Low-cost cathode material for alkaline secondary batteries, its manufacturing method 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] The present invention relates to the technical field of positive electrode materials for alkaline secondary batteries, and more particularly to a low-cost positive electrode material for alkaline secondary batteries, a manufacturing method thereof, and applications thereof. [Background technology]

[0002] Compared to other batteries, zinc-manganese alkaline secondary batteries have advantages such as low cost, environmental friendliness, non-toxicity, and excellent safety, and are expected to be widely used in the energy storage and consumer market fields. MnO2 is a metal oxide and a semiconductor material, and is a cathode material commonly used in primary dry batteries. In zinc-manganese alkaline secondary batteries, the MnO2 cathode has low conductivity (conductivity of 10 -5 ~10 -6 S cm -1 ), poor structural stability, and other problems severely limit the widespread use of zinc-manganese alkaline secondary batteries. MnO2 undergoes large volume expansion and contraction during charging and discharging and is prone to producing electrochemically inactive low-valent manganese oxides, such as Mn3O4, which destroy the structure of the positive electrode material, reduce the amount of active material, and thereby affect the electrochemical performance of the battery. Therefore, the capacity performance, rate performance, and cycle stability of zinc-manganese alkaline secondary batteries still do not meet the needs of practical applications.

[0003] Zinc-manganese secondary batteries consist of several main components, including a positive electrode, separator, electrolyte, and negative electrode. Research on the positive electrode has focused on the development of new positive electrode materials and the modification of manganese dioxide materials. Modified MnO2, obtained through physical doping, chemical doping, and electrochemical deposition doping, has significantly improved its rechargeability. Furthermore, the reversibility of various crystalline forms of MnO2 has also been improved to a certain extent after modification. However, rechargeable zinc-manganese secondary batteries are still limited by poor cycle stability in practical applications. Therefore, the development of new positive electrode materials remains the key to technological advancement of zinc-manganese secondary batteries. Summary of the Invention [Means for solving the problem]

[0004] The present invention provides a low-cost cathode material for alkaline secondary batteries and a manufacturing method thereof to overcome the drawbacks of the MnO2 cathode material currently used in zinc-manganese alkaline secondary batteries. The cathode material manufactured by this method has higher discharge capacity, a higher discharge platform, and better cycle stability, and can be used to manufacture the cathode of zinc-manganese secondary batteries.

[0005] In order to solve the above technical problems, the technical solution used in the present invention is as follows: A low-cost cathode material for alkaline secondary batteries, the cathode material being composed of manganese dioxide and layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O], or a composite cathode material consisting of manganese dioxide and a partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b ·mH2O], or a composite cathode material consisting of manganese dioxide and layered oxyhydroxide [Ni x M y A ZOOH], or a composite cathode material consisting of manganese dioxide, a conductive material, and a 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 OOH], the composite positive electrode material having one or a mixture of a three-dimensional structure, a hierarchical porous structure, and a clad structure, M is Bi or Ti, A is one or two of Ce, Al, Zn, Ca, Mg, Co, Y, Ga, Sb, Yb, and Cu, B a- OH - , Cl - , F - , PO4 3- , SO4 2- , CO3 2- , NO3 - , BO2 - , MoO4 2- or WO4 2- and wherein 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 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 ZOOH] is 5% to 75% by mass, preferably 10% to 40% by mass.

[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, and titanium nitride, the mass percentage of the conductive material in the composite positive electrode material is 0.5% to 20%, and the manganese dioxide is one or more of α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, and 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: ball milling and sieving the manganese dioxide precursor to obtain the manganese dioxide precursor for use; A composite salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, 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 composite salt solution at 15-50°C and stirred until the pH of the suspension reaches 7-11 after the reaction is complete. 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 resulting powder is transferred to a solution prepared with one or more of alkaline hydroxides, phosphates, tungstates, molybdates, chlorides, fluorides, carbonates, metaborates, or borates, and treated at 25-200°C for 1-24 hours under inert atmosphere or air conditions. The resulting powder is then 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 and step S3 of mixing the resulting mixture with the alkaline secondary battery positive electrode material and the resulting mixture with the alkaline secondary battery positive electrode material.

