Low-cost cathode material for alkaline secondary batteries, method for manufacturing the same, and applications

Abstract

The present invention discloses a low-cost positive electrode material for alkaline secondary batteries and its manufacturing method and application, belonging to the technical field of alkaline secondary batteries. The gist of the technical solution of the present invention is a low-cost positive electrode material for alkaline secondary batteries, or a composite positive electrode material consisting of manganese dioxide and a partially oxidized layered hydroxide, or a composite positive electrode material consisting of manganese dioxide and a layered oxyhydroxide, or a composite positive electrode material consisting of manganese dioxide, a conductive material, and a layered hydroxide or a partially oxidized layered hydroxide or a layered oxyhydroxide. The present invention also specifically discloses a manufacturing method for the zinc negative electrode material for alkaline secondary batteries and a zinc-nickel secondary battery using the negative electrode material. Compared with conventional manganese electrodes, the composite positive electrode material prepared by the present invention has advantages such as a higher discharge platform, a higher gram capacity, and better cycle stability, significantly improving the cycle stability and reversibility of zinc-manganese alkaline secondary batteries and improving their cycle life.

Description

[Technical Field]

[0001] This invention belongs to the technical field of positive electrode materials for alkaline secondary batteries, and more specifically, relates to a low-cost positive electrode material for alkaline secondary batteries, a method for manufacturing the same, and its applications. [Background technology]

[0002] Zinc-manganese alkaline secondary batteries have advantages over other batteries, such as lower cost, environmental friendliness, non-toxicity, and superior safety, and have the potential for widespread use in energy storage and consumer markets. MnO2 is a metal oxide and semiconductor material, and is a commonly used positive electrode material in primary dry batteries. In zinc-manganese alkaline secondary batteries, the MnO2 positive electrode has low conductivity (conductivity of 10⁻¹⁰). -5 ~10 -6 S·cm -1 Problems such as poor structural stability significantly limit the widespread use of zinc-manganese alkaline secondary batteries. MnO2 exhibits large volume expansion and contraction during the charge-discharge process and readily generates electrochemically inert low-valence manganese oxides, such as Mn3O4, which disrupt the structure of the positive electrode material, reduce the amount of active material, and thereby affect the electrochemical performance of the battery. Consequently, the capacity performance, rate performance, and cycle stability performance of zinc-manganese alkaline secondary batteries still struggle to meet the needs of practical applications.

[0003] The zinc-manganese secondary battery mainly consists of several main parts such as a positive electrode, a separator, an electrolyte, and a negative electrode. Among them, the research on the positive electrode focuses on the development of new positive electrode materials and the modification of manganese dioxide materials. The modified MnO2 obtained by physical doping, chemical doping, and electrochemical deposition doping has greatly improved its chargeability. In addition, MnO2 in various crystal forms has also obtained a certain improvement in its reversibility after modification. However, the rechargeable zinc-manganese secondary battery is still limited by the disadvantage of poor cycle stability in actual applications. Therefore, the development of new positive electrode materials is still the key to the technological progress of the zinc-manganese secondary battery.

Summary of the Invention

Means for Solving the Problems

[0004] In order to overcome the disadvantages existing in the MnO2 positive electrode material of the current zinc-manganese alkaline secondary battery, the present invention provides a low-cost positive electrode material for alkaline secondary batteries and a manufacturing method thereof. The positive electrode material manufactured by this method has a higher discharge capacity, a higher discharge platform, and better cycle stability performance, and can be used in the manufacture of the positive electrode of a zinc-manganese secondary battery.

[0005] In order to solve the above technical problems, the technical solution used in the present invention is as follows. A low-cost positive electrode material for alkaline secondary batteries, wherein the positive electrode material is a composite positive electrode material composed of manganese dioxide and layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O], or a composite positive electrode material composed of manganese dioxide and partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O], or a composite positive electrode material composed of manganese dioxide and layered oxyhydroxide [Ni x M y A ZA composite cathode material consisting of [OOH], or manganese dioxide, a conductive material and layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or layered oxyhydroxide [Ni x M y A Z A composite cathode material consisting of OOH, wherein the composite cathode material has one or more mixed structures of a three-dimensional structure, a hierarchical porous structure, or a clad structure, where M is Bi or Ti, A is one or two of Ce, Al, Zn, Ca, Mg, Co, Y, Ga, Sb, Yb, or Cu, and B a- , OH - Cl - F - , PO4 3- SO4 2- CO3 2- NO3 - , BO2 - MoO4 2- or WO4 2- A low-cost positive electrode material for alkaline secondary batteries, characterized in that one or more of the following conditions are met: 0.9≧x≧0.5, 0.3≧y≧0.1, 0.2≧z≧0.01, x+y+z=1, b>0, and m>0.

[0006] More specifically, the layered hydroxide [Ni in the composite cathode material] x M y A Z (OH)2]·[(B a- ) b ·mH2O] or partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or layered oxyhydroxide [Ni x M y A ZThe mass percentage of OOH is 5% to 75%, preferably 10% to 40%.

[0007] More specifically, the conductive material is one or two of graphene, carbon nanotubes, acetylene black, flake graphite, cobalt oxyhydroxide, nitrogen carbide, titanium carbide, niobium carbide, or titanium nitride, and the mass percentage of the conductive material in the composite cathode material is 0.5% to 20%, and the manganese dioxide is one or more of α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, or ε-MnO2, preferably γ-MnO2.

[0008] The manganese dioxide and layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b The specific manufacturing process for the composite cathode material consisting of [mH2O] is as follows: Step S1 involves ball milling the manganese dioxide precursor and sieving it to obtain the manganese dioxide precursor for use, A complex salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, or a soluble titanium salt, or a metal A salt in deionized water. An alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water. The alkaline solution is added to the complex salt solution at 15-50°C, and the mixture is stirred until the pH of the suspension after the reaction is 7-11. The resulting suspension is reacted at 50-95°C for 5-48 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder is transferred to a solution prepared with one or more of the following: alkaline hydroxide, phosphate, tungstate, molybdate, chloride, fluoride, carbonate, metaborate, or borate. The solution is treated at 25-200°C for 1-24 hours under an inert atmosphere or air conditions, filtered, washed, and dried to obtain a layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b Step S2 to obtain [mH2O], The manganese dioxide precursor obtained in step S1 and the layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b A method for producing a cathode material for alkaline secondary batteries at low cost, comprising step S3 of mixing with [mH2O] and then performing a high-energy ball milling process to obtain a composite cathode material.

