Zinc-manganese battery sealing compound and preparation method thereof

Abstract

The invention discloses a sealing adhesive for a zinc-manganese battery. The sealing adhesive is prepared from the following components in parts by weight: 60 to 80 parts of polybutylene, 10 to 30 parts of C5 petroleum resin, 10 to 30 parts of amorphous alpha-olefin copolymer, 0.1 to 1.0 part of antioxidant B225 and 0.05 to 0.5 part of red dye, the invention also discloses a preparation method of the zinc-manganese battery sealing compound. When in use, the zinc-manganese battery sealing glue needs to be heated to 130-140 DEG C for gluing; the zinc-manganese battery sealing compound has good adhesion, creep resistance and aging resistance, does not deform and flow at high temperature, has good low-temperature adhesion and does not crack, so that the storage stability of a battery is improved, and the service life of the battery is prolonged. The preparation method of the sealing compound is simple, short in technological process and convenient for industrialization.

Description

Technical Field

[0001] The invention relates to a zinc-manganese battery sealing adhesive and a preparation method thereof. Background Art

[0002] Carbon batteries (also known as zinc-manganese batteries) are the most common type of dry cell battery on the market, widely used in household appliances, toys, flashlights, and other everyday applications. Battery sealing adhesive plays a crucial role in the manufacturing process of zinc-manganese batteries, and its quality directly impacts the battery's overall performance and reliability. The primary function of battery sealing adhesive is to ensure a tight seal inside the battery, preventing the ingress of air and moisture. It also maintains the stability of the battery's internal chemical structure, preventing liquid leakage and gas emissions, thereby ensuring battery safety and longevity.

[0003] The sealing compound used in zinc-manganese batteries relies heavily on multiple factors, including product structural design, component material selection, and processing precision. The compound must possess appropriate adhesion, toughness, and pressure resistance to effectively fill gaps during battery assembly, maintain a closed seal, prevent excessive gas generation during battery discharge, and ensure the seal is unaffected by external pressure and temperature fluctuations. Furthermore, the compound must be able to withstand pressure fluctuations both inside and outside the battery to prevent the leakage of degradation fluids generated by the reaction.

[0004] In recent years, with the continuous development of zinc-manganese battery manufacturing technology, the traditional sealing adhesive coating method has gradually improved. Battery manufacturers have begun to adopt a coating method, that is, applying a thin layer of sealing adhesive to the upper surface of the zinc cylinder and carbon rod. This method not only increases battery capacity and reduces costs, but also extends battery life.

[0005] Given the characteristics of zinc-manganese batteries, the sealing adhesive must meet multiple performance requirements. First, it needs to have excellent chemical and water resistance, and be able to have good wettability and bonding strength with other battery components (such as carbon rods, sealing rings, etc.); second, the sealing adhesive should have appropriate viscosity, be able to maintain a consistent coating thickness during use, and not flow or creep under the influence of long-term temperature and pressure. In addition, the battery sealing adhesive also needs to have a high softening point or melting point to ensure that it will not leak in high temperature environments and can still maintain good adhesion in low temperature environments.

[0006] Currently, zinc-manganese battery sealing adhesives are primarily categorized into asphalt-based and rubber-based sealants. Asphalt-based sealants are made from asphalt, blended with materials like rosin and motor oil. They offer excellent adhesion and sealing properties and are relatively low-cost, but they tend to harden and lose their viscosity at low temperatures. They also age and dry out over time, reducing their sealing effectiveness. Rubber-based sealants offer better low-temperature performance and aging resistance, but are more expensive and require more precise control during use. Summary of the Invention

[0007] The purpose of the present invention is to provide a zinc-manganese battery sealing glue and a preparation method thereof, which has good heat resistance, aging resistance and low temperature performance, and has performance significantly better than asphalt series battery sealing glue, and meets the use requirements of carbon battery manufacturers.