[0009] The manganese dioxide and the partially oxidized layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b The composite cathode material is composed of 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: ball milling and sieving the manganese dioxide precursor to obtain the manganese dioxide precursor for use; A composite salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, 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 composite salt solution at 15-50°C and stirred until the pH of the suspension reaches 7-11 after the reaction is complete. 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 resulting powder is transferred to a solution prepared with one or more of alkaline hydroxides, phosphates, tungstates, molybdates, chlorides, fluorides, carbonates, metaborates, or borates, and treated at 25-200°C for 1-24 hours under an inert atmosphere or air condition. The resulting powder is then filtered, washed, and dried to obtain a layered hydroxide. The layered hydroxide is then 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 fully oxidized layered oxyhydroxide [Ni x M y A Z OOH], and 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 fully oxidized layered oxyhydroxide [Ni x M y A Z and step S3 of mixing the resulting mixture with the ammonium hydroxide and the ammonium hydroxide, followed by high-energy ball milling to obtain a composite cathode material.

[0010] The manganese dioxide, 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 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: ball milling and sieving the manganese dioxide precursor to obtain the manganese dioxide precursor for use; A composite salt solution is prepared by dissolving a soluble nickel salt, a soluble bismuth salt, 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 composite salt solution at 15-50°C and stirred until the pH of the suspension reaches 7-11 after the reaction is complete. 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 resulting powder is transferred to a solution prepared with one or more of alkaline hydroxides, phosphates, tungstates, molybdates, chlorides, fluorides, carbonates, metaborates, or borates, and treated at 25-200°C for 1-24 hours under inert atmosphere or air conditions. The resulting powder is then filtered, washed, and dried to obtain a layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b mH2O], and then oxidizing the layered hydroxide 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 fully oxidized layered oxyhydroxide [Ni x M y A Z OOH], and step S2 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 fully oxidized layered oxyhydroxide [Ni x M y A Zand step S3 of uniformly dispersing [OOH] in water or an organic solvent, reacting them at 15 to 90°C in a normal pressure vessel, and drying the product to obtain a composite positive electrode 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; 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 salt is one or more of potassium chloride or sodium chloride; the fluoride salt is one or more of potassium fluoride or sodium fluoride; the carbonate salt 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 an alkaline secondary battery, characterized in that it is produced from the above-mentioned low-cost positive electrode material for an alkaline secondary battery.

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

[0014] An alkaline secondary battery comprising: a battery case; and an electrode plate assembly and an electrolyte sealed in the battery case, the electrode plate assembly including a positive electrode plate, a negative electrode plate, and a separator, the positive electrode plate using the positive electrode plate for an alkaline secondary battery, and the electrolyte using an alkaline solution of potassium hydroxide, to which sodium hexafluoroantimonate is added at 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 according to the present invention is a material containing manganese dioxide and layered hydroxide [Ni x M y A Z (OH)2]·[(B a- ) b The composite negative electrode material is composed of [MnO2·mH2O], which has a three-dimensional structure. First, Bi or Ti fills the tunnels and interlayers of MnO2 during the charge and discharge process, allowing protons and electrons to flow freely between the lattices, suppressing lattice expansion, and stabilizing the lattice and active sites. Second, the introduction of other elements into the layered hydroxide strengthens the interlayer bonding force between the metal and oxygen, effectively improving the structural stability and cycle reversibility of the composite positive electrode material during the charge and discharge process. Electrochemical tests have demonstrated that, compared with non-composite positive electrode materials, the composite positive electrode material prepared by this invention has higher discharge capacity, a higher discharge platform, and better cycle stability as a positive electrode active material for alkaline secondary batteries. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a scanning electron microscope photograph of the composite positive electrode material prepared in Example 1. [Figure 2] FIG. 2 is an element distribution diagram of the composite positive electrode material produced in Example 1. [Figure 3] FIG. 1 is an XRD diagram of the composite positive electrode material prepared in Example 1. [Figure 4] 1 shows the discharge curves of the composite positive electrode material prepared in Example 1 and MnO2. [Figure 5] 1 is a scanning electron microscope photograph of the composite positive electrode material prepared in Example 13. [Figure 6] FIG. 1 is an XRD diagram of the composite cathode materials prepared in Examples 13 and 14. [Figure 7] FIG. 10 is a discharge curve diagram of the composite positive electrode material prepared in Example 13 and MnO2. DETAILED DESCRIPTION OF THE INVENTION

[0017] The above content of the present invention will be explained in more detail below using examples. However, it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples, and all technologies realized based on the above 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 - , b=0.1, m=2) composite cathode material

[0020] First, nickel nitrate, bismuth nitrate, and aluminum chloride were mixed in a molar ratio of Ni / Bi / Al = 0.8 / 0.1 / 0.1 in a draft chamber, and a 0.5 mol / L composite salt solution 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 stirred 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 resulting powder was then transferred to a 0.5 mol / L sodium chloride solution and treated at 150 °C for 12 hours under inert nitrogen gas protection. It was then filtered, washed, and dried to obtain the layered hydroxide.