[0009] The aforementioned manganese dioxide and partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b A composite cathode material consisting of [mH2O], manganese dioxide, and layered oxyhydroxide [Ni x M y A Z The specific manufacturing process for the composite cathode material consisting of OOH is as follows: Step S1 involves ball milling the manganese dioxide precursor and sieving it to obtain the manganese dioxide precursor for use, A complex salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, or a soluble titanium salt, or an A metal salt in deionized water. An alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water. The alkaline solution is added to the complex salt solution at 15-50°C, and the mixture is stirred until the pH of the suspension after the reaction is 7-11. The resulting suspension is reacted at 50-95°C for 5-48 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder is transferred to a solution prepared with one or more of the following: alkaline hydroxide, phosphate, tungstate, molybdate, chloride, fluoride, carbonate, metaborate, or borate. The solution is treated at 25-200°C for 1-24 hours under an inert atmosphere or air conditions, filtered, washed, and dried to obtain a layered hydroxide. The layered hydroxide is oxidized by chemical oxidation or electrolytic oxidation to obtain a partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b·mH2O] or completely oxidized layered oxyhydroxide [Ni x M y A Z OOH] to obtain step S2, The manganese dioxide precursor obtained in step S1 and the partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or completely oxidized layered oxyhydroxide [Ni x M y A Z OOH] are mixed, and then high-energy ball milling treatment is performed to obtain a composite cathode material in step S3, characterized in that it is a method for manufacturing a cathode material for a low-cost alkaline secondary battery.

[0010] The specific manufacturing process of the composite cathode material composed of the manganese dioxide, the conductive material and the layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or the partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or the layered oxyhydroxide [Ni x M y A Z OOH] is as follows, Performing ball milling treatment on the manganese dioxide precursor, sieving to obtain the manganese dioxide precursor and preparing it for use in step S1, A complex salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, or a soluble titanium salt, or a metal A salt in deionized water. An alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water. The alkaline solution is added to the complex salt solution at 15-50°C, and the mixture is stirred until the pH of the suspension after the reaction is 7-11. The resulting suspension is reacted at 50-95°C for 5-48 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder is transferred to a solution prepared with one or more of the following: alkaline hydroxide, phosphate, tungstate, molybdate, chloride, fluoride, carbonate, metaborate, or borate. The solution is treated at 25-200°C for 1-24 hours under an inert atmosphere or air conditions, filtered, washed, and dried to obtain a layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b Obtaining [mH2O], the layered hydroxide is oxidized by chemical oxidation or electrolytic oxidation to obtain partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or completely oxidized layered oxyhydroxide [Ni x M y A Z Step S2 to obtain OOH, The manganese dioxide precursor obtained in step S1, the conductive material, and the layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O] or completely oxidized layered oxyhydroxide [Ni x M y A ZA method for producing a cathode material for alkaline secondary batteries at low cost, comprising step S3: uniformly dispersing OOH in water or an organic solvent, reacting it in a vessel under atmospheric pressure at 15 to 90°C, and drying the product to obtain a composite cathode material.

[0011] More specifically, the soluble nickel salt is one or more of nickel nitrate, nickel sulfate, nickel acetate, or nickel chloride; the soluble bismuth salt is bismuth nitrate; the soluble titanium salt is titanium sulfate; the A metal salt is one or more of cerium nitrate, cerium chloride, aluminum nitrate, aluminum chloride, aluminum sulfate, zinc nitrate, zinc sulfate, zinc chloride, calcium acetate, calcium chloride, magnesium acetate, magnesium chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, yttrium nitrate, yttrium sulfate, yttrium chloride, gallium nitrate, antimony sulfate, antimony chloride, ytterbium nitrate, ytterbium chloride, copper chloride, copper sulfate, or copper nitrate; and the phosphate is one or more of potassium phosphate, sodium hydrogen phosphate, or sodium phosphate. The tungstate is one or more of potassium tungstate, sodium tungstate, or lithium tungstate; the molybdate is one or more of potassium molybdate or sodium molybdate; the chloride is one or more of potassium chloride or sodium chloride; the fluoride is one or more of potassium fluoride or sodium fluoride; the carbonate is one or more of potassium carbonate or sodium carbonate; the metaborate is one or more of potassium metaborate, sodium metaborate, or lithium metaborate; the borate is one or more of potassium metaborate, sodium metaborate, or lithium metaborate; and the alkaline hydroxide is one or more of sodium hydroxide, potassium hydroxide, or lithium hydroxide.

[0012] A positive electrode plate for alkaline secondary batteries, characterized by being manufactured using the above-mentioned low-cost positive electrode material for alkaline secondary batteries.

[0013] More specifically, the low-cost alkaline secondary battery positive electrode material is to which an additive in a mass fraction of 0.5% to 10% is added, and the additive is one or two of the following: chromium oxide, chromium hydroxide, strontium oxide, strontium hydroxide, ytterbium oxide, or antimond-doped tin oxide.

[0014] An alkaline secondary battery comprising a battery case, a group of electrode plates sealed within the battery case, and an electrolyte, wherein the group of electrode plates includes a positive electrode plate, a negative electrode plate, and a separator, the positive electrode plate being a positive electrode plate for alkaline secondary batteries, and the electrolyte being a potassium hydroxide alkaline solution with the addition of sodium hexafluoroantimonate in a mass fraction of 0.1% to 2%. [Effects of the Invention]

[0015] The present invention has the following advantages and beneficial effects compared to the prior art. The positive electrode material for alkaline secondary batteries described in the present invention is made of manganese dioxide and layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b The composite negative electrode material consists of [mH2O] and has a three-dimensional structure. First, Bi or Ti fills the tunnels and interlayers during the charge-discharge process of MnO2, allowing protons and electrons to flow freely between the lattice, suppressing lattice expansion, and stabilizing the lattice and active sites. Next, by introducing other elements into the layered hydroxide, the interlayer bonding force between the metal and oxygen is strengthened, effectively improving the structural stability and cycle reversibility of the composite positive electrode material during the charge-discharge process. Electrochemical tests have shown that, compared to non-composite positive electrode materials, the composite positive electrode material produced in this invention has a higher discharge capacity, a higher discharge platform, and better cycle stability performance as a positive electrode active material for alkaline secondary batteries. [Brief explanation of the drawing]

[0016] [Figure 1] This is a scanning electron microscope image of the composite cathode material manufactured in Example 1. [Figure 2] This is an elemental distribution diagram of the composite cathode material manufactured in Example 1. [Figure 3] This is an XRD diagram of the composite cathode material manufactured in Example 1. [Figure 4] This is the discharge curve of the composite cathode material and MnO2 produced in Example 1. [Figure 5] This is a scanning electron microscope image of the composite cathode material manufactured in Example 13. [Figure 6] These are XRD diagrams of the composite cathode materials manufactured in Examples 13 and 14. [Figure 7] This is a discharge curve diagram of the composite cathode material and MnO2 manufactured in Example 13. [Modes for carrying out the invention]

[0017] The above-mentioned content of the present invention will be described in more detail below with reference to examples, but it should not be understood that the scope of the subject matter of the present invention is limited to the following examples only, and all technologies realized based on the above-mentioned content of the present invention belong to the scope of the present invention.

