead paste on a negative plate are 0.4mm and 0.3mm respectively, the positive plate and the negative plate are separated by a partition plate, the thickness of the partition plate is 1.60mm, and the deep-circulation long-life lead-acid storage battery also comprises a battery activated acid with the density of 1.20g/cm3The electrolyte of (1).
The lead-acid storage battery adopts a two-step charging method: the charging current of the battery is 0.5C, the voltage is 2.40V/cell, and the charging time is limited to 4 h.
The lead-acid storage battery prepared and used by the method has qualified initial performance, the charging time is shortened to 4h, the cycle life reaches more than 600 times, and the specific experimental result is shown in figure 3.
EXAMPLE III
The deep-circulation long-life lead-acid storage battery is characterized in that the length-width ratio of positive and negative electrode plates 1 of the battery is 0.80, the thickness of lead paste on a positive plate and the thickness of lead paste on a negative plate are 0.25mm and 0.2mm respectively, the positive plate and the negative plate are separated by a partition plate, the thickness of the partition plate is 1.80mm, and the deep-circulation long-life lead-acid storage battery also comprises a battery activated acid with the density of 1.25g/cm3The electrolyte of (1).
The lead-acid storage battery adopts a two-step charging method: the charging current of the battery is 0.25C, the voltage is 2.30V/cell, and the charging time is limited to 8 h.
The lead-acid storage battery prepared and used by the method has qualified initial performance, the charging time is shortened to 4h, the cycle life reaches more than 600 times, and the specific experimental result is shown in figure 3.
Example four
The deep-circulation long-life lead-acid storage battery is characterized in that the length-width ratio of positive and negative electrode plates 1 of the battery is 1.0, the thickness of lead paste on a positive plate and the thickness of lead paste on a negative plate are 0.35mm and 0.25mm respectively, the positive plate and the negative plate are separated by a partition plate, the thickness of the partition plate is 1.70mm, and the deep-circulation long-life lead-acid storage battery also comprises a battery activated acid with the density of 1.24g/cm3The electrolyte of (1).
The lead-acid storage battery adopts a two-step charging method: the charging current of the battery is 0.4C, the voltage is 2.35V/cell, and the charging time is limited to 5 h.
The lead-acid storage battery prepared and used by the method has qualified initial performance, the charging time is shortened to 4h, the cycle life reaches more than 800 times, and the specific experimental result is shown in figure 3.
Comparing the experimental data of the first to fourth examples and the first to second comparative examples, it can be seen that the battery and the usage method in the first example are the best, the charging cycle life reaches more than 1000 times, the lead-acid battery and the usage method in the fourth example are the next, the charging cycle life reaches more than 800 times, the lead-acid battery and the usage method in the first comparative example are the worst, and the charging cycle life is only about 300 times.
Therefore, when the length-width ratio of the positive electrode plate and the negative electrode plate of the lead-acid storage battery is in the range of (0.8-1.6):1, the cycle life of the battery can be greatly prolonged. Preferably, the effect is optimal when the length-width ratio range of the positive electrode plate and the negative electrode plate is (0.9-1): 1.
The ratio of the thickness of the lead paste on the positive plate to the thickness of the lead paste on the negative plate is set according to the aspect ratio of the positive plate to the negative plate, and when the aspect ratio of the positive plate to the negative plate is closer to 1, the ratio of the thickness of the lead paste on the positive plate to the thickness of the lead paste on the negative plate is smaller.
And, lead acid battery that the side was put and is used (positive plate and negative plate equal level setting promptly) compare the lead acid battery of vertical setting, have better charge cycle life, this is because the battery jar of every lead acid battery is airtight, the height that normally vertically places utmost point crowd is exactly the height of polar plate, and the height that the utmost point crowd was put to the side is the width of battery jar (the width of former utmost point crowd, namely the thickness of polar plate plus the thickness of compression back baffle) and is less than the height of former utmost point crowd far away, the reduction of utmost point crowd height can effectively reduce the layering of acid, make the upper and lower acid density keep unanimous, improve the utilization ratio of lower part polar plate, thereby increase the cycle life of battery.