[0021] Next, the manganese dioxide was ball-milled and sieved to obtain the manganese dioxide precursor, which was then ready for use. The manganese dioxide precursor was mixed with the layered hydroxide prepared above in a mass ratio of 3:1, followed by high-energy ball-milling to obtain a manganese dioxide composite nickel-bismuth multi-layered hydroxide composite cathode material. Scanning electron microscope (SEM) images, elemental distribution, XRD spectra, 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- , O.H. - , n=0.2, m=2) composite positive electrode material

[0024] First, nickel chloride, bismuth nitrate, and copper chloride were mixed in a molar ratio of Ni / Bi / Cu=0.7 / 0.2 / 0.1 in a draft chamber, and then a composite salt solution with a molar concentration of 0.4 mol / L was prepared at room temperature. Sodium 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 stirring was continued until the pH of the reaction suspension reached 9. After the reaction was completed, the resulting suspension was reacted at 90°C for 10 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The resulting powder was transferred to an alkaline solution of sodium tungstate with a molar concentration of 0.5 mol / L and treated at 120°C for 15 hours under the protection of inert gas nitrogen, filtered, and washed to obtain a layered hydroxide sample. Then, 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] The manganese dioxide is then ball milled and sieved to obtain the manganese dioxide precursor, which is then ready for use. The manganese dioxide precursor is mixed with the partially oxidized layered hydroxide prepared above in a mass ratio of 2:1, followed by high-energy ball milling to obtain a MnO2 / partially oxidized layered hydroxide composite cathode material.

[0026] Example 3

[0027] MnO2 / layered oxyhydroxide [Ni 0.6 Bi 0.2 Sb 0.2 OOH·[(A a- ) b ·mH2O](A=MoO4 2- , O.H. - , b=0.2, m=2) composite cathode material

[0028] First, nickel sulfate, bismuth nitrate, and antimony chloride were mixed in a molar ratio of Ni / Bi / Sb=0.6 / 0.2 / 0.2 in a draft chamber, and then a composite salt solution with a molar concentration of 1.0 mol / L was prepared at room temperature. Sodium hydroxide was dissolved in deionized water to prepare an alkaline solution with a molar concentration of 1 mol / L. The alkaline solution was added dropwise to the mixed salt solution at room temperature, and stirring was continued until the pH of the reaction suspension reached 8.5. After the reaction was completed, the resulting suspension was reacted at 60°C for 24 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The resulting powder was transferred to an alkaline solution of sodium molybdate with a molar concentration of 3 mol / L and treated at 180°C for 4 hours under the protection of inert gas nitrogen, filtered, washed, and dried to obtain a layered hydroxide. Then, 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] The manganese dioxide is then ball milled and sieved to obtain a manganese dioxide precursor for use. The manganese dioxide precursor and the layered oxyhydroxide prepared 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 - , n=0.2, m=2) composite positive electrode material

[0032] First, nickel acetate, bismuth nitrate, cerium nitrate, and zinc chloride were mixed in a molar ratio of Ni / Bi / Ce / Zn = 0.8 / 0.1 / 0.05 / 0.05 in a draft chamber, and then a 2.0 mol / L composite salt solution 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 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 resulting powder was then transferred to a 3.0 mol / L mixed solution of sodium fluoride, sodium phosphate, and sodium metaborate (the molar ratio of sodium fluoride, sodium phosphate, and sodium metaborate was 0.2:0.2:1) and treated at 150 °C for 12 hours under inert nitrogen gas protection. The mixture was then filtered, washed, and dried to obtain a layered hydroxide.

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

[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 - , n=0.2, m=2) / graphene composite

[0036] First, manganese dioxide was ball milled and sieved to obtain the manganese dioxide precursor for use. Next, nickel nitrate, bismuth nitrate, aluminum chloride, and yttrium nitrate were mixed in a molar ratio of Ni / Bi / Al / Y = 0.8 / 0.1 / 0.05 / 0.05 in a draft chamber, and a 0.5 mol / L composite salt solution was prepared at 25°C. Solid potassium hydroxide was dissolved in deionized water to prepare a 3 mol / L alkaline solution. The alkaline solution was added dropwise to the mixed salt solution using a peristaltic pump at 25°C, and the reaction suspension was stirred until the pH 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 resulting powder was then transferred to a 0.5 mol / L sodium chloride solution and treated at 150°C for 12 hours under inert nitrogen gas protection. It was then filtered, washed, and dried to obtain the layered hydroxide. Manganese dioxide precursor, graphene, and the layered hydroxide prepared above are dispersed in an aqueous solution in a mass ratio of 4:1:1 using ultrasonic waves, followed by freeze-drying to obtain a composite cathode material of MnO2 / layered hydroxide / graphene.

