CN113258075B - Light bipolar lead-acid battery grid and preparation method thereof - Google Patents
Light bipolar lead-acid battery grid and preparation method thereof Download PDFInfo
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- CN113258075B CN113258075B CN202110404935.6A CN202110404935A CN113258075B CN 113258075 B CN113258075 B CN 113258075B CN 202110404935 A CN202110404935 A CN 202110404935A CN 113258075 B CN113258075 B CN 113258075B
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/666—Composites in the form of mixed materials
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/82—Multi-step processes for manufacturing carriers for 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/029—Bipolar electrodes
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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
Abstract
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a light-weight bipolar lead-acid battery grid and a preparation method thereof. The density of the light-weight high-performance bipolar grid is 35% of that of a lead alloy grid, the specific resistance is low, meanwhile, the surface of the grid can be in electronic and physical connection with an active substance, and the gravimetric specific energy and power characteristics of the bipolar battery are improved.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a light bipolar lead-acid battery grid and a preparation method thereof.
Background
The traditional lead-acid storage battery has mature technology and low cost, but always has the defect of lower energy-specific energy, so that the application of the traditional lead-acid storage battery in certain fields is limited. Compared with the traditional battery, the bipolar lead-acid battery has the characteristics of low lead consumption, light weight, small volume, high energy density, high mass power density, low price, easy recovery and the like, and provides wide development space for the lead-acid battery to be used as a power supply of a new energy automobile, particularly a hybrid power automobile. The lead alloy grid has good conductivity, is easy to generate a corrosion layer in the curing process with active substances, improves the electronic connection and mechanical connection between the grid and the active substances, and has excellent comprehensive electrical property. The titanium oxide ceramic material reported in the literature has high cost and large resistivity of conductive plastics, and a silicon crystal matrix grid is protected by foreign technologies.
Lead acid barium (BaPbO)3) Is a functional material, and has the function of obviously improving the utilization rate and the formation efficiency of active substances. BaPbO3The conductive ceramic has metal conductive property and resistivity less than 10-2Omega cm, and has high-temperature PTC characteristic, is a novel conductive material, the application field of the material is continuously expanded, and the material relates to the fields of electronics, machinery, chemical engineering, aerospace, communication, household and the like, but the synthesis of lead acid barium, in particular to the forming process of the plate and the aspect of how to improve the combination of a lead acid barium plate grid and lead plaster, has no identifiable experience at present.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method comprises the steps of synthesizing lead-acid barium powder, sintering the lead-acid barium powder and an additive, and finally depositing a lead layer by cathode polarization, thereby realizing the characteristics of light weight and low resistance of the grid and solving the problems of forming a lead-acid barium plate and combining the grid and lead paste.
The invention relates to a light bipolar lead-acid battery grid, which comprises the following raw materials in percentage by mass:
lead-acid barium powder (BaPbO)3) 96-100% fumed Silica (SiO)2) 0-3% of rare earth fluoride and 0-1% of rare earth fluoride.
The rare earth fluoride is one or two of ytterbium fluoride or lanthanum fluoride.
The light bipolar lead-acid battery grid is composed of a substrate with the middle thickness of 0.5mm-1mm and a sealing frame with the periphery thickness of 5mm-10 mm.
The preparation method of the light bipolar lead-acid battery grid is characterized in that lead-acid barium powder, fumed silica and rare earth fluoride are sintered and pressed and then subjected to electrochemical cathode polarization treatment to obtain the light bipolar lead-acid battery grid.
Preferably, the preparation method of the light bipolar lead-acid battery grid comprises the following steps:
barium carbonate and lead tetraoxide (red lead) are adopted to synthesize lead-acid barium powder, fumed silica and rare earth fluoride are added after the barium carbonate and the lead tetraoxide (red lead) are crushed and ground, the grid is shaped by a pressure die after the uniform mixing, then sintering is carried out, cathode polarization treatment is carried out after the sintering is finished, cyclic voltammetry surface activation is carried out after the treatment is finished, and the lead-acid barium powder is prepared after water washing, anti-oxidation treatment and natural air drying.