[0018] (Example 1)

[0019] MnO2 / [Ni 0.8 Bi 0.1 Al 0.1 (OH)2·[(A a- ) b ·mH2O](A=Cl - Manufacturing of composite cathode materials (b=0.1, m=2)

[0020] First, nickel nitrate, bismuth nitrate, and aluminum chloride were mixed in a fume hood in a molar ratio of Ni / Bi / Al = 0.8 / 0.1 / 0.1. A complex salt solution with a molar concentration of 0.5 mol / L was prepared at 25°C. Potassium hydroxide was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 3 mol / L. The alkaline solution was added dropwise to the mixed salt solution using a peristaltic pump at 25°C, and the mixture was stirred continuously until the pH of the reaction suspension reached 7.5. After the reaction was complete, the resulting suspension was reacted at 80°C for 20 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a sodium chloride solution with a molar concentration of 0.5 mol / L, treated at 150°C for 12 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide.

[0021] Next, manganese dioxide is ball-milled and sieved to obtain a manganese dioxide precursor for use. The manganese dioxide precursor and the layered hydroxide produced above are mixed in a mass ratio of 3:1, and then subjected to high-energy ball milling to obtain a composite cathode material of manganese dioxide-compound nickel-bismuth multilayered hydroxide. Scanning electron microscope images, elemental distribution, XRD spectrum, and charge-discharge curves of the sample are shown in Figures 1-5.

[0022] (Example 2)

[0023] MnO2 / Partially oxidized layered hydroxide [Ni 0.7 Bi 0.2 Cu 0.1 (OH)2·[(A a- ) b ·mH2O](A=WO4 2- , OH - Manufacturing of composite cathode materials (n=0.2, m=2)

[0024] First, nickel chloride, bismuth nitrate, and copper chloride are mixed in a fume hood in a molar ratio of Ni / Bi / Cu = 0.7 / 0.2 / 0.1. A complex salt solution with a molar concentration of 0.4 mol / L is then prepared at room temperature. Sodium hydroxide is dissolved in deionized water to prepare an alkaline solution with a molar concentration of 2 mol / L. At room temperature, the alkaline solution is added dropwise to the mixed salt solution, and the mixture is stirred continuously until the pH of the reaction suspension reaches 9. After the reaction was complete, the resulting suspension was reacted at 90°C for 10 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to an alkaline sodium tungstate solution with a molar concentration of 0.5 mol / L, treated at 120°C for 15 hours under the protection of an inert gas (nitrogen), filtered, and washed to obtain a layered hydroxide sample. Subsequently, under the protection of nitrogen gas, 5 g of the layered hydroxide sample was added to 100 mL of a solution containing 5 g of potassium persulfate and 2 M potassium hydroxide, stirred for 20 minutes, filtered, washed, and vacuum-dried at 80°C for 5 hours to obtain a partially oxidized layered hydroxide.

[0025] Next, manganese dioxide is ball-milled and sieved to obtain a manganese dioxide precursor for use. The manganese dioxide precursor and the partially oxidized layered hydroxide produced above are mixed in a mass ratio of 2:1, and then subjected to high-energy ball milling to obtain a composite cathode material of MnO2 / partially oxidized layered hydroxide.

[0026] (Example 3)

[0027] MnO2 / Layered oxyhydroxide [Ni 0.6 Bi 0.2 S 0.2 OOH·[(A a- ) b ·mH2O](A=MoO4 2- , OH - Manufacturing of composite cathode material with b=0.2 and m=2

[0028] First, nickel sulfate, bismuth nitrate, and antimony chloride are mixed in a fume hood in a molar ratio of Ni / Bi / Sb = 0.6 / 0.2 / 0.2. A complex salt solution with a molar concentration of 1.0 mol / L is prepared at room temperature, and sodium hydroxide is dissolved in deionized water to prepare an alkaline solution with a molar concentration of 1 mol / L. At room temperature, the alkaline solution is added dropwise to the mixed salt solution, and the mixture is stirred until the pH of the reaction suspension reaches 8.5. After the reaction was complete, the resulting suspension was reacted at 60°C for 24 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a 3 mol / L sodium molybdate alkaline solution, treated at 180°C for 4 hours under the protection of an inert gas (nitrogen), filtered, washed, and dried to obtain a layered hydroxide. Subsequently, under the protection of nitrogen gas, 5 g of the layered hydroxide was added to 100 mL of a solution containing 15 g of potassium persulfate and 4 M potassium hydroxide, stirred for 60 minutes, filtered, washed, and vacuum-dried at 80°C for 5 hours to obtain a layered oxyhydroxide.

[0029] Next, manganese dioxide is ball-milled and sieved to obtain a manganese dioxide precursor, which is then prepared for use. The manganese dioxide precursor and the layered oxyhydroxide produced above are mixed in a mass ratio of 4:1, and then subjected to high-energy ball milling to obtain a MnO2 / layered oxyhydroxide composite cathode material.

[0030] (Example 4)

[0031] MnO2 / Layered hydroxide [Ni 0.8 Bi 0.1 Ce 0.05 Zn 0.05 (OH)2·[(A a- ) b ·mH2O](A=F - , PO4 3- , BO2 - Manufacturing of composite cathode materials (n=0.2, m=2)

[0032] First, nickel acetate, bismuth nitrate, cerium nitrate, and zinc chloride were mixed in a fume hood in a molar ratio of Ni / Bi / Ce / Zn = 0.8 / 0.1 / 0.05 / 0.05. A complex salt solution with a molar concentration of 2.0 mol / L was prepared at room temperature, and potassium hydroxide was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 2 mol / L. The alkaline solution was added dropwise to the mixed salt solution at room temperature, and the mixture was stirred until the pH of the reaction suspension reached 9. After the reaction was complete, the resulting suspension was reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a mixed solution of sodium fluoride, sodium phosphate, and sodium metaborate with a molar concentration of 3.0 mol / L (the molar ratio of sodium fluoride, sodium phosphate, and sodium metaborate was 0.2:0.2:1), treated at 150°C for 12 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide.