[0037] Example 6

[0038] MnO2 / layered oxyhydroxide [Ni 0.6 Bi 0.2 Sb 0.2 OOH·[(A a- ) n ·mH2O](A=MoO4 2- , O.H. - , n=0.2, m=2) / acetylene black composite cathode material

[0039] The manganese dioxide solid powder was ground and sieved to obtain the manganese dioxide precursor for use. The manganese dioxide precursor, acetylene black, and the layered oxyhydroxide prepared in Example 3 were subjected to high-energy ball milling in a mass ratio of 5:2:3 to obtain a composite cathode material of MnO2 / layered oxyhydroxide / acetylene black.

[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 - , n=0.2, m=2) / carbon nanotube composite cathode material

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

[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 - , n=0.2, m=2) / flake graphite composite positive electrode material

[0045] First, nickel acetate, bismuth nitrate, cerium nitrate, and yttrium sulfate were mixed in a draft chamber in a molar ratio of Ni / Bi / Ce / Y=0.8 / 0.1 / 0.06 / 0.04, and then a composite salt solution with a molar concentration of 2.0 mol / L was prepared at room temperature. Graphite flakes were weighed and dispersed in the composite salt solution using ultrasound. The graphite flakes and the layered hydroxide [Ni 0.8 Bi 0.1 Ce 0.06 Y 0.04 (OH)2·(A a- ) nThe mass ratio of potassium hydroxide to the mixed salt solution was controlled to 1:3. 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 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 resulting powder was then transferred to a mixed solution of sodium chloride with a molar concentration of 1.0 mol / L and treated at 100°C for 4 hours under the protection of inert nitrogen gas. It was then filtered, washed, and dried to obtain a layered hydroxide / flake graphite composite.

[0046] The manganese dioxide solid powder is ground and sieved to obtain a manganese dioxide precursor for use. The manganese dioxide precursor and the layered hydroxide / flake graphite composite material prepared above are subjected to high-energy ball milling in a mass ratio of 3:4 to obtain a MnO2 / layered hydroxide / flake graphite composite cathode material.

[0047] Fabrication of a positive electrode plate based on the composite positive electrode materials obtained in Examples 1 to 8: 0.4 g of the composite positive electrode material prepared in each Example and 0.1 g of superconducting carbon black were ground 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 prepare a positive electrode slurry. This slurry was applied to foamed nickel using a slurry mold, dried in vacuum at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to prepare a positive electrode plate.

[0048] Example 9

[0049] Preparation of 5wt% Cr(OH)3 doped positive electrode plate

[0050] 0.375 g of the composite positive electrode material prepared in Example 1, 0.025 g of chromium hydroxide, and 0.1 g of superconducting carbon black were ground in an agate mortar for 20 minutes and then uniformly mixed. Next, 0.05 g of a 2.5% by mass CMC solution and 0.05 g of a 60% by mass PTFE aqueous solution were added and uniformly mixed to prepare a positive electrode slurry. The slurry was applied to a nickel foam using a slurry mold, dried in a vacuum at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to prepare a positive electrode plate.

[0051] Example 10

[0052] Preparation of 1wt% Sr(OH)2 and 2wt% Cr2O3 doped positive electrode plate

[0053] 0.385 g of the composite positive electrode material prepared in Example 2, 0.005 g of strontium hydroxide, 0.01 g of chromium oxide, and 0.1 g of superconducting carbon black were ground 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 prepare a positive electrode slurry. The slurry was applied to a nickel foam using a slurry mold, dried in vacuum at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to prepare a positive electrode plate.

[0054] Example 11

[0055] Preparation of 2wt% Cr2O3 and 2wt% antimony-doped tin oxide doped positive electrode plates

[0056] 0.38 g of the composite positive electrode material prepared in Example 3, 0.01 g of chromium oxide, 0.01 g of antimony-doped tin oxide, and 0.1 g of superconducting carbon black were ground 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 prepare a positive electrode slurry. The slurry was applied to a nickel foam using a slurry mold, dried in vacuum at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to prepare a positive electrode plate.

