Electrolyte for zinc-manganese batteries

Abstract

The present application relates to the technical field of methods or devices for directly converting chemical energy into electrical energy, and particularly relates to an electrolyte for a zinc-manganese battery. The electrolyte comprises potassium hydroxide, modified zinc oxide and water. The present application also provides a preparation method thereof. Compared with the prior art, the electrolyte has excellent corrosion inhibition effect and good conductivity, and can prolong the service life of the battery.

Description

Technical Field

[0001] This invention relates to the field of methods or apparatus for directly converting chemical energy into electrical energy, and more particularly to an electrolyte for zinc-manganese batteries. Background Technology

[0002] Compared to rechargeable batteries (secondary batteries) such as nickel-cadmium, nickel-metal hydride, and lithium, disposable zinc-manganese batteries offer the following advantages: First, in terms of safety, disposable batteries provide greater assurance, are less prone to leakage or explosion, and can be used safely without relying on protective circuit boards. Second, they exhibit better stability, are unaffected by the memory effect, and do not require worry about over-discharge; they are also more adaptable to different environments and less prone to damage. Third, disposable batteries eliminate the need for chargers, typically have longer discharge cycles than rechargeable batteries, and are plug-and-play, offering greater convenience to users. Furthermore, disposable batteries are less expensive than rechargeable batteries, making them more cost-effective for small or low-power electronic devices. Finally, most current disposable zinc-manganese batteries are mercury-free or low-mercury, minimizing their environmental impact and facilitating recycling and disposal.

[0003] Alkaline zinc-manganese batteries are characterized by low internal resistance, strong voltage recovery after discharge, and a wide operating temperature range (-20℃ to 60℃), making them suitable for use in extremely cold regions. Their continuous discharge capacity at high current is approximately five times that of acidic zinc-manganese batteries. Furthermore, they exhibit excellent low-temperature discharge performance and are free of mercury and cadmium, making them environmentally friendly. Alkaline zinc-manganese batteries are widely used in various everyday applications, such as electric toys, home appliances, smart homes, home medical equipment, and outdoor electronic devices. With technological advancements, the performance of alkaline zinc-manganese batteries has been significantly improved, including higher energy density, a wider operating temperature range, and a lower self-discharge rate.

[0004] CN108172854A discloses a zinc-manganese battery, specifically an alkaline zinc-manganese battery containing zinc oxide and its preparation method. The battery includes a negative electrode zinc paste made of zinc powder, zinc oxide, sodium silicate, and a binder; a positive electrode ring made of electrolytic manganese dioxide and a conductive agent; a separator made of a pulp or fiber mixture; and electrolytes for the positive electrode ring, negative electrode zinc paste, and separator, respectively. All electrolytes are aqueous solutions of potassium hydroxide, and the electrolyte used for the negative electrode zinc paste contains zinc oxide. This invention is based on the increasing market demand for high-power alkaline zinc-manganese batteries. It increases the utilization rate of zinc powder while suppressing hydrogen evolution from zinc powder to a certain extent. Combined with optimized positive and negative electrodes and an optimized alkaline solution concentration ratio, the alkaline zinc-manganese battery produced by this formulation exhibits significantly improved high-current discharge performance.

[0005] CN107275655A discloses a natural extract composition for zinc-manganese battery electrolyte, its uses, and a zinc-manganese battery electrolyte and a zinc-manganese battery. The composition includes imidazoline derivatives, amino acid derivatives, and sterol derivatives. This composition exhibits excellent corrosion inhibition and good conductivity, as well as low-temperature and high-temperature resistance. When used as an electrolyte in zinc-manganese batteries, it can suppress the self-discharge performance of the negative electrode material in non-operating states, thereby reducing battery self-depletion and significantly extending battery life. During battery operation, its good conductivity allows it to perform normally. More importantly, this composition does not contain mercury, avoiding heavy metal pollution that may result from discarded batteries and reducing subsequent processing costs and environmental pollution risks. Its low-temperature resistance can reach -30℃, and its high-temperature resistance can reach 100℃.