Further preferably, the preparation method of the light bipolar lead-acid battery grid comprises the following steps:
grinding and uniformly mixing barium carbonate, lead tetraoxide (red lead), fumed silica and rare earth fluoride, shaping the grid by using a pressure die, sintering, performing cathode polarization treatment after sintering, performing cyclic voltammetry surface activation after treatment, washing with water, performing anti-oxidation treatment, and naturally drying to obtain the catalyst.
Preferably, barium carbonate and lead tetraoxide are mixed according to the molar ratio of Ba to Pb, namely 3-7 to 2-6, are ground and uniformly mixed, and react for 4-6 hours at the temperature of 900-1100 ℃ in an air atmosphere to synthesize the lead-acid barium powder.
Preferably, the clamping pressure value of the pressure die is 0.5-1MPa, and the material is stainless steel.
Preferably, the sintering temperature is 900-.
Preferably, the cathodic polarization treatment is: the pressed barium plumbate sintered plate is used as a working electrode, a pure lead plate is used as a counter electrode, 10 percent of lead nitrate and 35 percent of sulfuric acid aqueous solution are used as electrolyte, and Hg/Hg is used2SO4/H2SO4As a reference electrode, cathodic polarization is performed at a low polarization potential of less than-1.25V (preferably-1.1V) by a potentiostatic method 5-7h, and then carrying out cathodic polarization for 1-3h at a high polarization potential of more than-1.25V (-1.3V), thus completing the polarization.
Cyclic voltammetric surface activation, potential range: -0.6V to-1.65V, a scanning speed of 10mv/s, an electrolyte density of 1.28g/ml, a temperature of 25 ℃ and a scanning period of 300 times.
The invention uses lead tetraoxide and barium carbonate as main materials for synthesizing the lead-acid barium, thereby not only obviously reducing the lead consumption of the battery and improving the mass specific energy of the battery, but also realizing the mass production of plates.
The addition of the fumed silica can improve the porosity of the electrode, and the use of the rare earth fluoride can improve the hydrogen evolution potential of the negative electrode side and reduce the hydrogen evolution quantity.
When the cathode polarization treatment is carried out, the plate is subjected to cathode polarization by using a low polarization potential of-1.1V, so that a compact lead deposition layer is generated on the surface of the electrode, the corrosion resistance of the electrode is improved, and then a loose and porous lead deposition layer is generated on the surface of the electrode by using high polarization of-1.3V, so that the subsequent electrode curing process is facilitated, and the combination of an electrode active substance and the plate is enhanced.
The invention uses cyclic voltammetry surface activation, further increases the surface activity of the plate, improves the electronic connection and mechanical connection between the active substance and the plate, and has important effects on improving the conductivity, power performance and service life of the battery.
Compared with the prior art, the invention has the following beneficial effects:
the density of the light high-performance bipolar grid provided by the invention is 35% of that of a lead alloy grid, the resistivity is low, meanwhile, the surface of the grid can realize electronic and physical connection with an active substance, and the gravimetric specific energy and power characteristics of a bipolar battery are improved.
Drawings
FIG. 1 is a schematic structural view of a bipolar grid according to the present invention;
in the figure: 1. a base plate; 2. and sealing the frame.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Weighing 1460g of BaCO3And 1180g of Pb3O4The preparation method comprises the steps of weighing 60g of fumed silica and 20g of ytterbium fluoride at the same time, grinding and mixing for 10min by using a planetary ball mill at 1000 rpm, putting the powder into a die, wherein the size of an inner cavity of the die is 100mm multiplied by 100mm, the thickness of an inner cavity of a substrate is 0.5mm, the thickness of a frame is 10mm, the die closing pressure value is 0.5MPa, the material is stainless steel, fixing the powder, putting the powder into a muffle furnace, and keeping the temperature in the air atmosphere for 1000 ℃ for 5 h. And opening the die after natural cooling, taking out the plate, and removing burrs.
The pressed barium plumbate sintered plate is used as a working electrode, a pure lead plate is used as a counter electrode, 10 percent of lead nitrate and 35 percent of sulfuric acid aqueous solution are used as electrolyte, and Hg/Hg is used2SO4/H2SO4Performing cathodic polarization for 6h at-1.1V and 2h at-1.3V by a potentiostatic method as a reference electrode, and performing cyclic voltammetry surface activation after polarization is completed, wherein the potential range is as follows: -0.6V to-1.65V, a scanning speed of 10mv/s, an electrolyte density of 1.28g/ml, a temperature of 25 ℃ and a scanning period of 300 times. Thoroughly washing with water for 10h, performing oxidation prevention treatment (soaking in anhydrous ethanol for 2h, and soaking in diethyl ether for 10min), and naturally air drying.
