Positive and negative electrodes of high-humidity-resistant high-low-temperature-alternating long-service-life lead-acid storage battery and preparation method and application of positive and negative electrodes

Abstract

According to the positive electrode and the negative electrode of the high-humidity high-low-temperature-alternating-resistant long-service-life lead-acid storage battery and the preparation method and application of the positive electrode and the negative electrode, high-humidity high-low-temperature alternating can be resisted, after a high-humidity high-low-temperature alternating experiment, the battery capacity preservation rate is 60% or above, the capacity recovery rate is larger than or equal to 95%, and the positive electrode and the negative electrode are suitable for being used in the environment with the humidity being 85% and the large alternating temperature difference of minus 40 DEG C and 65 DEG C.

Description

Technical Field

[0001] This invention relates to the positive and negative electrode formulations of lead-acid batteries, and more particularly to the positive and negative electrodes of a long-life lead-acid battery resistant to high humidity and high and low temperature alternation, as well as their preparation method and application. Background Technology

[0002] The photovoltaic (PV) energy storage market is currently vast, with numerous PV energy storage systems installed in deserts worldwide. Due to the extreme temperature differences in deserts (around -40°C at night and around 65°C during the day), a temperature difference of nearly 105°C, stringent requirements are placed on the lead-acid batteries used. Lead-acid batteries are a core component of PV energy storage, with substantial global usage. They operate in environments with alternating humidity levels of 85%, temperatures ranging from -40°C to 65°C, driving PV modules, tracking sunlight and wind resistance to maximize power generation and protect the modules from wind. Lead-acid batteries used in environments with large temperature fluctuations require reasonable design, strict and precise process control, and a certain lifespan. Currently, lead-acid batteries primarily improve low-temperature performance by adding organic expanding agents, mainly lignin, to the negative electrode lead paste. While these organic expanding agents can improve discharge performance in low-temperature environments to some extent, the improvement is limited in environments with large temperature differences between -40°C and 65°C, failing to meet the required performance.

[0003] For example, CN117423830A, "A positive and negative electrode paste for an ultra-low temperature lead-acid battery, its preparation method, and a lead-acid battery containing the same," although it can achieve high capacity and relatively stable capacity at -43℃, and can start and ignite at a high current at -43℃, and has good charging acceptance at -43℃, it only solves the problem of use in ultra-low temperature environments with rapid temperature alternation between -40℃ and 65℃. It does not solve the problem of use in high humidity and high temperature environments, and in particular, it is not suitable for "high humidity and high and low temperature alternation applications."

[0004] CN109904448A describes a super-energy polymer lead-acid battery electrode plate paste. Although its operating temperature range is as high as -65℃ to 90℃, it only solves the problem of use in low-temperature and high-temperature environments, such as high-humidity environments and environments with rapid temperature changes between -40℃ and 65℃. It does not solve the problem of use in high-humidity environments and environments with rapid temperature changes between high and low temperatures. In particular, it is not suitable for "high-humidity and high-low temperature alternation". Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a positive and negative electrode formulation for a long-life lead-acid battery resistant to high humidity and alternating high and low temperatures, along with its preparation method and application. This effectively solves the problem that lead-acid batteries need to provide power to drive photovoltaic modules to track sunlight and overcome wind resistance under alternating environments of 85% humidity, -40°C, and 65°C, maximizing photovoltaic power generation, while the cycle life of lead-acid batteries rapidly declines under these conditions.

[0006] The object of this invention is achieved in the following manner: The positive and negative electrodes of a long-life lead-acid battery resistant to high humidity and high / low temperature alternation, by weight... The positive electrode comprises the following raw materials: 1000 parts lead powder, 105-125 parts deionized water, 85-105 parts 51% sulfuric acid solution (by mass percentage), 0.6-1.0 parts ultra-strong fiber, 1.5-3.5 parts colloidal graphite, 0.5-1.5 parts bismuth trioxide, 0.5-2 parts carbon fiber, 10-20 parts tetrabasic lead sulfate, and 0.5-1.5 parts stannous sulfate. The negative electrode contains the following raw materials: 1000 parts lead powder, 95-115 parts deionized water, 75-95 parts 51% sulfuric acid solution (by mass percentage), 0.6-1.0 parts super-strong fiber, 0.5-2 parts carbon fiber, 1-6 parts acetylene black, 1.5-4 parts lignin, 2-5 parts humic acid, 8-14 parts barium sulfate, and 2-5 parts carbon black.

[0007] Colloidal graphite has a particle size of less than 30 micrometers and a carbon content of more than 99.95%.