[0057] Example 12

[0058] Preparation of 5wt% YbO doped positive electrode plate

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

[0060] Assembly of batteries in Examples 1 to 12: The manufactured positive electrode plate and a conventional zinc negative electrode plate were placed in a specially made mock battery case with a separator dedicated to zinc-nickel batteries between them, and an electrolyte (a 6 mol / L KOH solution containing saturated zinc oxide and 0.2% sodium hexafluoroantimonate) was poured in 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 ground 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 a nickel foam using a slurry mold, dried in vacuum at 60°C for 12 hours, and then pressed at 12 MPa for 10 seconds to produce a positive electrode plate. The resulting positive electrode plate and a conventional zinc negative electrode plate were placed in a specially designed battery case with a separator designed for zinc-nickel batteries between them. An electrolyte (6 mol / L saturated zinc oxide solution in KOH) was then poured into the battery to assemble a semi-sealed zinc-manganese secondary battery.

[0063] Battery performance test: The zinc-manganese secondary batteries prepared in Examples 1 to 12 and Comparative Example 1 were activated at 0.2 C, and then tested for capacity performance and cycle stability. After charging at 0.2 C, the batteries were left for 10 minutes, then left at 0.2 C until the voltage reached 1.0 V, 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 the above test results in Table 1 and Figure 4, the composite positive electrode material prepared according to the present invention has good cycle stability and a high discharge voltage platform. The improved cycle stability is primarily due to the modifying effect of the layered hydroxide material on the structural lattice of the MnO2 positive electrode material, particularly the presence of a large amount of beneficial metal elements and the nanolayered structure. This significantly reduces the deformation of the positive electrode during the reaction process and suppresses the generation of inactive irreversible materials, thereby improving the reversible charge-discharge performance of the positive electrode during the charge-discharge process. By doping with different excellent positive electrode additives and improving the properties of the MnO2 electrode, the cycle stability of the positive electrode can be improved. At the same time, the use of an effective electrolyte additive, sodium hexafluoroantimonate, can improve the overall electrical performance of the battery, favoring the improvement of the discharge platform and capacity of the battery.

[0066] Example 13

[0067] MnO2 / layered hydroxide [Ni 0.8 Ti 0.2 (OH)2·[(A a- ) n ·mH2O](A=NO3 - , n=0.1, m=2) composite positive electrode material

[0068] First, nickel nitrate and titanium sulfate were mixed in a molar ratio of Ni / Ti = 0.8 / 0.2, followed by a 0.5 mol / L composite salt solution 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 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 resulting powder was transferred to a 0.5 mol / L sodium nitrate solution and treated at 130°C for 1 hour under inert nitrogen gas protection. It was then filtered, washed, and dried to obtain the layered hydroxide. Next, the electrolytic manganese dioxide precursor and the resulting layered hydroxide were mixed in a mass ratio of 3:1 and subjected to high-energy ball milling to obtain the MnO2 / layered hydroxide [Ni 0.8 Ti 0.2 (OH)2·[(A a- ) n A composite cathode material with a hydroxyl group 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- , O.H. - , n=0.1, m=2) composite positive electrode material

[0071] First, nickel sulfate, titanium sulfate, and zinc sulfate were mixed in a molar ratio of Ni / Ti / Cu = 0.7 / 0.2 / 0.1 to prepare a composite salt solution with a molar concentration of 0.4 mol / L at room temperature. Sodium 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 stirred until the pH of the reaction suspension reached 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 the layered hydroxide. Manganese dioxide was ball-milled and sieved to obtain a manganese dioxide precursor. The manganese dioxide precursor and the resulting layered hydroxide were mixed in a mass ratio of 2:1 and then subjected to high-energy ball-milling to obtain a manganese dioxide composite nickel-titanium multi-layered hydroxide composite cathode material.

[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- , O.H. - , n=0.1, m=2) composite positive electrode material

[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 to prepare a composite salt solution with a molar concentration of 1.6 mol / L at room temperature. 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 stirred until the pH of the reaction suspension reached 8. After the reaction was completed, the resulting suspension was reacted at 60°C for 18 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The resulting powder was transferred to a sodium tungstate alkaline solution with a molar concentration of 2 mol / L and treated at 120°C for 4 hours under the protection of inert nitrogen gas. Then, 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 1:1, and then subjected to high-energy ball milling to obtain a MnO2 / layered hydroxide composite positive electrode material.