Preparing positive pole lead plaster, wherein the formula comprises 40kg of lead powder, 10kg of red lead, 5000ml of sulfuric acid (1.4g/ml), 3000g of deionized water and 10g of polypropylene fiber, and preparing for 25min by a vacuum paste mixer to obtain the apparent density of 4.3g/cm3The positive electrode lead paste of (1) was coated on the positive electrode side of the substrate 1 at a coating thickness of 2mm and a weight of 80 g.
Preparing a negative pole lead plaster, wherein the formula comprises 50kg of lead powder, 4500ml of sulfuric acid (1.4g/ml), 3100g of deionized water and 10g of polypropylene fiber, and preparing for 25min by a vacuum paste mixer to obtain an apparent density of 4.25g/cm3The positive electrode lead paste of (1) was coated on the negative electrode side of the substrate 1 to a thickness of 1.5mm and a weight of 60 g.
Curing and drying the electrode coated with the positive/negative lead paste, wherein the method comprises the following steps:
the first step is as follows: 100% humidity, 60 ℃, 2 h;
the second step is that: 100% humidity, 50 ℃, 6 h;
the third step: 80% humidity, 50 ℃, 6 h;
the fourth step: 50% humidity, 60 ℃, 6 h;
the fifth step: 60 ℃ for 24 h.
After the operation is finished, 10 bipolar electrodes, 1 positive plate, 1 negative plate and 10 AGM glass fiber separators with the thickness of 2mm are assembled, the bipolar plates are sealed and fixed through sealing frames by using sealant to form the 4Ah/24V bipolar lead-acid storage battery, and acid adding holes are reserved on the upper portion of each separator on the upper portion of the battery. And (3) installing a temporary funnel at the acid adding hole, filling 1.25g/ml sulfuric acid electrolyte, standing for 1h, and forming the battery. And after the battery is formed for 72 hours, sucking out redundant electrolyte, removing the acid adding funnel, and installing a safety valve at the liquid injection hole to obtain a sample battery to be tested.
The test method comprises the following steps:
(1) weighing: the weight of the battery after the safety valve was installed was recorded, and the mass specific energy was calculated from the initial 2hr discharge capacity.
(2)2hr capacity test: the discharge was carried out at a current of 2A, and the discharge end voltage was 1.75V, and the discharge time was recorded.
(3)2C capacity test: the discharge was carried out at a current of 8A, and the discharge end voltage was 1.30V, and the discharge time was recorded.
(4)4C capacity test: the discharge was carried out at a current of 16A, and the discharge end voltage was 1.30V, and the discharge time was recorded.
(5) And (3) cycle testing: and (3) charging procedure: 1A, 2.5V constant current voltage limiting for 6h, 0.3A, 1 h;
(6) and (3) resistance measurement: and testing the internal resistance of the battery by using the EIS constant current function of the electrochemical workstation.
And (3) discharging procedure: 2A is discharged to 1.75V;
when the discharge time is less than 84min, the battery is defined as dead.
The equivalent comparison is carried out with the 12V/10Ah battery of the traditional electric bicycle.
The test results are shown in Table 1.
TABLE 1 test results of sample and reference cells
| Battery with a battery cell | Internal resistance of | 2hr capacity | Specific energy of mass | 2C discharge | 4C discharge | Life span |
| Sample cell | 7.8mΩ | 113.3％ | 45wh/kg | 41min | 15min | 556 |
| Reference cell | 12mΩ | 112.4％ | 35wh/kg | 17min | 3min | 489 |
Example 2
Weighing 1460g of BaCO3And 1180g of Pb3O4The preparation method comprises the steps of weighing 60g of fumed silica and 20g of ytterbium fluoride at the same time, grinding and mixing for 10min by using a planetary ball mill at 1000 rpm, putting the powder into a mold, wherein the size of an inner cavity of the mold is 150mm multiplied by 150mm, the thickness of an inner cavity of a substrate is 1mm, the thickness of a frame is 10mm, the mold closing pressure value is 0.8Mpa, the material is stainless steel, fixing the powder, putting the powder into a muffle furnace, and keeping the temperature in the air atmosphere for 1000 ℃ for 6 h. And opening the die after natural cooling, taking out the plate, and removing burrs.