[0008] Super-strong fiber is a type of super-strong polyester fiber. The fineness of a single super-strong polyester fiber is less than 2D, the length is 2-4mm, and the breaking strength is greater than or equal to 8CN / dtex.

[0009] The fineness of a single carbon fiber is less than 2D, the length is 2-4mm, and the resistivity is less than 17 microohms·meter.

[0010] A method for preparing the positive and negative electrodes of a long-life lead-acid battery resistant to high humidity and high / low temperature alternation. The preparation of the positive electrode includes the following steps: Step 1: Material preparation: Weigh the raw materials for the positive electrode: 1000 parts lead powder, 105-125 parts deionized water, 85-105 parts 51% sulfuric acid solution (by mass percentage), 0.6-1.0 parts super-strong fiber, 1.5-3.5 parts colloidal graphite, 0.5-1.5 parts bismuth trioxide, 0.5-2 parts carbon fiber, 10-20 parts tetrabasic lead sulfate, and 0.5-1.5 parts stannous sulfate. Step 2: Dry mixing: Mix all raw materials except for deionized water and sulfuric acid, and stir until homogeneous; Step 3: Wet mixing: Add deionized water to the dry-mixed raw materials and mix well. This is wet mixing. Step 4: Acid stirring: Add sulfuric acid to the wet and well-stirred raw materials. Add the sulfuric acid in at least three portions, adding it over 15 minutes. Stir well after each addition. This is acid stirring. Step 5: Electrode fabrication: Apply lead paste to the grid skeleton to form electrode plates, and then cure them; The preparation of the negative electrode includes the following steps: Step 1: Material preparation: Weigh the raw materials for the negative electrode: 1000 parts lead powder, 95-115 parts deionized water, 75-95 parts 51% sulfuric acid solution (by mass percentage), 0.6-1.0 parts super-strong fiber, 0.5-2 parts carbon fiber, 1-6 parts acetylene black, 1.5-4 parts lignin, 2-5 parts humic acid, 8-14 parts barium sulfate, and 2-5 parts carbon black.

[0011] Step 2: Dry mixing: Mix all raw materials except for deionized water and sulfuric acid, and stir until homogeneous; Step 3: Wet mixing: Add deionized water to the dry-mixed raw materials and mix well. This is wet mixing. Step 4: Acid stirring: Add sulfuric acid to the wet and well-stirred raw materials. Add the sulfuric acid in at least three portions, adding it over 15 minutes. Stir well after each addition. This is acid stirring. Step 5: Electrode fabrication: Apply lead paste to the grid skeleton to form the electrode, and then cure it.

[0012] A lead-acid battery, characterized in that: the positive and negative electrodes of the lead-acid battery are as described in any one of claims 1-6.

[0013] Compared with the prior art, the present invention provides positive and negative electrodes of a long-life lead-acid battery resistant to high humidity and high and low temperature alternation, as well as its preparation method and application. It can withstand high humidity and high and low temperature alternation. After the high humidity and high and low temperature alternation test, the battery capacity retention rate is more than 60% and the capacity recovery rate is ≥95%. It is suitable for use in environments with large temperature differences between 85% humidity, -40℃ and 65℃ alternation.

[0014] It can effectively solve the problem of rapidly declining battery cycle life when photovoltaic modules need to be driven in alternating environments of 85% humidity, -40℃ and 65℃, tracking sunlight and wind resistance, maximizing photovoltaic power generation and protecting photovoltaic modules from wind. Attached Figure Description

[0015] Figure 1 This is a flowchart illustrating the manufacturing process of the positive and negative electrodes for a battery. Detailed Implementation

[0016] The present invention will now be described in detail with reference to specific embodiments. It should be noted that these embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above description of the present invention.

[0017] Raw material source: Lead powder: homemade, using a Shimadzu lead powder mill to oxidize electrolytic lead into powder. The lead powder has an oxidation degree of 75-80%, an apparent specific gravity of 1.2-1.3 g / cm3, and Fe content of less than 0.0005%.

[0018] Deionized water: Homemade, water is made into deionized water using an anion exchange resin water purification device, and its conductivity is less than 0.5 μS / cm.

[0019] 51% sulfuric acid solution (by mass percentage): homemade.

[0020] Super strong polyester fiber: purchased from Jinkeli Company, model X2D3L.

[0021] Carbon fiber: Purchased from Jinkeli Company, model C17-2D3L Colloidal graphite: purchased from Jinkeli Company, model C9995.

[0022] Bismuth trioxide: Purchased from Longxi Chemical Company, analytical grade.