[0008] The technical solution adopted by the present invention to solve its technical problem is:

[0009] A zinc-manganese battery sealing adhesive comprising the following components:

[0010] Polybutene: 60 to 80 parts;

[0011] Tackifying resin: 10 to 30 parts;

[0012] Amorphous α-olefin copolymer: 10 to 30 parts;

[0013] Antioxidant: 0.1 to 1.0 parts;

[0014] Red dye: 0.05 to 0.5 parts.

[0015] Preferably, the tackifying resin is C5 petroleum resin.

[0016] Preferably, the amorphous α-olefin copolymer is an amorphous copolymer polymerized from α-olefin.

[0017] Preferably, the antioxidant is antioxidant B225.

[0018] Preferably, the red dye is azo red.

[0019] Another technical problem to be solved by the present invention is to provide a method for preparing a zinc-manganese battery sealing adhesive, comprising the following steps:

[0020] First, add 60 to 80 parts of polybutene into the blending tank, start the heat transfer oil to heat up, start the mechanical stirring, and raise the temperature to 120℃ to 130℃;

[0021] Second, add 10 to 30 parts of tackifying resin, 10 to 30 parts of amorphous α-olefin copolymer, 0.1 to 1.0 parts of antioxidant and 0.05 to 0.5 parts of red dye, start stirring, and raise the temperature to 140°C;

[0022] Third, maintain the temperature at 140°C to 150°C and stir for 6 hours until the mixture is completely dissolved.

[0023] Fourth, take samples and test them. After passing the test, filter them with a 100-mesh filter and then pack them into barrels.

[0024] Preferably, the polybutene is a copolymer of isobutylene and n-butene.

[0025] Preferably, the molecular weight of the polybutene is between 500-2500.

[0026] The beneficial effects of the present invention are:

[0027] The zinc-manganese battery sealing adhesive of the present invention needs to be heated to 130°C to 140°C before application. The zinc-manganese battery sealing adhesive has excellent adhesion, creep resistance, and aging resistance, and does not deform or flow at high temperatures or crack at low temperatures, thereby improving battery storage stability and extending battery life. The preparation method of the sealing adhesive is simple, the process flow is short, and it is easy to industrialize. Specific implementation methods

[0028] The principles and features of the present invention are described below. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used in this specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0030] Example 1

[0031] A sealing adhesive for zinc-manganese battery sealing, comprising the following components:

[0032] Polybutene: 70 parts, tackifying resin (C5 petroleum resin): 15 parts, amorphous α-olefin copolymer (amorphous copolymer polymerized from α-olefin): 18 parts, antioxidant B225: 0.2 parts, red dye (azo red): 0.1 parts.

[0033] A method for preparing a sealing adhesive for sealing zinc-manganese battery, comprising the following specific steps:

[0034] Add 70 parts of polybutene into the blending tank, start the heat transfer oil to heat up, start mechanical stirring, and raise the temperature to 120℃~130℃;

[0035] Add 9.7 parts of C5 petroleum resin, 20 parts of amorphous α-olefin copolymer, 0.2 parts of antioxidant B225 and 0.1 parts of red dye, continue stirring, and raise the temperature to 140°C;

[0036] Maintain the temperature at 140-150°C and stir for 6 hours to ensure that the ingredients are completely dissolved;

[0037] After sampling and testing, if qualified, filter it with a 100-mesh filter and finally pack it into barrels.

[0038] The use of 70 parts of polybutene enhances the adhesion and flexibility of the sealing glue, helps to improve the sealing effect of the battery and prevent leakage of internal battery substances; the combination of 15 parts of C5 petroleum resin and 18 parts of amorphous α-olefin copolymer optimizes the fluidity and adhesion properties of the sealing glue, so that it can still maintain excellent adhesion and flexibility under high temperature conditions; the use of antioxidant B225 effectively delays the oxidation process and ensures the stability of the sealing glue during long-term use; the addition of red dye (azo red) makes the sealing glue more vivid in color, so that it can be observed whether it is broken or leaked during the coating process.

[0039] The main purpose of this embodiment is to provide a sealing glue that is efficient, stable, anti-oxidation and has strong adhesion, which is suitable for sealing zinc-manganese batteries, can maintain excellent sealing performance in high temperature environments, extend the service life of the battery, and has good appearance and color stability.