The pressed barium plumbate sintered plate is used as a working electrode, a pure lead plate is used as a counter electrode, 10 percent of lead nitrate and 35 percent of sulfuric acid aqueous solution are used as electrolyte, and Hg/Hg is used2SO4/H2SO4Performing cathodic polarization for 6h at-1.1V and 2h at-1.3V by a potentiostatic method as a reference electrode, and performing cyclic voltammetry surface activation after polarization is completed, wherein the potential range is as follows: -0.6V to-1.65V, a scanning speed of 10mv/s, an electrolyte density of 1.28g/ml, a temperature of 25 ℃ and a scanning period of 300 times. Thoroughly washing with water for 10h, performing oxidation prevention treatment (soaking in anhydrous ethanol for 2h, and soaking in diethyl ether for 10min), and naturally air drying.
Preparing positive pole lead plaster with the formula of 40kg of lead powder, 10kg of red lead, 5000ml of sulfuric acid (1.4g/ml), 3000g of deionized water and 10g of polypropylene fiber, and preparing for 25min by using a vacuum paste mixer to obtain the lead plaster with the apparent density of 4.28g/cm3The positive electrode lead paste of (1) was coated on the positive electrode side of the substrate 1 at a coating thickness of 2mm and a weight of 190 g.
Preparing a negative pole lead plaster, wherein the formula comprises 50kg of lead powder, 4500ml of sulfuric acid (1.4g/ml), 3100g of deionized water and 10g of polypropylene fiber, and preparing for 25min by a vacuum paste mixer to obtain an apparent density of 4.26g/cm3The positive electrode lead paste of (1) was coated on the negative electrode side of the substrate 1 to a thickness of 1.5mm and a weight of 140 g.
Curing and drying the electrode coated with the positive/negative lead paste, wherein the method comprises the following steps:
the first step is as follows: 100% humidity, 60 ℃, 2 h;
the second step is that: 100% humidity, 50 ℃, 6 h;
the third step: humidity of 80%, 50 ℃, 6 h;
the fourth step: 50% humidity, 60 ℃, 6 h;
the fifth step: 60 ℃ for 24 h.
After the operation is finished, 10 bipolar electrodes, 1 positive plate, 1 negative plate and 10 AGM glass fiber separators with the thickness of 2mm are assembled, the bipolar plates are sealed and fixed through sealing frames by using sealant to form the 15Ah/24V bipolar lead-acid storage battery, and acid adding holes are reserved on the upper portion of each separator on the upper portion of the battery. And (3) installing a temporary funnel at the acid adding hole, filling 1.25g/ml sulfuric acid electrolyte, standing for 1h, and forming the battery. And after the battery is formed for 72 hours, sucking out redundant electrolyte, removing the acid adding funnel, and installing a safety valve at the liquid injection hole to obtain a sample battery to be tested.
The test method comprises the following steps: (1) weighing: the weight of the battery after the safety valve was installed was recorded, and the mass specific energy was calculated from the initial 2hr discharge capacity. (2)2hr capacity test: the discharge was carried out at a current of 7.5A, and the discharge end voltage was 1.75V, and the discharge time was recorded. (3)2C capacity test: the discharge was carried out at a current of 30A, and the discharge end voltage was 1.30V, and the discharge time was recorded. (4) And (3) cycle testing: and (3) charging procedure: 3.5A, 2.5V constant current voltage limiting 6h, 1.5A, 1 h; (5) and (3) weight loss test: the difference in weight of the battery after formation and after 300 cycles was measured.
And (3) discharging procedure: 7.5A to 1.75V;
when the discharge time is less than 84min, the battery is defined as dead.
The equivalent comparison is carried out with the 12V/10Ah battery of the traditional electric bicycle.
The test results are shown in Table 2.