[0023] Stannous sulfate: Purchased from Longxi Chemical Company, analytical grade.

[0024] Tetrabasic lead sulfate: Purchased from Jinkeli Company, model 4BS.

[0025] Lignin: Purchased from Jinkeli Company, model N.

[0026] Carbon black: Purchased from Jinkeli Company, model PBX09.

[0027] Acetylene black is purchased from Jiaozuo Hexing Chemical Company; the grade is analytical grade, specifically for storage batteries.

[0028] The humic acid was purchased from Jinkeli Company; the model number is high-purity humic acid.

[0029] Barium sulfate was purchased from Nanfeng Group Company; model: ultrafine precipitated barium sulfate.

[0030] Example 1: Positive and negative electrodes of a long-life lead-acid battery resistant to high humidity and high / low temperature alternation. The positive electrode formulation, by weight, includes: 1000 parts lead powder, 105 parts deionized water, 85 parts 51% sulfuric acid solution, 0.6 parts high-strength polyester fiber, 1.5 parts colloidal graphite, 0.5 parts bismuth trioxide, 0.5 parts carbon fiber, 10 parts tetrabasic lead sulfate, and 0.5 parts stannous sulfate. The negative electrode formulation, by weight, includes: 1000 parts lead powder, 95 parts deionized water, 75 parts 51% sulfuric acid solution, 0.6 parts high-strength polyester fiber, 0.5 parts carbon fiber, 1 part acetylene black, 1.5 parts lignin, 2 parts humic acid, 8 parts barium sulfate, and 2 parts carbon black.

[0031] like Figure 1 The preparation method of the positive and negative electrodes of the long-life lead-acid battery resistant to high humidity and high and low temperature alternation includes the preparation of the positive and negative electrodes, as detailed below: The method for preparing the positive electrode includes the following steps: Step 1: Material preparation: Weigh the above-mentioned raw materials for the positive electrode; Step 2: Dry mixing: Add all raw materials except deionized water and sulfuric acid to the paste mixer and dry mix for 10 minutes until well mixed; Step 3: Wet mixing: Add deionized water to the paste mixer and mix for 10 minutes until well mixed. This is wet mixing. Step 4: Acid stirring: Add sulfuric acid to the paste mixer in three parts, adding it over 15 minutes. Then stir for another 10 minutes until the mixture is homogeneous. This is acid stirring. Step 5: Electrode fabrication: Apply lead paste to the grid skeleton to form the electrode; Step 6: Curing: Remove the electrode plate and place it on the curing rack. Then push the curing rack into the curing chamber for curing. The curing process includes a high temperature and high humidity stage, an oxidation stage, and a drying stage. The high temperature and high humidity stage lasts for 23 hours, the oxidation stage lasts for 17 hours, and the drying stage lasts for 20 hours. Step 7: Separation: Place the cured electrode plates from step 6 into the separation machine for separation; Step 8: Formation: Assemble the plates separated in Step 7 into a semi-finished battery, then fill the semi-finished battery with electrolyte, and perform formation using a process of 6 charge cycles and 5 discharge cycles.

[0032] The method for preparing the negative electrode includes the following steps: Step 1: Material preparation: Weigh the raw materials for the negative electrode as described above; Step 2: Dry mixing: Add all raw materials except deionized water and sulfuric acid to the paste mixer and dry mix for 10 minutes until well mixed; Step 3: Wet mixing: Add deionized water to the paste mixer and mix for 10 minutes until well mixed. This is wet mixing. Step 4: Acid stirring: Add sulfuric acid to the paste mixer in three parts, adding it over 15 minutes. Then stir for another 10 minutes until the mixture is homogeneous. This is acid stirring. Step 5: Electrode fabrication: Apply lead paste to the grid skeleton to form the electrode; Step 6: Curing: Remove the electrode plate and place it on the curing rack. Then push the curing rack into the curing chamber for curing. The curing process includes a high temperature and high humidity stage, an oxidation stage, and a drying stage. The high temperature and high humidity stage lasts for 23 hours, the oxidation stage lasts for 17 hours, and the drying stage lasts for 20 hours. Step 7: Separation: Place the cured electrode plates from step 6 into the separation machine for separation; Step 8: Formation: Assemble the plates separated in Step 7 into a semi-finished battery, then fill the semi-finished battery with electrolyte, and perform formation using a process of 6 charge cycles and 5 discharge cycles; to produce a 24V 8Ah battery.