[0006] Alkaline zinc-manganese batteries exhibit a certain degree of self-corrosion at the electrodes, which reduces their storage life. Therefore, improving the storage life of alkaline zinc-manganese batteries can be achieved by addressing the root cause of this self-corrosion. In alkaline zinc-manganese batteries, metallic zinc is thermodynamically unstable in an alkaline environment, making it prone to chemical reactions that produce hydrogen gas, leading to self-corrosion. This is because zinc, being a reactive metal, reacts with potassium hydroxide (KOH) in an alkaline electrolyte, causing zinc to dissolve and form corrosion products such as zinc hydroxide (Zn(OH)₂) and zinc oxide (ZnO). Furthermore, during discharge, zinc at the negative electrode loses electrons and undergoes oxidation, producing zinc ions. These zinc ions combine with hydroxide ions to form zinc hydroxide, which is another cause of self-corrosion. To mitigate this self-corrosion, researchers have implemented various measures. For example, corrosion-resistant zinc alloys can be used as the negative electrode, or zinc corrosion inhibitors can be added, such as inorganic corrosion inhibitors like metal oxides, hydroxides, and inorganic salts, as well as organic corrosion inhibitors like surfactants and hydrogen-removing additives. These corrosion inhibitors can form a protective film on the zinc surface, preventing or reducing the absorption of OH groups. - Ions contact the zinc surface, thereby inhibiting electrode corrosion. However, it should be noted that non-mercury corrosion inhibitors may have some drawbacks, such as increasing the internal resistance of the battery, affecting the contact between zinc powder particles and between zinc powder and the current collector, reducing the battery's vibration resistance, and having lower leakage resistance during discharge compared to mercury-containing batteries. In the process of manufacturing mercury-free batteries, the first problem to be solved is the corrosion of the battery anode, which is also the key to solving the current battery storage life problem. Summary of the Invention

[0007] In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is to provide an electrolyte for zinc-manganese batteries and a method for preparing the same.

[0008] The negative electrode electrolyte of alkaline zinc-manganese batteries mainly consists of KOH and ZnO. KOH provides conductive ions during battery discharge, and its concentration affects the charge transfer capability during discharge. ZnO primarily inhibits the self-dissolution of zinc at the negative electrode, i.e., zinc self-corrosion. The role of ZnO in alkaline zinc-manganese batteries is mainly to form a protective film to suppress the self-dissolution of zinc at the negative electrode. As an amphoteric substance, ZnO can form a dissolution equilibrium with zincates in potassium hydroxide (KOH) solution. When the battery discharges, zincates are produced at the negative electrode, and ZnO is deposited when the concentration reaches saturation. This ZnO protective film slows down further reactions of zinc, thus protecting the zinc electrode from excessive dissolution or corrosion. Furthermore, the addition of ZnO also helps improve the electrochemical performance of the battery. In some studies, in-situ growth of a ZnO protective layer on the zinc metal surface can significantly improve the cycle stability of the zinc negative electrode and inhibit dendrite growth, thereby extending the battery's lifespan. The presence of the ZnO protective layer helps form a stable electrode / electrolyte interface, reduces the occurrence of side reactions, and thus improves the overall performance of the battery. This invention provides a modified ZnO by grafting pyridine groups onto its surface. The pyridine groups contain nitrogen atoms with lone pairs of electrons, which can form coordinate bonds with atoms on the metal surface, achieving chemisorption. Furthermore, the π electrons on the pyridine ring can form coordinate bonds with empty orbitals on the metal surface, enhancing the corrosion inhibition effect. Therefore, after the modified zinc oxide forms a protective layer on the zinc anode surface, the corrosion inhibition effect is enhanced. Applying this modified zinc oxide to the electrolyte for zinc-manganese batteries can further improve battery life.