[0033] Next, manganese dioxide is ball-milled and sieved to obtain a manganese dioxide precursor, which is then prepared for use. The manganese dioxide precursor and the layered hydroxide produced above are mixed in a mass ratio of 5:2, and then subjected to high-energy ball milling to obtain a composite cathode material of manganese dioxide-compound nickel-bismuth multilayered hydroxide.

[0034] (Example 5)

[0035] MnO2 / Layered hydroxide [Ni 0.8 Bi 0.1 Al 0.05 Y 0.05 (OH)2·[(A a- ) n ·mH2O](A=Cl - Manufacturing of graphene composite materials (n=0.2, m=2)

[0036] First, manganese dioxide was ball-milled and sieved to obtain a manganese dioxide precursor for use. Next, nickel nitrate, bismuth nitrate, aluminum chloride, and yttrium nitrate were mixed in a fume hood in a molar ratio of Ni / Bi / Al / Y = 0.8 / 0.1 / 0.05 / 0.05. A complex salt solution with a molar concentration of 0.5 mol / L was prepared at 25°C, and potassium hydroxide solid was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 3 mol / L. The alkaline solution was added dropwise to the mixed salt solution using a peristaltic pump at 25°C, and the mixture was stirred until the pH of the reaction suspension reached 8. After the reaction was complete, the resulting suspension was reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a sodium chloride solution with a molar concentration of 0.5 mol / L, treated at 150°C for 12 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide. A composite cathode material of MnO2 / layered hydroxide / graphene can be obtained by dispersing manganese dioxide precursor, graphene, and the layered hydroxide produced above in an aqueous solution using ultrasound in a mass ratio of 4:1:1, followed by freeze-drying.

[0037] (Example 6)

[0038] MnO2 / Layered oxyhydroxide [Ni 0.6 Bi 0.2 S 0.2 OOH·[(A a- ) n ·mH2O](A=MoO4 2- , OH - Manufacturing of composite cathode material of acetylene black (n=0.2, m=2)

[0039] Solid manganese dioxide powder is polished and sieved to obtain a manganese dioxide precursor, which is then prepared for use. When the manganese dioxide precursor, acetylene black, and the layered oxyhydroxide produced in Example 3 are subjected to high-energy ball milling in a mass ratio of 5:2:3, a composite cathode material of MnO2 / layered oxyhydroxide / acetylene black can be obtained.

[0040] (Example 7)

[0041] MnO2 / Layered hydroxide [Ni 0.8 Bi 0.1 Ce 0.05 Zn 0.05 (OH)2·[(A a- ) n ·mH2O](A=F - , PO4 3- , BO2 - Manufacturing of composite cathode materials of carbon nanotubes (n=0.2, m=2)

[0042] First, manganese dioxide solid powder is polished and sieved to obtain a manganese dioxide precursor, which is then prepared for use. Next, the manganese dioxide precursor, carbon nanotubes, and the layered hydroxide produced in Example 4 are subjected to high-energy ball milling in a mass ratio of 6:1:2 to obtain a composite cathode material of MnO2 / layered hydroxide / carbon nanotubes.

[0043] (Example 8)

[0044] MnO2 / Layered hydroxide [Ni 0.8 Bi 0.1 Ce 0.06 Y 0.04 (OH)2·(A a- ) n ·mH2O](A=Cl - Manufacturing of composite cathode material of flake graphite (n=0.2, m=2)

[0045] First, nickel acetate, bismuth nitrate, cerium nitrate, and yttrium sulfate are mixed in a fume hood in a molar ratio of Ni / Bi / Ce / Y = 0.8 / 0.1 / 0.06 / 0.04. Then, a complex salt solution with a molar concentration of 2.0 mol / L is prepared at room temperature. Flake graphite is weighed and dispersed in the complex salt solution using ultrasound. The flake graphite in this solution is then mixed with the target layered hydroxide [Ni 0.8 Bi 0.1 Ce 0.06 Y 0.04 (OH)2·(A a- ) nThe mass ratio with [mH2O] is controlled to 1:3. Potassium hydroxide is dissolved in deionized water to prepare an alkaline solution with a molar concentration of 2 mol / L. At room temperature, the alkaline solution is added dropwise to the mixed salt solution and stirred until the pH of the reaction suspension reaches 9. After the reaction is complete, the resulting suspension is reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder is transferred to a mixed solution of sodium chloride with a molar concentration of 1.0 mol / L, treated at 100°C for 4 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide / flak graphite composite material.

[0046] Solid manganese dioxide powder is polished and sieved to obtain a manganese dioxide precursor, which is then prepared for use. When the manganese dioxide precursor and the layered hydroxide / flak graphite composite material produced above are subjected to high-energy ball milling in a mass ratio of 3:4, a MnO2 / layered hydroxide / flak graphite composite cathode material can be obtained.

[0047] Manufacturing of cathode plates based on the composite cathode materials obtained in Examples 1-8: 0.4 g of the composite cathode material manufactured in each example and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 min and then uniformly mixed. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and uniformly mixed to produce a cathode slurry. This slurry was then applied to foamed nickel using a slurry mold, vacuum dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce a cathode plate.

[0048] (Example 9)

[0049] Fabrication of a positive electrode plate doped with 5 wt% Cr(OH)3.

[0050] 0.375 g of the composite cathode material produced in Example 1 above, 0.025 g of chromium hydroxide, and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 minutes and then uniformly mixed. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and uniformly mixed to produce a cathode slurry. This slurry was then applied to foamed nickel using a slurry mold, vacuum-dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce a cathode plate.

[0051] (Example 10)

[0052] Fabrication of a positive electrode plate doped with 1 wt% Sr(OH)2 and 2 wt% Cr2O3.

[0053] 0.385 g of the composite cathode material produced in Example 2 above, 0.005 g of strontium hydroxide, 0.01 g of chromium oxide, and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 minutes and then uniformly mixed. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and uniformly mixed to produce a cathode slurry. This slurry was then applied to foamed nickel using a slurry mold, vacuum-dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce a cathode plate.