[0040] Example 2

[0041] A sealing adhesive for zinc-manganese battery sealing, comprising the following components:

[0042] Polybutene: 65 parts, tackifying resin (C5 petroleum resin): 18 parts, amorphous α-olefin copolymer (amorphous copolymer polymerized from α-olefin): 22 parts, antioxidant B225: 0.3 parts, red dye (azo red): 0.1 parts.

[0043] A method for preparing a sealing adhesive for sealing zinc-manganese battery, comprising the following specific steps:

[0044] Add 65 parts of polybutene into the blending tank, start heating the thermal oil, start mechanical stirring, and raise the temperature to 120℃~130℃;

[0045] Add 12.6 parts of C5 petroleum resin, 22 parts of amorphous α-olefin copolymer, 0.3 parts of antioxidant B225 and 0.1 parts of red dye, continue stirring, and raise the temperature to 140°C;

[0046] Maintain the temperature at 140-150°C and stir for 6 hours to ensure that the ingredients are completely dissolved;

[0047] After sampling and testing, if qualified, filter it with a 100-mesh filter and finally pack it into barrels.

[0048] The use of 65 parts of polybutene provides better flexibility and adhesion, which can effectively seal zinc-manganese batteries and prevent battery fluid leakage; the addition of 18 parts of C5 petroleum resin further enhances the adhesion and fluidity of the sealing glue, improves its adhesion to the battery shell, and ensures the sealing effect; the addition of 22 parts of amorphous α-olefin copolymer enhances the bonding strength of the sealing glue, which can maintain its physical properties during battery operation and prevent glue or liquid leakage caused by high temperature; the proportion of antioxidant B225 (0.3 parts) in this formula is slightly increased, which helps to enhance the antioxidant properties of the sealing glue, so that it can maintain stable performance over a longer period of time.

[0049] The purpose of this embodiment is to optimize the fluidity, adhesion and thermal stability of the sealing glue by increasing the proportion of C5 petroleum resin and amorphous α-olefin copolymer, so that it can still maintain good sealing properties under higher temperatures and harsh environments, extend the service life of the battery, and improve durability.

[0050] Example 3

[0051] A sealing adhesive for zinc-manganese battery sealing, comprising the following components:

[0052] Polybutene: 68 parts, tackifying resin (C5 petroleum resin): 12 parts, amorphous α-olefin copolymer (amorphous copolymer polymerized from α-olefin): 20 parts, antioxidant B225: 0.2 parts, red dye (azo red): 0.1 parts.

[0053] A method for preparing a sealing adhesive for sealing zinc-manganese battery, comprising the following specific steps:

[0054] Add 68 parts of polybutene into the blending tank, start the heat transfer oil to heat up, start mechanical stirring, and raise the temperature to 120℃~130℃;

[0055] Add 11.7 parts of C5 petroleum resin, 20 parts of amorphous α-olefin copolymer, 0.2 parts of antioxidant B225 and 0.1 parts of red dye, continue stirring, and raise the temperature to 140°C;

[0056] Maintain the temperature at 140-150°C and stir for 6 hours to ensure that the ingredients are completely dissolved;

[0057] After sampling and testing, if qualified, filter it with a 100-mesh filter and finally pack it into barrels.

[0058] The use of 68 parts of polybutene ensures the adhesion and flexibility of the sealing glue, which can effectively seal the battery and prevent leakage; the use of 12 parts of C5 petroleum resin enhances the adhesion and fluidity of the sealing glue, enabling it to be evenly coated to ensure the sealing effect; the addition of 20 parts of amorphous α-olefin copolymer improves the bonding strength of the sealing glue, enabling it to cope with the high temperature environment that may occur during the operation of the battery; by adding antioxidant B225, the oxidation process of the sealing glue is effectively delayed, ensuring that the sealing glue maintains its performance for a long time.