[0009] To achieve the above objectives, the present invention provides an electrolyte for zinc-manganese batteries, comprising potassium hydroxide, modified zinc oxide, and water;

[0010] The preparation method of the modified zinc oxide includes the following steps:

[0011] After vacuum drying of zinc oxide, anhydrous ethanol and water are mixed in a certain proportion. The dried zinc oxide is added to the mixture of ethanol and water and ultrasonically dispersed at 400-500W for 30-50 min. After ultrasonication, the mixture is stirred for 1-2 h. Then, an equal volume of ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridinyl)-4-pyridinyl]butyl]silane is added dropwise. After the addition is completed, the mixture is heated and stirred for 1-3 h. After cooling to room temperature, the mixture is washed three times with anhydrous ethanol, centrifuged, and the supernatant is discarded. The lower precipitate is vacuum dried to obtain modified zinc oxide.

[0012] Furthermore, the mass ratio of the anhydrous ethanol to water is 1:1 to 2.

[0013] Furthermore, the mass ratio of the zinc oxide to the mixture of ethanol and water is 1:80 to 100.

[0014] Furthermore, the temperature range for the heating is 60–80°C.

[0015] Furthermore, the concentration of the ethanol solution of the trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane is 4-5 wt%.

[0016] Furthermore, the vacuum drying temperature is 50–60°C.

[0017] Furthermore, the vacuum drying time is 8 to 10 hours.

[0018] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0019] The mixture is prepared by mixing potassium hydroxide, modified zinc oxide, and water, and stirring until homogeneous.

[0020] Furthermore, the concentration of the potassium hydroxide is 25–40 wt%.

[0021] Furthermore, the concentration of the modified zinc oxide is 2–8 wt%.

[0022] The beneficial effects of this invention are:

[0023] Compared with existing technologies, this invention provides a modified ZnO by grafting pyridine groups onto its surface. These pyridine groups contain nitrogen atoms with lone pairs of electrons, which can form coordinate bonds with atoms on the metal surface, achieving chemisorption. Furthermore, the π electrons on the pyridine ring can form coordinate bonds with empty orbitals on the metal surface, enhancing the corrosion inhibition effect. Therefore, after the modified zinc oxide forms a protective layer on the zinc anode surface, the corrosion inhibition effect is enhanced. Applying this modified zinc oxide to the electrolyte for zinc-manganese batteries can further improve battery life. Detailed Implementation

[0024] Trimethoxy-[4-[2-(4-methyl-2-pyridinyl)-4-pyridinyl]butyl]silane, CAS No.: 1588918-82-4.

[0025] 2-(2-pyridin-2-ylethyl)silane, CAS No.: 27326-65-4.

[0026] Zinc oxide, particle size: 20-30 nm.

[0027] Example 1

[0028] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0029] Mix 40g of potassium hydroxide, 6g of modified zinc oxide, and 54mL of water, and stir until homogeneous.

[0030] The preparation method of the modified zinc oxide includes the following steps:

[0031] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0032] Example 2

[0033] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0034] Mix 25g of potassium hydroxide, 6g of modified zinc oxide, and 69mL of water, and stir until homogeneous.

[0035] The preparation method of the modified zinc oxide includes the following steps:

[0036] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0037] Example 3

[0038] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0039] Mix 30g of potassium hydroxide, 6g of modified zinc oxide, and 64mL of water, and stir until homogeneous.

[0040] The preparation method of the modified zinc oxide includes the following steps:

[0041] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0042] Example 4

[0043] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0044] Mix 35g of potassium hydroxide, 6g of modified zinc oxide, and 59mL of water, and stir until homogeneous.

[0045] The preparation method of the modified zinc oxide includes the following steps:

[0046] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0047] Example 5

[0048] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0049] Mix 45g of potassium hydroxide, 6g of modified zinc oxide, and 49mL of water, and stir until homogeneous.

[0050] The preparation method of the modified zinc oxide includes the following steps:

[0051] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0052] Example 6

[0053] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0054] Mix 40g of potassium hydroxide, 2g of modified zinc oxide, and 58mL of water, and stir until homogeneous.

[0055] The preparation method of the modified zinc oxide includes the following steps:

[0056] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0057] Example 7

[0058] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0059] Mix 40g of potassium hydroxide, 4g of modified zinc oxide, and 56mL of water, and stir until homogeneous.

[0060] The preparation method of the modified zinc oxide includes the following steps:

[0061] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0062] Example 8

[0063] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0064] Mix 45g of potassium hydroxide, 8g of modified zinc oxide, and 46mL of water, and stir until homogeneous.