[0054] (Example 11)

[0055] Fabrication of a positive electrode plate doped with 2 wt% Cr2O3 and 2 wt% antimond-doped tin oxide.

[0056] 0.38 g of the composite cathode material produced in Example 3 above, 0.01 g of chromium oxide, 0.01 g of antimond-doped tin oxide, and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 minutes and mixed uniformly. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and mixed uniformly to produce a cathode slurry. This slurry was then applied to foamed nickel using a slurry mold, vacuum-dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce a cathode plate.

[0057] (Example 12)

[0058] Fabrication of a positive electrode plate doped with 5 wt% YbO.

[0059] 0.375 g of the composite cathode material produced in Example 4 above, 0.025 g of ytterbium oxide, and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 minutes and then uniformly mixed. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and uniformly mixed to produce a cathode slurry. This slurry was then applied to foamed nickel using a slurry mold, vacuum-dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce a cathode plate.

[0060] Assembly of batteries in Examples 1-12: A specially made simulated battery case was placed between the manufactured positive electrode plate and the conventional zinc negative electrode plate, with a separator specifically designed for zinc-nickel batteries in between. An electrolyte (6 mol / L KOH solution containing 0.2% sodium hexafluoroantimonate of saturated zinc oxide) was injected to assemble a semi-sealed zinc-manganese secondary battery.

[0061] (Comparative Example 1)

[0062] Commercially available manganese dioxide was used as the active material. Positive electrode plate preparation: 0.4 g of manganese dioxide and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 minutes and then uniformly mixed. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and uniformly mixed to produce a positive electrode slurry. This slurry was applied to foamed nickel using a slurry mold, vacuum dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce the positive electrode plate. The manufactured positive electrode plate and the conventional zinc negative electrode plate were placed in a specially made simulated battery case with a separator specifically for zinc-nickel batteries in between, and an electrolyte (6 mol / L KOH solution of saturated zinc oxide) was injected to assemble a semi-sealed zinc-manganese secondary battery.

[0063] Battery Performance Test: After activating the zinc-manganese secondary batteries prepared in specific Examples 1-12 and Comparative Example 1 at 0.2C, capacity performance and cycle stability performance tests were conducted. After charging at 0.2C, the batteries were left for 10 minutes, then left at 0.2C until the voltage reached 1.0V, and the capacity performance of the positive electrode material was measured after 150 cycles. The test results for the electrical performance of the zinc-manganese secondary batteries are shown in Table 1.

[0064] Table 1 Battery charge / discharge performance test [Table 1]

[0065] As can be seen from Table 1 and Figure 4 of the above test results, the composite cathode material manufactured according to the present invention has good cycle stability performance and a high discharge voltage platform. The improvement in cycle stability performance is mainly due to the modification effect of the layered hydroxide material on the lattice structure of the MnO2 cathode material, in particular the presence of a large amount of beneficial metal elements and the nanolayered structural form, which greatly reduces the deformation of the cathode during the reaction process, suppresses the generation of inert and irreversible substances, and thereby improves the reversible charge and discharge performance of the cathode during the charge and discharge process. By doping with different excellent cathode additives and improving the properties of the MnO2 electrode, the cycle stability of the cathode can be improved. At the same time, by using sodium hexafluoroantimonate, an effective electrolyte additive, the overall electrical performance of the battery can be improved, which is advantageous for improving the battery's discharge platform and capacity.

[0066] (Example 13)

[0067] MnO2 / Layered hydroxide [Ni 0.8 Ti 0.2 (OH)2·[(A a- ) n ·mH2O](A=NO3 - Manufacturing of composite cathode materials (n=0.1, m=2)

[0068] First, nickel nitrate and titanium sulfate were mixed in a molar ratio of Ni / Ti = 0.8 / 0.2. A complex salt solution with a molar concentration of 0.5 mol / L was prepared at 25°C. Potassium hydroxide was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 3 mol / L. The alkaline solution was added dropwise to the mixed salt solution using a peristaltic pump at 25°C, and the mixture was stirred until the pH of the reaction suspension reached 9. After the reaction was complete, the resulting suspension was reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a sodium nitrate solution with a molar concentration of 0.5 mol / L, treated at 130°C for 1 hour under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide. Next, an electrolytic manganese dioxide precursor and the prepared layered hydroxide were mixed in a mass ratio of 3:1, and then subjected to high-energy ball milling to obtain MnO2 / layered hydroxide [Ni 0.8 Ti 0.2 (OH)2·[(A a- ) n A composite cathode material of [mH2O] can be obtained.

[0069] (Example 14)

[0070] MnO2 / Layered hydroxide [Ni 0.75 Ti 0.15 Zn 0.1 (OH)2·[(A a- ) n ·mH2O](A=SO4 2- , OH - Manufacturing of composite cathode materials (n=0.1, m=2)

[0071] First, nickel sulfate, titanium sulfate, and zinc sulfate are mixed in a molar ratio of Ni / Ti / Cu = 0.7 / 0.2 / 0.1. A composite salt solution with a molar concentration of 0.4 mol / L is prepared at room temperature. Sodium hydroxide is dissolved in deionized water to prepare an alkaline solution with a molar concentration of 2 mol / L. The alkaline solution is added dropwise to the mixed salt solution at room temperature, and the mixture is stirred until the pH of the reaction suspension reaches 9. After the reaction is complete, the resulting suspension is reacted at 90°C for 10 hours, cooled to room temperature, filtered, washed, and dried to obtain a layered hydroxide. Manganese dioxide is ball-milled and sieved to obtain a manganese dioxide precursor. The manganese dioxide precursor and the produced layered hydroxide are mixed in a mass ratio of 2:1, and then subjected to high-energy ball milling to obtain a composite cathode material of manganese dioxide composite nickel titanium multilayered hydroxide.