[0033] Example 2: Positive and negative electrodes of a long-life lead-acid battery resistant to high humidity and high / low temperature alternation. The positive electrode formulation, by weight, includes: 1000 parts lead powder, 115 parts deionized water, 95 parts 51% sulfuric acid solution, 0.8 parts high-strength polyester fiber, 2.5 parts colloidal graphite, 1 part bismuth trioxide, 1.25 parts carbon fiber, 15 parts tetrabasic lead sulfate, and 1 part stannous sulfate.

[0034] The negative electrode formulation, by weight, includes: 1000 parts lead powder, 105 parts deionized water, 85 parts 51% sulfuric acid solution, 0.8 parts high-strength polyester fiber, 1.25 parts carbon fiber, 3.5 parts acetylene black, 2.75 parts lignin, 3.5 parts humic acid, 11 parts barium sulfate, and 3.5 parts carbon black.

[0035] The preparation method of the positive and negative electrodes of the high-humidity and high-low temperature alternating long-life lead-acid battery is the same as that in Example 1, except that in step 6, the high temperature and high humidity stage lasts for 25 hours, the oxidation stage lasts for 20 hours, and the drying stage lasts for 20 hours. The battery is made into a 24V 8Ah battery.

[0036] Example 3: The positive electrode formulation, by weight, includes: 1000 parts lead powder, 125 parts deionized water, 105 parts 51% sulfuric acid solution, 1.0 part high-strength polyester fiber, 3.5 parts colloidal graphite, 1.5 parts bismuth trioxide, 2 parts carbon fiber, 20 parts tetrabasic lead sulfate, and 1.5 parts stannous sulfate.

[0037] The negative electrode formulation, by weight, includes: 1000 parts lead powder, 115 parts deionized water, 95 parts 51% sulfuric acid solution, 1.0 part high-strength polyester fiber, 2 parts carbon fiber, 6 parts acetylene black, 4 parts lignin, 5 parts humic acid, 14 parts barium sulfate, and 5 parts carbon black.

[0038] The preparation method of the positive and negative electrode formulations of the high-humidity and high-low temperature alternating long-life lead-acid battery is the same as that in Example 1, except that in step 6, the high-temperature and high-humidity stage lasts for 20 hours, the oxidation stage lasts for 15 hours, and the drying stage lasts for 20 hours. The battery is made into a 24V 8Ah battery.

[0039] Comparative Example 1 shows the positive and negative electrode formulations of a conventional low-temperature lead-acid battery: The positive electrode formulation, by weight, includes: 1000 parts lead powder, 120 parts deionized water, 100 parts 51% sulfuric acid solution, 0.8 parts high-strength polyester fiber, 2.5 parts colloidal graphite, and 0.5 parts stannous sulfate.

[0040] The negative electrode formulation, by weight, includes: 1000 parts lead powder, 100 parts deionized water, 90 parts 51% sulfuric acid solution, 0.8 parts high-strength polyester fiber, 5 parts acetylene black, 2.5 parts lignin, 1.5 parts humic acid, and 6 parts barium sulfate.

[0041] The preparation method of the positive and negative electrodes of the low-temperature lead-acid battery is the same as that in Example 1, except that the raw materials are not added in the corresponding steps, and a 24V 8Ah battery is made.

[0042] For the 24V 8Ah batteries of Examples 1-3 and Comparative Example 1, a standard high humidity and low temperature alternating life test was conducted: in an environment with 85% humidity, the temperature was lowered from 25°C to -40°C for 1 hour, held at -40°C for 10 minutes, raised from -40°C to 65°C for 2 hours, held at 65°C for 10 minutes, and then lowered from 65°C to 25°C for 1 hour. This alternating test was repeated 200 times. Then the test was continued: at 85% humidity, the temperature was held at 65°C for 20 hours, lowered from 65°C to -40°C for 1.75 hours, held at -40°C for 0.5 hours, and then raised from -40°C to 25°C for 1.75 hours. The battery was brought to 65℃, and this alternating experiment was repeated 10 times. Then the experiment continued: 85% humidity, 65℃ maintained for 20 hours, then the temperature was lowered from 65℃ to 25℃ for 1 hour and maintained for 2 hours, then the temperature was raised from 25℃ to 65℃ for 1 hour and maintained for 20 hours. This alternating experiment was repeated 100 times. The battery voltage was recorded for each alternating experiment. The cycle continued when the battery open-circuit voltage was greater than 1.9V / division; otherwise, the cycle life was terminated. The battery capacity was then verified: the cycle life battery capacity and retention rate were verified, as well as the cycle life battery recovery capacity and recovery rate were verified. The test results are shown in the table below. The data in the table shows that, in Examples 1-3, the batteries made using the formulation of this invention exhibit significantly higher high-humidity and high-low temperature alternating cycle life compared to Comparative Example 1. Furthermore, after the end of the cycle life, the capacity and retention rate of the verified batteries are significantly higher than those of Comparative Example 1, and the recovered capacity and recovery rate are also significantly higher. This demonstrates that the positive and negative electrode formulations of this invention significantly improve high-humidity and high-low temperature performance, thereby increasing the battery's lifespan in high-humidity and high-low temperature alternating environments and enabling the battery to meet the 310-cycle life requirement in such environments.