[0065] The preparation method of the modified zinc oxide includes the following steps:

[0066] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6 g of the dried zinc oxide was added to the mixture of 600 g of ethanol and water and ultrasonically dispersed at 450 W for 40 min. After ultrasonication, the mixture was stirred for 1 h. Then, an equal volume of 4 wt% ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2 h. After cooling to room temperature, the mixture was washed three times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10 h to obtain modified zinc oxide.

[0067] Compare with Example 1

[0068] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0069] Mix 40g of potassium hydroxide, 6g of zinc oxide, and 54mL of water, and stir until homogeneous.

[0070] Compare with Example 2

[0071] A method for preparing an electrolyte for zinc-manganese batteries includes the following steps:

[0072] Mix 45g of potassium hydroxide, 8g of modified zinc oxide, and 46mL of water, and stir until homogeneous.

[0073] The preparation method of the modified zinc oxide includes the following steps:

[0074] After drying zinc oxide under vacuum at 60℃ for 8 hours, anhydrous ethanol and water were mixed at a mass ratio of 1:1.6. 6g of the dried zinc oxide was added to the mixture of 600g of ethanol and water and ultrasonically dispersed at 450W for 40min. After ultrasonication, the mixture was stirred for 1h. Then, an equal volume of 4wt% ethanol solution of 2-(2-pyridyl)ethyltrimethoxysilane was added dropwise. After the addition was completed, the temperature was raised to 70℃ and stirred for 2h. After cooling to room temperature, the mixture was washed 3 times with anhydrous ethanol, centrifuged, and the supernatant was discarded. The lower precipitate was dried under vacuum at 60℃ for 10h to obtain modified zinc oxide.

[0075] Test Example 1

[0076] 60 wt% nano zinc powder, 3 wt% sodium silicate, and 2 wt% sodium acrylate were dry-mixed. After thorough mixing, the mixture was then vacuum-wet-mixed. During stirring, 35 wt% electrolyte was added to obtain a negative electrode zinc paste. The positive electrode ring was assembled, and electrolyte was injected. Electrolyte was then injected into the separator. After standing until the separator was completely wetted, the negative electrode zinc paste was injected into the battery. Alkaline zinc-manganese batteries containing the electrolytes described in each example and the comparative example were assembled. The performance of the prepared alkaline zinc-manganese batteries was tested, and the specific results are shown in Table 1.

[0077] Table 1. Discharge performance test results of batteries containing electrolytes for zinc-manganese batteries.

[0078]

[0079]

[0080] The discharge performance test of alkaline zinc-manganese batteries is an important indicator for evaluating the battery's ability to provide electrical energy under actual use conditions. Discharge capacity, or battery capacity, represents the amount of electricity the battery can release under certain conditions (standard discharge rate, temperature, termination voltage, etc.). Alkaline zinc-manganese batteries are widely used due to their high energy density, high power density, good low-temperature performance, and long storage life. They typically use potassium hydroxide as the electrolyte, electrolytic manganese dioxide as the positive electrode active material, and zinc powder as the negative electrode active material. The discharge performance of alkaline zinc-manganese batteries is characterized by low internal resistance, the ability to maintain a high stable voltage under heavy loads, and high MnO2 utilization. Table 1 shows that the alkaline zinc-manganese battery obtained in this invention has long discharge times and a high number of discharge cycles, exhibiting excellent performance in high-current discharge and long-term battery storage. The test results show that the concentrations of potassium hydroxide and zinc oxide in the electrolyte have a certain impact on the discharge performance. Compared with Examples 1 to 5, increasing the KOH concentration is beneficial to the continuous discharge performance of the battery. Compared with Examples 6 to 8, increasing the ZnO content is beneficial to the electrical performance of the battery. However, after increasing to a certain extent, the performance will not continue to improve with the increase of concentration. This is because with the increase of concentration, the interaction between positive and negative ions increases, the ion movement rate decreases, and the conductivity decreases.