[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- , n=0.2, m=2) composite positive electrode material

[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, and then a 2.0 mol / L composite salt solution 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 stirred until the pH of the reaction suspension reached 9. After the reaction was completed, the resulting suspension was reacted at 80°C for 12 hours, cooled to room temperature, filtered, washed, and dried to obtain a powder. The resulting powder was then transferred to a 3.0 mol / L mixed solution of sodium fluoride and sodium molybdate (the molar ratio of sodium fluoride to sodium molybdate was 2:1), and treated under inert nitrogen gas protection at 150°C for 12 hours. The mixture was then filtered, washed, and dried to obtain a layered hydroxide. Then, under nitrogen gas protection, 5 g of the layered hydroxide was added to 100 mL of a solution containing 5 g of potassium persulfate and 1.0 M potassium hydroxide, stirred for 30 min, filtered, washed, and vacuum dried at 80°C for 5 h to obtain a partially oxidized layered hydroxide.

[0078] Manganese dioxide was ball-milled and sieved to obtain a manganese dioxide precursor. The manganese dioxide precursor and the partially oxidized layered hydroxide were mixed in a mass ratio of 5:3, and then subjected to high-energy ball-milling to obtain a MnO2 / partially oxidized layered hydroxide composite cathode material.

[0079] Example 17

[0080] MnO2 / layered oxyhydroxide [Ni 0.8 Ti 0.1 Al 0.1 OOH·[(A a- ) n ·mH2O](A=PO4 3- , n=0.2, m=2) / carbon nanotube composite cathode material

[0081] Nickel nitrate, titanium sulfate, and aluminum chloride were mixed in a molar ratio of Ni / Ti / Al = 0.8 / 0.1 / 0.1 to prepare a 0.5 mol / L composite salt solution at 25°C. Carbon nanotubes were then dispersed in the composite salt solution using ultrasound, resulting in a carbon nanotube mass percentage of approximately 2.5%. Solid 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 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 resulting powder was then transferred to a 0.5 mol / L sodium phosphate solution and treated at 150°C for 12 hours under inert nitrogen gas protection. The powder was then filtered, washed, and dried to obtain a layered hydroxide / carbon nanotube composite. Next, under nitrogen gas protection, 5 g of the layered hydroxide / carbon nanotube composite was added to 100 mL of a solution containing 15 g of potassium persulfate and 3 M potassium hydroxide, stirred for 70 minutes, filtered, washed, and vacuum dried at 60°C for 8 hours to obtain a layered oxyhydroxide / carbon nanotube composite. Finally, electrolytic manganese dioxide and the layered oxyhydroxide / carbon nanotube composite were mixed in a mass ratio of 3:2 and then ball milled to obtain a MnO2 / layered oxyhydroxide / carbon nanotube composite composite cathode material.

[0082] Example 18

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

[0084] 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 to prepare a 1.8 mol / L composite salt solution at room temperature. Potassium hydroxide solid was dissolved in deionized water to prepare a 2.5 mol / L alkaline solution. The alkaline solution was added dropwise to the mixed salt solution using a peristaltic pump at 25°C, and the resulting suspension was stirred until the pH 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 resulting powder was then transferred to a 1.0 mol / L sodium chloride solution and treated at 120°C for 3 hours under inert nitrogen gas protection. It was then filtered, washed, and dried to obtain the layered hydroxide. Next, under nitrogen gas protection, 5 g of the layered hydroxide was added to 100 mL of a solution containing 15 g of potassium persulfate and 3 M potassium hydroxide, stirred for 70 minutes, filtered, washed, and vacuum dried at 60°C for 8 hours to obtain the layered oxyhydroxide. The electrolytic manganese dioxide solid powder was polished and sieved to obtain the manganese dioxide precursor for use. The manganese dioxide precursor, titanium nitride, and the produced layered oxyhydroxide were ultrasonically dispersed in an aqueous solution in a mass ratio of 5:1:4, stirred at 50°C for 2 hours, and freeze-dried to obtain the MnO2 / layered oxyhydroxide / graphene composite cathode material.

[0085] Example 19

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

[0087] 0.385 g of the composite positive electrode material prepared in Example 15, 0.005 g of strontium hydroxide, 0.01 g of antimony-doped tin oxide, and 0.1 g of superconducting carbon black were ground 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 prepare a positive electrode slurry. The slurry was applied to foamed nickel using a slurry mold, dried in vacuum at 60°C for 12 hours, and then pressed at a pressure of 12 MPa for 10 seconds to prepare a positive electrode plate.