EXAMPLE five
The embodiment also provides a deep-cycle long-life lead-acid storage battery, and except that the shapes of the positive and negative electrode plates are different from those in the fourth embodiment, the rest parts are completely consistent. The positive and negative electrode plates in this embodiment are semicircular, as shown in fig. 4. In other embodiments, the positive and negative electrode plates may also be a combination of a semicircular shape and a rectangular shape, as shown in fig. 4, and the corresponding battery cases are also arranged according to the shapes of the positive and negative electrode plates, so that the circular characteristics are effectively utilized, the uniformity of electron migration can be increased, and the distances from ions in the electrolyte to the electrode plates are approximately equal. And, the contained position of battery does not need the edges and corners, can make things convenient for the extraction of battery, and the battery case bottom also does not have the edges and corners, can change the shortcoming that the edges and corners position easily takes place the weeping.
The lead-acid storage battery prepared and used by the method has qualified initial performance, the charging time is shortened to 6 hours, and the cycle life reaches more than 1030 times.
It will be understood by those skilled in the art that in the present disclosure, the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships that are based on those shown in the drawings, which are merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated, and thus the above-described terms should not be construed as limiting the invention.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. A deep cycle long life lead acid battery comprising:
a positive plate coated with a lead paste and having an aspect ratio of 0.8-0.9:1,
a negative plate coated with a lead paste and having an aspect ratio of 0.8-0.9:1,
the positive plate and the negative plate are separated by a separator, and the thickness of the separator ranges from 1.6mm to 1.8 mm;
the positive plate and the negative plate in the deep-cycle long-life lead-acid storage battery are both horizontally arranged;
the ratio of the thickness of the lead paste on the positive plate to the thickness of the lead paste on the negative plate is 1.4-1.5;
the length-width ratio of the negative plate is equal to that of the positive plate, the thickness ratio of the lead paste on the positive plate to the thickness ratio of the lead paste on the negative plate is set according to the length-width ratios of the positive plate and the negative plate, and when the length-width ratios of the positive plate and the negative plate are closer to 1, the ratio of the thickness of the lead paste on the positive plate to the thickness of the lead paste on the negative plate is smaller.
2. The deep cycle long life lead acid battery of claim 1 wherein said separator has a thickness in the range of 1.7mm to 1.75 mm.
3. The deep-cycle long-life lead-acid battery of any one of claims 1 to 2, further comprising a battery active acid density of 1.20g/cm3-1.25g/cm3The electrolyte of (1).
4. The deep cycle long life lead acid battery of any one of claims 1 to 2, wherein said positive plate is semi-circular and said negative plate is the same shape as said positive plate.
5. The deep cycle long life lead acid battery of any one of claims 1 to 2, wherein said positive plate is a combination of semicircular and rectangular in shape, and said negative plate is the same shape as said positive plate.
6. The deep-cycle long-life lead-acid battery of any one of claims 1 to 2, wherein the deep-cycle long-life lead-acid battery has a plurality of battery wells, the positive and negative plates being distributed within each battery well, the height of each battery well being less than the length and width of the positive plate; when n battery grooves are distributed in the height direction of the battery grooves, the height of each battery groove is 1/n of the length of the positive plate.
7. A deep cycle long life lead acid battery as claimed in any one of claims 1 to 2, wherein the aspect ratio of the positive and negative plates is 0.9, the thickness of the paste on the positive and negative plates is 0.3mm and 0.2mm respectively, and the thickness of the separator is 1.75 mm.
8. A charging method for use in a deep cycle long life lead-acid battery as claimed in any one of claims 1 to 7, said charging method being divided into two steps:
when charging is started, constant current charging at 0.25-0.5C is adopted;
then charging at constant voltage of 2.30V-2.35V/cell, and limiting charging time for 4h-8 h.
9. The charging method of claim 8, comprising:
when charging is started, constant current charging at 0.30-0.4C is adopted;
then the charging is carried out at constant voltage of 2.35V/unit cell, and the charging time is limited to 5h-6 h.
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