TABLE 2 test results of sample and reference cells
| Battery with a battery cell | 2hr | Specific energy of mass | 2C discharge time | Number of cycles | Cell weight loss |
| Sample cell | 115.3％ | 46wh/kg | 38min | 426 | 4.5％ |
| Reference cell | 112.4％ | 35wh/kg | 17min | 389 | 8.5％ |
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (8)
1. A light bipolar lead-acid battery grid is characterized in that: the material comprises the following raw materials in percentage by mass:
96-100% of lead-acid barium powder, 0-3% of fumed silica and 0-1% of rare earth fluoride;
the preparation method of the light bipolar lead-acid battery grid is characterized in that lead-acid barium powder, fumed silica and rare earth fluoride are sintered and pressed and then subjected to electrochemical cathode polarization treatment to obtain the light bipolar lead-acid battery grid;
the method comprises the following steps:
lead acid barium powder is synthesized by lead tetraoxide and barium carbonate, fumed silica and rare earth fluoride are added after the lead acid barium powder is crushed and ground, the grid is shaped by a pressure die after the lead acid barium powder and the barium carbonate are uniformly mixed, then sintering is carried out, cathode polarization treatment is carried out after the sintering is finished, cyclic voltammetry surface activation is carried out after the treatment is finished, and the lead acid barium powder is prepared after water washing, anti-oxidation treatment and natural air drying.
2. The lightweight bipolar lead acid battery grid of claim 1, wherein: the rare earth fluoride is one or two of ytterbium fluoride or lanthanum fluoride.
3. The lightweight bipolar lead acid battery grid of claim 1, wherein: consists of a substrate with the middle thickness of 0.5mm-1mm and a sealing frame with the periphery thickness of 5mm-10 mm.
4. The lightweight bipolar lead acid battery grid of claim 1, wherein: according to the molar ratio, barium carbonate and lead tetroxide are mixed according to the proportion of Ba: Pb =3-7:2-6, ground and mixed evenly, and reacted for 4-6 hours at the temperature of 900-1100 ℃ in the air atmosphere to synthesize the lead acid barium powder.
5. The lightweight bipolar lead acid battery grid of claim 1, wherein: the die closing pressure value of the pressure die is 0.5-1 MPa.
6. The lightweight bipolar lead acid battery grid of claim 1, wherein: the sintering temperature is 900-1100 ℃, and the time is 4-6 h.
7. The lightweight bipolar lead acid battery grid of claim 1, wherein: cathodically polarized to: the pressed barium plumbate sintered plate is used as a working electrode, a pure lead plate is used as a counter electrode, 10 percent of lead nitrate and 35 percent of sulfuric acid aqueous solution are used as electrolyte, and Hg/Hg is used2SO4/H2SO4And (3) as a reference electrode, performing cathodic polarization for 5-7h at a low polarization potential of less than-1.25V by a potentiostatic method, and performing cathodic polarization for 1-3h at a high polarization potential of more than-1.25V to finish polarization.
8. The lightweight bipolar lead acid battery grid of claim 1, wherein: cyclic voltammetric surface activation, potential range: -0.6V to-1.65V, a scanning speed of 10mv/s, an electrolyte density of 1.28g/ml, a temperature of 25 ℃ and a scanning period of 300 times.
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| JPH0817436A (en) * | 1994-06-29 | 1996-01-19 | Shin Kobe Electric Mach Co Ltd | Manufacture of collector for lead acid battery |
| JPH0837001A (en) * | 1994-07-26 | 1996-02-06 | Shin Kobe Electric Mach Co Ltd | Positive electrode plate for lead-acid battery and manufacture of the electrode plate |
| JP4613550B2 (en) * | 2004-08-26 | 2011-01-19 | 新神戸電機株式会社 | Lead-acid battery current collector and lead-acid battery |
| CN110336038B (en) * | 2019-04-12 | 2020-07-24 | 淄博火炬能源有限责任公司 | Bipolar battery plate and preparation method thereof |
| CN111599991A (en) * | 2019-06-24 | 2020-08-28 | 骆驼集团华中蓄电池有限公司 | Maintenance-free starting lead-acid storage battery with long service life and high specific energy and production method thereof |
| CN111697201B (en) * | 2019-08-12 | 2023-04-11 | 福州伯瑞电源科技有限公司 | Production of high-power lead-acid storage battery positive plate |
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