[0072] (Example 15)

[0073] MnO2 / Layered hydroxide [Ni 0.7 Ti 0.1 Co 0.1 Y 0.1 (OH)2·[(A a- ) n ·mH2O](A=WO4 2- , OH - Manufacturing of composite cathode materials (n=0.1, m=2)

[0074] First, nickel sulfate, titanium sulfate, cobalt sulfate, and yttrium nitrate were mixed in a molar ratio of Ni / Ti / Co / Y = 0.7 / 0.15 / 0.1 / 0.05. A complex salt solution with a molar concentration of 1.6 mol / L was prepared at room temperature, and sodium hydroxide was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 2.5 mol / L. The alkaline solution was added dropwise to the mixed salt solution at room temperature, and the mixture was stirred until the pH of the reaction suspension reached 8. After the reaction was complete, the resulting suspension was reacted at 60°C for 18 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a 2 mol / L sodium tungstate alkaline solution, treated at 120°C for 4 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide. By ball milling manganese dioxide and sieving it to obtain a manganese dioxide precursor, and then mixing the manganese dioxide precursor with the produced layered hydroxide in a mass ratio of 1:1, a composite cathode material of MnO2 / layered hydroxide can be obtained by performing high-energy ball milling.

[0075] (Example 16)

[0076] MnO2 / Partially oxidized layered hydroxide [Ni 0.8 Ti 0.1 Ca 0.1 (OH)2·[(A a- ) n ·mH2O](A=F - MoO4 3- Manufacturing of composite cathode materials (n=0.2, m=2)

[0077] First, nickel acetate, titanium sulfate, and calcium chloride were mixed in a molar ratio of Ni / Ti / Ca = 0.8 / 0.1 / 0.1. A complex salt solution with a molar concentration of 2.0 mol / L was prepared at room temperature. Potassium hydroxide was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 2 mol / L. The alkaline solution was added dropwise to the mixed salt solution at room temperature, and the mixture was stirred until the pH of the reaction suspension reached 9. After the reaction was complete, the resulting suspension was reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was then transferred to a mixed solution of sodium fluoride and sodium molybdate with a molar concentration of 3.0 mol / L (the molar ratio of sodium fluoride to sodium molybdate was 2:1), treated at 150°C for 12 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide. Subsequently, under the protection of nitrogen gas, 5 g of layered hydroxide was added to 100 mL of a solution containing 5 g of potassium persulfate and 1.0 M potassium hydroxide. The mixture was stirred for 30 minutes, filtered, washed, and vacuum-dried at 80°C for 5 hours to obtain partially oxidized layered hydroxide.

[0078] Manganese dioxide was ball-milled and sieved to obtain a manganese dioxide precursor. After mixing the manganese dioxide precursor with the produced partially oxidized layered hydroxide in a mass ratio of 5:3, high-energy ball milling was performed to obtain a composite cathode material of MnO2 / partially oxidized layered hydroxide.

[0079] (Example 17)

[0080] MnO2 / Layered oxyhydroxide [Ni 0.8 Ti 0.1 Al 0.1 OOH·[(A a- ) n ·mH2O](A=PO4 3- Manufacturing of composite cathode materials of carbon nanotubes (n=0.2, m=2)

[0081] First, nickel nitrate, titanium sulfate, and aluminum chloride were mixed in a molar ratio of Ni / Ti / Al = 0.8 / 0.1 / 0.1. A composite salt solution with a molar concentration of 0.5 mol / L was prepared at 25°C. Then, carbon nanotubes were dispersed in the composite salt solution using ultrasound, resulting in a carbon nanotube content of approximately 2.5% by mass. Potassium hydroxide solid was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 3 mol / L. This alkaline solution was added dropwise to the mixed salt solution using a peristaltic pump at 25°C, and the mixture was stirred continuously until the pH of the reaction suspension reached 8. After the reaction was complete, the resulting suspension was reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a sodium phosphate solution with a molar concentration of 0.5 mol / L, treated at 150°C for 12 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide / carbon nanotube composite material. Subsequently, under the protection of nitrogen gas, 5 g of the layered hydroxide / carbon nanotube composite material was added to 100 mL of a solution containing 15 g of potassium persulfate and 3 M potassium hydroxide. The mixture was stirred for 70 min, filtered, washed, and vacuum-dried at 60°C for 8 hours to obtain the layered oxyhydroxide / carbon nanotube composite material. Finally, after mixing electrolytic manganese dioxide and the layered oxyhydroxide / carbon nanotube composite material in a mass ratio of 3:2, ball milling was performed to obtain a composite cathode material of MnO2 / layered oxyhydroxide / carbon nanotube composite material.

[0082] (Example 18)

[0083] MnO2 / Layered oxyhydroxide [Ni 0.6 Ti 0.15 S 0.1 Ce 0.1 Bi 0.05 OOH·[(A a- ) n ·mH2O](A=Cl - Manufacturing of composite cathode materials of titanium nitride (n=0.2, m=2)

[0084] First, nickel chloride, titanium sulfate, antimony chloride, cerium nitrate, and bismuth nitrate were mixed in a molar ratio of Ni / Ti / Sb / Ce / Bi = 0.6 / 0.15 / 0.1 / 0.1 / 0.05. A complex salt solution with a molar concentration of 1.8 mol / L was prepared at room temperature. Potassium hydroxide solid was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 2.5 mol / L. The alkaline solution was added dropwise to the mixed salt solution using a peristaltic pump at 25°C, and the mixture was stirred continuously until the pH of the reaction suspension reached 8.5. After the reaction was complete, the resulting suspension was reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The obtained powder was transferred to a sodium chloride solution with a molar concentration of 1.0 mol / L, treated at 120°C for 3 hours under the protection of inert nitrogen gas, filtered, washed, and dried to obtain a layered hydroxide. Subsequently, under the protection of nitrogen gas, 5 g of layered hydroxide was added to 100 mL of a solution containing 15 g of potassium persulfate and 3 M potassium hydroxide, stirred for 70 min, filtered, washed, and vacuum-dried at 60°C for 8 hours to obtain layered oxyhydroxide. Electrolytic manganese dioxide solid powder was polished and sieved to obtain a manganese dioxide precursor for use. The manganese dioxide precursor, titanium nitride, and the prepared layered oxyhydroxide were dispersed in an aqueous solution in a mass ratio of 5:1:4 using ultrasound, stirred at 50°C for 2 hours, and freeze-dried to obtain a composite cathode material of MnO2 / layered oxyhydroxide / graphene.

[0085] (Example 19)

[0086] Fabrication of positive electrode plates doped with 1 wt% Sr(OH)2 and 2 wt% Sb-doped SnO.

[0087] 0.385 g of the composite cathode material produced in Example 15 above, 0.005 g of strontium hydroxide, 0.01 g of antimond-doped tin oxide, and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 minutes and mixed uniformly. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and mixed uniformly to produce a cathode slurry. This slurry was then applied to foamed nickel using a slurry mold, vacuum-dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce a cathode plate.