[0081] Test Example 2

[0082] The alkaline zinc-manganese batteries prepared in Test Example 1 were subjected to expansion and gas evolution performance tests. The performance results are shown in Table 2. The amount of gas evolution was measured using a gas collecting device. After the batteries were discharged, they were disassembled, and the amount of gas evolved per gram of battery was measured using the gas collecting device. The leakage test involved placing a certain number of samples from the experimental group in a 60°C high-temperature chamber and maintaining this temperature for 168 hours, then observing whether the batteries leaked. The safety test indicates whether the battery can maintain normal operation under safety hazards caused by short circuits, over-discharge, and forced current (i.e., forced current cathodic protection).

[0083] Table 2 shows the performance test results of batteries containing electrolytes used in zinc-manganese batteries.

[0084]

[0085] As can be seen from the tests in Table 2, the battery prepared with the electrolyte of the present invention exhibits good safety performance. Compared with Examples 1-5, a low KOH concentration increases the amount of gas evolution after partial discharge. Similarly, compared with Examples 6-8, a low ZnO content in Example 1 also increases the amount of gas evolution. Therefore, there is an optimal addition amount for both KOH and ZnO. Compared with Control Example 1, Example 1 modifies the zinc oxide by grafting pyridine groups onto its surface. The pyridine groups contain nitrogen atoms with lone pairs of electrons, which can form coordinate bonds with atoms on the metal surface, achieving chemisorption. Furthermore, the π electrons on the pyridine ring can form coordinate bonds with empty orbitals on the metal surface, enhancing the corrosion inhibition effect. The improved corrosion inhibition effect means a reduction in the activity of the zinc electrode, thereby effectively suppressing the self-corrosion of the zinc electrode and reducing the amount of gas evolution. Therefore, the modified zinc oxide can further improve battery life. Compared with Comparative Example 2, the trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane used in the grafting modification of Example 1 has more pyridine groups, so the corrosion inhibition effect is better than that of Comparative Example 2, and therefore the amount of gas evolution is less.

[0086] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. An electrolyte for zinc-manganese batteries, characterized in that, Including potassium hydroxide, modified zinc oxide, and water; The method for preparing the modified zinc oxide includes the following steps: After vacuum drying of zinc oxide, anhydrous ethanol and water are mixed in a certain proportion. The dried zinc oxide is added to the mixture of ethanol and water and ultrasonically dispersed at 400-500W for 30-50 min. After ultrasonication, the mixture is stirred for 1-2 h. Then, an equal volume of ethanol solution of trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane is added dropwise. After the addition is completed, the mixture is heated and stirred for 1-3 h. After cooling to room temperature, the mixture is washed three times with anhydrous ethanol, centrifuged, and the supernatant is discarded. The lower precipitate is vacuum dried to obtain modified zinc oxide. The concentration of potassium hydroxide is 25-40 wt%; The concentration of the modified zinc oxide is 2-8 wt%.

2. The electrolyte for zinc-manganese batteries as described in claim 1, characterized in that, The mass ratio of anhydrous ethanol to water is 1:1~2.

3. The electrolyte for zinc-manganese batteries as described in claim 1, characterized in that, The mass ratio of the zinc oxide to the mixture of ethanol and water is 1:80~100.

4. The electrolyte for zinc-manganese batteries as described in claim 1, characterized in that, The temperature range for the heating is 60~80℃.

5. The electrolyte for zinc-manganese batteries as described in claim 1, characterized in that, The concentration of the ethanol solution of the trimethoxy-[4-[2-(4-methyl-2-pyridyl)-4-pyridyl]butyl]silane is 4~5 wt%.

6. The electrolyte for zinc-manganese batteries as described in claim 1, characterized in that, The vacuum drying temperature is 50~60℃.

7. The electrolyte for zinc-manganese batteries as described in claim 1, characterized in that, The vacuum drying time is 8-10 hours.

8. A method for preparing an electrolyte for a zinc-manganese battery as described in any one of claims 1 to 7, characterized in that, Includes the following steps: The mixture is prepared by mixing potassium hydroxide, modified zinc oxide, and water, and stirring until homogeneous.

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