[0059] The purpose of this embodiment is to provide a more balanced sealing adhesive formula. By adjusting the ratio of polybutene, C5 petroleum resin and amorphous α-olefin copolymer, the adhesion, thermal stability and oxidation resistance of the sealing adhesive are optimized, so that it can maintain good sealing performance in various working environments, thereby improving the safety and life of the battery.

[0060] Example 4

[0061] A sealing adhesive for zinc-manganese battery sealing, comprising the following components:

[0062] Polybutene: 72 parts, tackifying resin (C5 petroleum resin): 13 parts, amorphous α-olefin copolymer (amorphous copolymer polymerized from α-olefin): 18 parts, antioxidant B225: 0.25 parts, red dye (azo red): 0.05 parts.

[0063] A method for preparing a sealing adhesive for sealing zinc-manganese battery, comprising the following specific steps:

[0064] Add 72 parts of polybutene into the blending tank, start heating the thermal oil, start mechanical stirring, and raise the temperature to 120℃~130℃;

[0065] Add 9.6 parts of C5 petroleum resin, 18 parts of amorphous α-olefin copolymer, 0.3 parts of antioxidant B225 and 0.1 parts of red dye, continue stirring, and raise the temperature to 140°C;

[0066] Maintain the temperature at 140-150°C and stir for 6 hours to ensure that the ingredients are completely dissolved;

[0067] After sampling and testing, if qualified, filter it with a 100-mesh filter and finally pack it into barrels.

[0068] 72 parts of polybutene give the sealing glue strong adhesion and flexibility, which can effectively seal zinc-manganese batteries and prevent leakage; the appropriate use of 13 parts of C5 petroleum resin further improves the adhesion of the sealing glue, making its contact with the battery shell closer and ensuring the sealing effect; the use of 18 parts of amorphous α-olefin copolymer provides good bonding strength, and the sealing glue can withstand the high temperature conditions that the battery may encounter during use; the addition of antioxidant B225 (0.3 parts) effectively enhances the antioxidant ability of the sealing glue, ensuring that it does not oxidize during long-term use and maintains stable performance; the use of a small amount of red dye (azo red) can not only optimize the appearance of the sealing glue, but also improve its color stability.

[0069] The purpose of this embodiment is to provide a sealing adhesive with strong adhesion, thermal stability and oxidation resistance by optimizing the ratio of each component. The sealing adhesive is suitable for sealing zinc-manganese batteries, can maintain sealing performance in high temperature environments, and has good color stability. The sealing adhesive can not only ensure the safety of the battery, but also improve the appearance quality and service life of the battery.

[0070] Experimental Example 1

[0071] In the present invention, the testing standards are formulated according to the actual requirements of battery coating and heat resistance, as shown in Table 1.

[0072] Table 1 Sealing glue performance test standard

[0073] project Quality indicators Appearance red Melting point / ℃ 65～80 Melt viscosity (130℃) / mPa·s 190～230

[0074] The battery sealing adhesives obtained in Examples 1 to 4 were tested according to the testing standards described in Table 1. Table 2 lists the performance test results of the four sealing adhesives. It can be seen from Table 2 that the zinc-manganese battery sealing adhesives of the present invention all meet the requirements of the indicators in Table 1. Their melting points are all within the range of 65 to 80°C, ensuring that the battery sealing adhesive has excellent heat resistance. When the battery is made at a high temperature of 60°C, it will not flow down from the zinc cylinder and carbon rod, and no glue will leak. The melt viscosity of the battery sealing adhesive at 130°C is within the range of 190 to 230 mPa·s, ensuring that the battery sealing adhesive is evenly coated at a coating temperature of 130°C without interruption or missing coating, thereby ensuring that the sealing adhesive plays a sealing role in the battery seal.

[0075] Table 2 Sealing glue performance test results

[0076]

[0077]

[0078] Experimental Example 2

[0079] The sealing adhesives prepared in Examples 1-4 were prepared according to the proportions and cured to prepare molding samples.

[0080] Asphalt series sealant: used for comparative experiments.

[0081] Zinc-manganese battery casing: used for coating experiments of sealing glue.