[0088] Assembly of batteries in Examples 13 to 19: The manufactured positive electrode plate and a conventional zinc negative electrode plate were placed in a specially made mock battery case with a separator dedicated to zinc-manganese batteries between them, and an electrolyte (a 6 mol / L KOH solution containing saturated zinc oxide and 0.2 wt% sodium hexafluoroantimonate) was poured in to assemble a semi-sealed zinc-manganese secondary battery.

[0089] (Comparative Example 2)

[0090] Commercially available manganese dioxide was used as the active material. Positive electrode plate preparation: 0.39 g of manganese dioxide, 0.01 g of bismuth oxide, and 0.1 g of superconducting carbon black were ground in an agate mortar for 20 min 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 positive electrode slurry. This slurry was applied to a nickel foam using a slurry mold, dried in vacuum at 60°C for 12 h, and then pressed at 12 MPa for 10 s to produce a positive electrode plate. The resulting positive electrode plate and a conventional zinc-manganese battery-specific separator were placed between them, placed in a specially designed simulated battery case, and electrolyte (6 mol / L saturated zinc oxide in KOH solution) was poured into the case to assemble a semi-sealed zinc-manganese secondary battery.

[0091] Battery performance test: The batteries prepared in Examples 13 to 21 and Comparative Example 2 were activated at 0.2 C, and then tested for capacity performance and cycle stability. After charging at 0.2 C, the batteries were left for 10 minutes, then allowed to cool to 1.0 V at 0.2 C, 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 the above test results in Table 2 and Figure 7, the composite positive electrode material prepared according to the present invention has good cycle stability and a high discharge voltage platform. The improved cycle stability is primarily due to the modification effect of the layered hydroxide on the lattice structure of the MnO2 positive electrode material, particularly the presence of a large amount of beneficial metal elements and the nanolayered structure. This significantly reduces the deformation of the positive electrode during the reaction process and suppresses the generation of inactive irreversible materials, thereby improving the reversible charge-discharge performance of the positive electrode during the charge-discharge process. By doping with different excellent additives and improving the properties of the MnO2 electrode, the cycle stability of the positive electrode can be improved. At the same time, the use of an effective electrolyte additive, sodium hexafluoroantimonate, can improve the overall electrical performance of the battery, favoring the improvement of the discharge platform and capacity of the battery.

[0094] The above embodiments have described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and that the above embodiments and the description are merely for illustrating the principles of the present invention. Various modifications and improvements can be made to the present invention without departing from the principles of the present invention, and all such modifications and improvements are within the scope of protection of the present invention.

Claims

1. A low-cost cathode material for alkaline secondary batteries, the cathode material comprising manganese dioxide and layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O], or a composite cathode material consisting of manganese dioxide and a partially oxidized layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O], or a composite positive electrode material consisting of manganese dioxide and layered oxyhydroxide [Ni ｘ M ｙ A Ｚ OOH], or a composite positive electrode material consisting of manganese dioxide, a conductive material and a layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] or partially oxidized layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] or layered oxyhydroxide [Ni ｘ M ｙ A Ｚ OOH], the composite positive electrode material has one or a mixture of a three-dimensional structure, a hierarchical porous structure, and a clad structure, M is Bi or Ti, A is one or two of Ce, Al, Zn, Ca, Mg, Co, Y, Ga, Sb, Yb, and Cu, B ａ- Ha, OH - , Cl - , F - , P.O. ４ ３- , S.O. ４ ２- , CO ３ ２- , NO ３ - , B.O. ２ - , MoO ４ ２- or W.O. ４ ２- and wherein 0.9≧x≧0.5, 0.3≧y≧0.1, 0.2≧z≧0.01, x+y+z=1, b>0, and m>0.

2. The layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] or partially oxidized layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] or layered oxyhydroxide [Ni ｘ M ｙ A Ｚ 2. The low-cost cathode material for alkaline secondary batteries according to claim 1, wherein the mass percentage of [OOH] is 5% to 75%.

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

4. The manganese dioxide and layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ The specific manufacturing process of the composite positive electrode material consisting of [O] is as follows: Step S1: ball milling and sieving a manganese dioxide precursor to obtain a manganese dioxide precursor for use; A soluble nickel salt, a soluble bismuth salt, a soluble titanium salt, or an A metal salt is dissolved in deionized water to prepare a composite salt solution, an alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water, the alkaline solution is added to the composite salt solution at 15-50°C, and stirring is continued until the pH of the suspension after the reaction is completed reaches 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, which is transferred to a solution prepared with one or more of alkaline hydroxides, phosphates, tungstates, molybdates, chlorides, fluorides, carbonates, metaborates, or borates, and treated in an inert atmosphere or under air conditions at 25-200°C for 1-24 hours, filtered, washed, and dried to obtain a layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] in step S2; The manganese dioxide precursor obtained in step S1 and the layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ and step S3 of mixing the mixture with the ammonium hydroxide and the ammonium hydroxide, followed by high-energy ball milling to obtain a composite cathode material.