[0088] Battery assembly for Examples 13-19: A specially designed simulated battery case was placed between the manufactured positive electrode plate and the conventional zinc negative electrode plate, with a separator specifically for zinc-manganese batteries in between. An electrolyte (6 mol / L KOH solution of saturated zinc oxide containing 0.2 wt% sodium hexafluoroantimonate) was injected to assemble a semi-sealed zinc-manganese secondary battery.

[0089] (Comparative Example 2)

[0090] Commercially available manganese dioxide was used as the active material. Preparation of the positive electrode plate: 0.39 g of manganese dioxide, 0.01 g of bismuth oxide, and 0.1 g of superconducting carbon black were polished in an agate mortar for 20 minutes and then mixed uniformly. Next, 0.05 g of a 2.5% CMC solution and 0.05 g of a 60% PTFE aqueous solution were added and mixed uniformly to produce a positive electrode slurry. This slurry was applied to foamed nickel using a slurry mold, vacuum-dried at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to produce the positive electrode plate. The manufactured positive electrode plate and the conventional zinc negative electrode plate were placed in a specially made simulated battery case with a separator specifically for zinc-manganese batteries in between, and an electrolyte (6 mol / L KOH solution of saturated zinc oxide) was injected to assemble a semi-sealed zinc-manganese secondary battery.

[0091] Battery Performance Test: After activating the batteries prepared in specific Examples 13-21 and Comparative Example 2 at 0.2C, capacity performance and cycle stability tests were performed. After charging at 0.2C, the batteries were left for 10 minutes, then left at 0.2C until the voltage reached 1.0V, and the capacity performance of the positive electrode material was measured after 150 cycles. The test results for the electrical performance of the batteries are shown in Table 2.

[0092] Table 2 Battery charge / discharge performance test [Table 2]

[0093] As can be seen from Table 2 and Figure 7 of the above test results, the composite cathode material manufactured according to the present invention has good cycle stability performance and a high discharge voltage platform. The improvement in cycle stability performance is mainly due to the modification effect of the layered hydroxide on the lattice structure of the MnO2 cathode material, in particular the presence of a large amount of beneficial metal elements and the nanolayered structural form, which greatly reduces the deformation of the cathode during the reaction process, suppresses the generation of inert and irreversible substances, and thereby improves the reversible charge and discharge performance of the cathode during the charge and discharge process. The cycle stability performance of the cathode can be improved by doping with different excellent additives and improving the properties of the MnO2 electrode. At the same time, by using sodium hexafluoroantimonate, an effective electrolyte additive, the overall electrical performance of the battery can be improved, which is advantageous for improving the battery's discharge platform and capacity.

[0094] The above embodiments illustrate the basic principles, main features, and advantages of the present invention. Those skilled in the art will understand that the present invention is not limited to the above embodiments, and that the above embodiments and specification are merely for illustrating the principles of the present invention. The present invention can be modified and improved in various ways without departing from the principles of the present invention, and all such modifications and improvements will fall within the scope of protection of the present invention.

Claims

1. A low-cost positive electrode material for alkaline secondary batteries, The positive electrode material for the alkaline secondary battery is manganese dioxide and a layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ·[(B ａ－ ) ｂ ·mH ２ O], or the composite positive electrode material composed of the manganese dioxide and a partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ·[(B ａ－ ) ｂ ·mH ２ O], or the composite positive electrode material composed of the manganese dioxide and a layered oxyhydroxide [Ni ｘ M ｙ A ｚ OOH], or the composite positive electrode material composed of the manganese dioxide, a conductive material and the layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ·[(B ａ－ ) ｂ ·mH ２ O] or the partially of the partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ·[(B ａ－ ) ｂ ·mH ２ O] or the layered oxyhydroxide [Ni ｘ M ｙ A ｚ OOH], and The composite cathode material has a three-dimensional structure, where M is Bi or Ti, A is one or two of Ce, Al, Zn, Ca, Mg, Co, Y, Ga, Sb, Yb, or Cu, and B ａ－ OH-, Cl-, F-, PO ４ ３－ SO ４ ２－ CO ３ ２－ NO ３ － , BO ２ － MoO ４ ２－ or WO ４ ２－ One or more of the following conditions must be met: 0.9≧x≧0.5, 0.3≧y≧0.1, 0.2≧z≧0.01, x+y+z=1, b>0, m>0. A low-cost cathode material for alkaline secondary batteries, characterized in that the mass percentage range of the layered hydroxide [Ni x My A z (OH) 2]・[(Ba-) b・mH 2 O] or the partially oxidized layered hydroxide [Ni x My A z (OH) 2]・[(Ba-) b・mH 2 O] or the layered oxyhydroxide [Ni x My A z OOH] in the composite cathode material is 5% to 75%.

2. The conductive material is one or two of the following: graphene, carbon nanotubes, acetylene black, flake graphite, cobalt oxyhydroxide, nitrogen carbide, titanium carbide, niobium carbide, or titanium nitride. The mass percentage range of the conductive material in the composite cathode material is 0.5% to 20%, and the manganese dioxide is α-MnO ２ β-MnO ２ γ-MnO ２ δ-MnO ２ or ε-MnO ２ A low-cost positive electrode material for an alkaline secondary battery according to claim 1, characterized in that it is one or more of the following.

3. The manganese dioxide and the layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ ・mH ２ The manufacturing process for composite cathode materials consisting of O is as follows: Step S1 involves ball milling a manganese dioxide precursor and sieving it to obtain a manganese dioxide precursor ready for use. A complex salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, or a soluble titanium salt, or an A metal salt in deionized water. An alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water. The alkaline solution is added to the complex salt solution at 15-50°C, and the mixture is stirred until the pH of the suspension after the reaction is 7-11. The suspension is reacted at 50-95°C for 5-48 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The powder is transferred to a solution prepared with one or more of the alkaline hydroxide, phosphate, tungstate, molybdate, chloride, fluoride, carbonate, metaborate, or borate, treated at 25-200°C for 1-24 hours under an inert atmosphere or air conditions, filtered, washed, and dried to obtain the layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ ・mH ２ Step S2 to obtain O, The manganese dioxide precursor prepared for use obtained in step S1 and the layered hydroxide [Ni obtained in step S2 ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ ・mH ２ A method for producing a low-cost cathode material for an alkaline secondary battery according to claim 1, characterized by comprising step S3 of mixing with [O] and then performing a high-energy ball milling process to obtain the composite cathode material.