[0082] Equipment required for the experiment:

[0083] Hot air circulation box (high temperature test)

[0084] Freezer (low temperature test)

[0085] Tensile testing machine (test adhesion)

[0086] Constant temperature aging box

[0087] Electronic universal testing machine (creep resistance test)

[0088] Viscometer (measures the fluidity of sealing adhesive)

[0089] Experimental methods:

[0090] Adhesion test:

[0091] step:

[0092] The sealing glue is applied on the shell of the zinc-manganese battery to form a certain thickness.

[0093] Cure the sealant to ensure that the glue layer is completely fixed.

[0094] The sealing adhesive was stretched using a tensile testing machine to test its adhesion (i.e., the adhesion strength between the sealing adhesive and the battery casing).

[0095] Measure the tensile strength and fracture mode and record the experimental data.

[0096] Comparison: Examples 1-4 are compared with asphalt series sealants.

[0097] Table 1: Adhesion test results

[0098]

[0099]

[0100] The sealing glues in Examples 1-4 all exhibited strong adhesion, among which Example 2 had the highest tensile strength, reaching 15N, indicating that this series of sealing glues had good adhesion properties and was suitable for occasions requiring high adhesion. The tensile strength of the asphalt series sealing glue was 7N, which was significantly lower than that of Examples 1-4, indicating that its adhesion properties were weak and it was not suitable for applications requiring strong adhesion.

[0101] Creep resistance test:

[0102] step:

[0103] Apply the sealing glue on the battery surface, solidify it, and place it in a 50°C environment.

[0104] Measure the deformation of the sealing glue after being compressed and record the deformation.

[0105] Creep tests were performed for different time periods (e.g., 1 hour, 5 hours, 10 hours).

[0106] Comparison: Record the deformation of the sealant at different time periods and compare it with the asphalt series sealant.

[0107] Table 2: Creep resistance test results

[0108]

[0109] The sealing glues of Examples 1-4 exhibited smaller deformation at high temperatures, especially Example 1, which had the smallest deformation, indicating that these sealing glues had better creep resistance and stability; the asphalt series sealing glue exhibited larger deformation, especially under long-term high temperature, the deformation was larger, indicating that its creep resistance was poor, which would lead to a decline in product performance during long-term use.

[0110] Aging resistance test:

[0111] step:

[0112] The sealing glue sample was placed in a constant temperature aging box set at 60°C to simulate the long-term storage state of the battery.

[0113] Take out the sealant samples every 500 hours and check their appearance, adhesion, toughness and thermal stability.

[0114] Test the adhesive strength and appearance changes of the sealant.

[0115] Comparison: The changes of the sealing adhesives of Examples 1-4 and the asphalt series sealing adhesives after 500 hours were compared.

[0116] Aging resistance test results

[0117]

[0118] In the aging test of the sealing glue of Examples 1-4, all showed good aging resistance, especially Example 1-2, where the adhesion strength remained high after 500 hours and there was no obvious change in appearance; the aging performance of the asphalt series sealing glue was poor, with obvious cracking and discoloration after 500 hours, and the adhesion strength decreased significantly, showing poor aging stability.

[0119] Test of no deformation and no flow under high temperature:

[0120] step:

[0121] Apply the sealing glue to the battery casing and cure it.

[0122] The samples were placed in a hot air circulation box at 85°C for 12 hours.

[0123] Check whether the sealing glue flows or deforms in a high temperature environment.

[0124] Measure the thickness and appearance changes of the sealant.

[0125] Comparison: The performance of the sealing adhesives of Examples 1-4 and asphalt series sealing adhesives at high temperatures was compared.

[0126] Table 4: Test results of no deformation and no flow at high temperature

[0127]

[0128] The sealing glues in Examples 1-4 showed no flow phenomenon in the high-temperature test and had small deformation, indicating that they had good stability at high temperatures; the asphalt series sealing glue showed large deformation and flow phenomenon at high temperatures, indicating that they had poor high-temperature stability and were not suitable for use in high-temperature environments.