Claims

1. A positive and negative electrode of a long-life lead-acid storage battery resistant to high humidity and high-temperature alternating, characterized by: By weight, The positive electrode comprises the following raw materials: lead powder 1000 parts, deionized water 105-125 parts, 51% sulfuric acid solution with a mass percentage concentration of 85-105 parts, super fiber 0.6-1.0 parts, colloidal graphite 1.5-3.5 parts, bismuth trioxide 0.5-1.5 parts, carbon fiber 0.5-2 parts, lead sulfate 10-20 parts, stannous sulfate 0.5-1.5 parts; The negative electrode comprises the following raw materials: lead powder 1000 parts, deionized water 95-115 parts, 51% sulfuric acid solution with a mass percentage concentration of 75-95 parts, super fiber 0.6-1.0 parts, carbon fiber 0.5-2 parts, acetylene black 1-6 parts, lignin 1.5-4 parts, humic acid 2-5 parts, barium sulfate 8-14 parts, carbon black 2-5 parts.

2. The positive and negative electrodes of the long-life lead-acid storage battery resistant to high humidity and high-low temperature alternation according to claim 1, characterized in that: The particle size of colloidal graphite is less than 30 microns, and the carbon content is greater than 99.95%.

3. The positive and negative electrodes of the long-life lead-acid storage battery resistant to high humidity and high-low temperature alternation according to claim 1, characterized in that: The super fiber is super polyester fiber, and the single fiber fineness of the super polyester fiber is less than 2D, the length is 2-4mm, and the breaking strength is greater than or equal to 8CN / dtex.

4. The positive and negative electrodes of the long-life lead-acid storage battery resistant to high humidity and high-low temperature alternation according to claim 1, characterized in that: The single fiber fineness of the carbon fiber is less than 2D, the length is 2-4mm, and the resistivity is less than 17 micro ohm·m.

5. A preparation method of positive and negative electrodes of a long-life lead-acid storage battery resistant to high humidity and high-low temperature alternation, characterized in that, The preparation of the positive electrode comprises the following steps: Step 1: Take the raw materials of the positive electrode: lead powder 1000 parts, deionized water 105-125 parts, 51% sulfuric acid solution with a mass percentage concentration of 85-105 parts, super fiber 0.6-1.0 parts, colloidal graphite 1.5-3.5 parts, bismuth trioxide 0.5-1.5 parts, carbon fiber 0.5-2 parts, lead sulfate 10-20 parts, stannous sulfate 0.5-1.5 parts; Step 2: Dry stirring: mix the other raw materials except deionized water and sulfuric acid, and stir evenly; Step 3: Wet stirring: add deionized water to the dry stirred raw materials, stir evenly, which is wet stirring; Step 4: Acid stirring: add sulfuric acid to the wet stirred raw materials, add sulfuric acid in at least three times, add completely in 15 minutes, stir evenly, which is acid stirring; Step 5: Plate making: coat the lead paste on the grid skeleton to form the plate, and then solidify; The preparation of the negative electrode comprises the following steps: Step 1: Take the raw materials of the negative electrode: lead powder 1000 parts, deionized water 95-115 parts, 51% sulfuric acid solution with a mass percentage concentration of 75-95 parts, super fiber 0.6-1.0 parts, carbon fiber 0.5-2 parts, acetylene black 1-6 parts, lignin 1.5-4 parts, humic acid 2-5 parts, barium sulfate 8-14 parts, carbon black 2-5 parts; Step 2: Dry stirring: mix the other raw materials except deionized water and sulfuric acid, and stir evenly; Step 3: Wet stirring: add deionized water to the dry stirred raw materials, stir evenly, which is wet stirring; Step 4: Acid stirring: add sulfuric acid to the wet stirred raw materials, add sulfuric acid in at least three times, add completely in 15 minutes, stir evenly, which is acid stirring; Step 5: Plate making: coat the lead paste on the grid skeleton to form the plate, and then solidify.

6. A lead-acid battery characterised in that: The positive and negative electrodes of the lead-acid battery are the positive and negative electrodes as claimed in any one of claims 1 to 5.

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