4. The manganese dioxide and the partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ ・mH ２ A composite cathode material consisting of [O], manganese dioxide and the layered oxyhydroxide [Ni ｘ M ｙ A ｚ The manufacturing process for composite cathode materials consisting of OOH is as follows: Step S1 involves ball milling a manganese dioxide precursor and sieving it to obtain a manganese dioxide precursor ready for use. Dissolve a soluble nickel salt, a soluble bismuth salt or a soluble titanium salt, and an A metal salt in deionized water to prepare a composite salt solution, dissolve an alkaline hydroxide in deionized water to prepare an alkaline solution, add the alkaline solution to the composite salt solution at 15-50 °C, continue stirring until the pH of the suspension after the reaction ends reaches 7-11, react the suspension at 50-95 °C for 5-48 h, cool to room temperature, then filter, wash, and dry to obtain a powder. Transfer the powder to a solution prepared with one or more of the alkaline hydroxide, phosphate, tungstate, molybdate, chloride, fluoride, carbonate, metaborate, or borate, and treat it at 25-200 °C for 1-24 h under an inert atmosphere or air conditions, filter, wash, and dry to obtain a layered hydroxide. Oxidize the layered hydroxide by a method of chemical oxidation or electrolytic oxidation to obtain the partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ・[(B ａ－ ) ｂ ・mH ２ O] or the completely oxidized layered oxyhydroxide [Ni ｘ M ｙ A ｚ OOH] in step S2; The manganese dioxide precursor for use obtained in step S1 and the partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ·[(B ａ－ ) ｂ ·mH ２ O] or the completely oxidized layered oxyhydroxide [Ni ｘ M ｙ A ｚ OOH] are mixed, and then a high-energy ball milling treatment is performed to obtain the composite cathode material in step S3, characterized in that it includes the method for manufacturing a cathode material for a low-cost alkaline secondary battery according to claim 1.

5. The manganese dioxide, the conductive material, and the layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ mH ２ O] or the partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ mH ２ O] or the layered oxyhydroxide [Ni ｘ M ｙ A ｚ The manufacturing process for composite cathode materials consisting of OOH is as follows: Step S1 involves ball milling a manganese dioxide precursor and sieving it to obtain a manganese dioxide precursor ready for use. A complex salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, or a soluble titanium salt, or an A metal salt in deionized water. An alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water. The alkaline solution is added to the complex salt solution at 15-50°C, and the mixture is stirred until the pH of the suspension after the reaction is 7-11. The suspension is reacted at 50-95°C for 5-48 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The powder is transferred to a solution prepared with one or more of the alkaline hydroxide, phosphate, tungstate, molybdate, chloride, fluoride, carbonate, metaborate, or borate, treated at 25-200°C for 1-24 hours under an inert atmosphere or air conditions, filtered, washed, and dried to obtain the layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ mH ２ Obtaining O, the layered hydroxide is oxidized by chemical oxidation or electrolytic oxidation to obtain the partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ mH ２ O] or the completely oxidized layered oxyhydroxide [Ni ｘ M ｙ A ｚ Step S2 to obtain OOH, The manganese dioxide precursor obtained in step S1, the conductive material, and the layered hydroxide [Ni obtained in step S2 ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ mH ２ O] or the partially oxidized layered hydroxide [Ni ｘ M ｙ A ｚ (OH) ２ ]・[(B ａ－ ) ｂ mH ２ O] or the completely oxidized layered oxyhydroxide [Ni ｘ M ｙ A ｚ A method for producing a low-cost cathode material for an alkaline secondary battery according to claim 1, characterized by comprising step S3: uniformly dispersing OOH in water or an organic solvent, reacting it in a vessel under atmospheric pressure at 15 to 90°C, and drying the product to obtain the composite cathode material.

6. The soluble nickel salt is one or more of nickel nitrate, nickel sulfate, nickel acetate, or nickel chloride; the soluble bismuth salt is bismuth nitrate; the soluble titanium salt is titanium sulfate; the A metal salt is one or more of cerium nitrate, cerium chloride, aluminum nitrate, aluminum chloride, aluminum sulfate, zinc nitrate, zinc sulfate, zinc chloride, calcium acetate, calcium chloride, magnesium acetate, magnesium chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, yttrium nitrate, yttrium sulfate, yttrium chloride, gallium nitrate, antimony sulfate, antimony chloride, ytterbium nitrate, ytterbium chloride, copper chloride, copper sulfate, or copper nitrate; the phosphate is one or more of potassium phosphate, sodium hydrogen phosphate, or sodium phosphate; the tungstate is potassium tungstate, tungsten A method for producing a low-cost positive electrode material for an alkaline secondary battery according to any one of claims 3 to 5, characterized in that the salt is one or more of sodium tungstate or sodium molybdate, the molybdate is one or more of potassium molybdate or sodium molybdate, the chloride is one or more of potassium chloride or sodium chloride, the fluoride is one or more of potassium fluoride or sodium fluoride, the carbonate is one or more of potassium carbonate or sodium carbonate, the metaborate is one or more of potassium metaborate, sodium metaborate or lithium metaborate, the borate is one or more of potassium metaborate, sodium metaborate or lithium metaborate, and the alkaline hydroxide is one or more of sodium hydroxide, potassium hydroxide or lithium hydroxide.

7. A positive electrode plate for an alkaline secondary battery, characterized in that it is manufactured using the low-cost positive electrode material for alkaline secondary batteries described in any one of claims 1 to 2.

8. The aforementioned low-cost alkaline secondary battery positive electrode material is to which an additive in a mass fraction range of 0.5% to 10% is added. The positive electrode plate for an alkaline secondary battery according to claim 7, characterized in that the additive is one or two of chromium oxide, chromium hydroxide, strontium oxide, strontium hydroxide, ytterbium oxide, or antimond-doped tin oxide.

9. The battery case comprises a battery case, a group of electrode plates sealed inside the battery case, and an electrolyte. The aforementioned electrode plate group includes a positive electrode plate, a negative electrode plate, and a separator. The positive electrode plate is the positive electrode plate for alkaline secondary batteries described in claim 7. The aforementioned electrolyte is characterized by using a potassium hydroxide alkaline solution and having sodium hexafluoroantimonate added in a mass fraction range of 0.1% to 2%.

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