[0129] Low temperature non-cracking test:

[0130] step:

[0131] Apply the sealing glue to the battery casing and cure it.

[0132] Place the sealing glue sample in a -20°C freezer for 12 hours.

[0133] Check whether the sealing glue has cracks or brittle fractures.

[0134] Measure the elasticity and surface cracks of the sealant.

[0135] Comparison: The performance of the sealing adhesives of Examples 1-4 and asphalt series sealing adhesives at low temperatures was compared.

[0136] Table 5: Low temperature non-cracking test results

[0137]

[0138]

[0139] The sealing glues of Examples 1, 2, and 4 did not crack at low temperatures and maintained good elasticity, indicating that they had good low-temperature adaptability; the sealing glue of Example 3 cracked at low temperatures and its elasticity deteriorated, indicating that its low-temperature adaptability was poor; the asphalt series sealing glue also showed cracks and poor elasticity at low temperatures, and had poor adaptability.

[0140] Storage stability and service life test:

[0141] step:

[0142] A zinc-manganese battery covered with sealing glue was prepared and stored at 25° C. and 50% humidity.

[0143] Conduct a discharge test on the battery every six months and record its power output, service life and other data.

[0144] Observe the changes in the sealing glue during long-term use, such as whether there are problems such as loosening and leakage.

[0145] Comparison: Comparison of the service life of batteries using the sealing glue of Examples 1-4 and the asphalt series sealing glue.

[0146] Table 6: Storage stability and service life test results

[0147]

[0148] The sealing glues of Examples 1-4 performed well in terms of battery life, especially Example 2, which had the longest battery life of 20 months and had good storage stability. The asphalt series sealing glue had a shorter service life of only 12 months, indicating that its stability was poor and performance would decline during use.

[0149] The above embodiments of the present invention are not intended to limit the scope of protection of the present invention, and the implementation methods of the present invention are not limited thereto. All other modifications, replacements or changes made to the above structures of the present invention based on the above contents of the present invention, in accordance with common technical knowledge and customary means in this field, without departing from the above basic technical ideas of the present invention, should fall within the scope of protection of the present invention.

Claims

1. A zinc-manganese battery sealing adhesive, characterized in that: Includes the following ingredients: Polybutene: 60 to 80 parts; Tackifying resin: 10 to 30 parts; Amorphous α-olefin copolymer: 10 to 30 parts; Antioxidant: 0.1 to 1.0 parts; Red dye: 0.05 to 0.5 parts.

2. The zinc-manganese battery sealing adhesive according to claim 1, characterized in that: The tackifying resin is C5 petroleum resin.

3. The zinc-manganese battery sealing adhesive according to claim 1, characterized in that: The amorphous α-olefin copolymer is an amorphous copolymer formed by polymerization of α-olefin.

4. The zinc-manganese battery sealing adhesive according to claim 1, characterized in that: The antioxidant is antioxidant B225.

5. The zinc-manganese battery sealing adhesive according to claim 1, characterized in that: The red dye is azo red.

6. A method for preparing a zinc-manganese battery sealing adhesive, characterized in that: The following steps are involved: First, add 60 to 80 parts of polybutene into the blending tank, start the heat transfer oil to heat up, start the mechanical stirring, and raise the temperature to 120℃ to 130℃; Second, add 10 to 30 parts of tackifying resin, 10 to 30 parts of amorphous α-olefin copolymer, 0.1 to 1.0 parts of antioxidant and 0.05 to 0.5 parts of red dye, start stirring, and raise the temperature to 140°C; Third, maintain the temperature at 140°C to 150°C and stir for 6 hours until the mixture is completely dissolved. Fourth, take samples and test them. After passing the test, filter them with a 100-mesh filter and then pack them into barrels.

7. The method for preparing the zinc-manganese battery sealing adhesive according to claim 1, characterized in that: The polybutene is a copolymer of isobutylene and normal butene.

8. The method for preparing the zinc-manganese battery sealing adhesive according to claim 1, characterized in that: The molecular weight of the polybutene is between 500 and 2500.

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