5. The manganese dioxide and the partially oxidized layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] and a composite positive electrode material consisting of manganese dioxide and layered oxyhydroxide [Ni ｘ M ｙ A Ｚ The specific manufacturing process of the composite positive electrode material consisting of [OOH] is as follows: Step S1: ball milling and sieving a manganese dioxide precursor to obtain a manganese dioxide precursor for use; A soluble nickel salt, a soluble bismuth salt, a soluble titanium salt, or an A metal salt is dissolved in deionized water to prepare a composite salt solution, an alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water, the alkaline solution is added to the composite salt solution at 15-50°C, and stirring is continued until the pH of the suspension after the reaction is completed reaches 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, which is transferred to a solution prepared with one or more of alkaline hydroxide, phosphate, tungstate, molybdate, chloride, fluoride, carbonate, metaborate, or borate, and treated at 25-200°C for 1-24 hours under an inert atmosphere or air condition, filtered, washed, and dried to obtain a layered hydroxide, which is then 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 ・mH ２ O] or fully oxidized layered oxyhydroxide [Ni ｘ M ｙ A Ｚ OOH] in 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 ・mH ２ O] or fully oxidized layered oxyhydroxide [Ni ｘ M ｙ A Ｚ and step S3 of mixing the sintered body with the sintered body and the sintered body with the sintered body and then subjecting the sintered body to a high-energy ball milling treatment to obtain a composite cathode material.

6. 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 partially oxidized layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] or layered oxyhydroxide [Ni ｘ M ｙ A Ｚ The specific manufacturing process of the composite positive electrode material consisting of [OOH] is as follows: Step S1: ball milling and sieving a manganese dioxide precursor to obtain a manganese dioxide precursor for use; A soluble nickel salt, a soluble bismuth salt, a soluble titanium salt, or an A metal salt is dissolved in deionized water to prepare a composite salt solution, an alkaline solution is prepared by dissolving an alkaline hydroxide in deionized water, the alkaline solution is added to the composite salt solution at 15-50°C, and stirring is continued until the pH of the suspension after the reaction is completed reaches 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, which is transferred to a solution prepared with one or more of alkaline hydroxides, phosphates, tungstates, molybdates, chlorides, fluorides, carbonates, metaborates, or borates, and treated in an inert atmosphere or under air conditions at 25-200°C for 1-24 hours, filtered, washed, and dried to obtain a layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O], and 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 ・mH ２ O] or fully oxidized layered oxyhydroxide [Ni ｘ M ｙ A Ｚ OOH] in step S2; 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 ・mH ２ O] or partially oxidized layered hydroxide [Ni ｘ M ｙ A Ｚ (OH) ２ ]・[(B ａ- ) ｂ ・mH ２ O] or fully oxidized layered oxyhydroxide [Ni ｘ M ｙ A Ｚ and step S3 of uniformly dispersing the [OOH] in water or an organic solvent, reacting them at 15 to 90°C in a normal pressure vessel, and drying the product to obtain a composite cathode material.

7. 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 the molybdate is one or more of potassium molybdate or sodium molybdate; the chloride salt is one or more of potassium chloride or sodium chloride; the fluoride salt is one or more of potassium fluoride or sodium fluoride; the carbonate salt 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.

8. A positive electrode plate for an alkaline secondary battery, characterized in that it is produced from the low-cost positive electrode material for an alkaline secondary battery according to any one of claims 1 to 3.

9. 9. The positive electrode plate for an alkaline secondary battery according to claim 8, wherein an additive is added to the low-cost positive electrode material for an alkaline secondary battery in a mass fraction of 0.5% to 10%, and the additive is one or two of chromium oxide, chromium hydroxide, strontium oxide, strontium hydroxide, ytterbium oxide, or antimony-doped tin oxide.

10. 10. An alkaline secondary battery comprising: a battery case; and an electrode plate assembly and an electrolyte sealed in the battery case, the electrode plate assembly including a positive electrode plate, a negative electrode plate, and a separator, the positive electrode plate using the positive electrode plate for an alkaline secondary battery according to claim 8, and the electrolyte using a potassium hydroxide alkaline solution to which 0.1% to 2% by mass of sodium hexafluoroantimonate is added.

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