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CN-122000332-A - Cerium doped MnCO3-Mn2O3Preparation method of composite material

CN122000332ACN 122000332 ACN122000332 ACN 122000332ACN-122000332-A

Abstract

The invention discloses a preparation method of a cerium doped MnCO 3 -Mn 2 O 3 composite material, and belongs to the technical field of water-based zinc ion batteries. Dissolving manganese nitrate aqueous solution, urea and cerium nitrate hexahydrate in purified water, and performing hydrothermal reaction, filtering, drying and calcination treatment to obtain the cerium doped MnCO 3 -Mn 2 O 3 composite material. The microstructure shows that the composite material consists of micron-sized blocky cubes with consistent orientation and triangular pyramid-shaped bulges and sphere-like particles stacked in a lamellar way, and 50-200 nm sphere-like nano particles are uniformly anchored on the surface and in gaps of the composite material. The directional anchoring structure is beneficial to constructing a continuous electron conduction network and exposing rich active interfaces to form a stable cerium doped double-phase composite system, so that the electrode reaction kinetic performance is obviously improved, and the electrochemical performance of the composite material is improved.

Inventors

  • LI LING
  • CHEN KELEI
  • YU CHUAN
  • GUO ZHIYING
  • ZHENG YONG
  • LIU LONG
  • FU NING
  • WU WEIMING
  • LIU CHAO
  • DU MENGHAN

Assignees

  • 安阳工学院

Dates

Publication Date
20260508
Application Date
20260212

Claims (9)

  1. 1. The cerium doped MnCO 3 -Mn 2 O 3 composite material is characterized by XRD diffraction peaks at 24.5 degrees, 31.65 degrees, 33.14 degrees and 55.33 degrees, XPS peaks at 288.77 eV, 529.02 eV, 530.98 eV, 641.72 eV, 653.10 eV, 884.46 eV and 916.3 eV, cerium coexists at +3 and +4 valences, and manganese coexists at +2 and +3 valences.
  2. 2. The method of preparing a cerium doped MnMnCO 3 -Mn 2 O 3 composite material as claimed in claim 1, comprising the steps of: firstly, dispersing a manganese nitrate aqueous solution in purified water, sequentially adding urea and cerium nitrate hexahydrate, and uniformly stirring; secondly, placing the uniformly stirred solution in a hydrothermal reaction kettle, performing constant-temperature reaction in an oven, and then naturally cooling; Thirdly, taking out the product from the hydrothermal reaction kettle, cleaning, filtering, and drying in an oven; And fourthly, calcining in a muffle furnace, and cooling to obtain the cerium-doped MnCO 3 -Mn 2 O 3 composite material.
  3. 3. The method for preparing the cerium doped MnCO 3 -Mn 2 O 3 composite material according to claim 2, wherein in the first step, the molar ratio of manganese nitrate to urea is 19:60.
  4. 4. The method for preparing the cerium doped MnCO 3 -Mn 2 O 3 composite material according to claim 2, wherein in the first step, the molar ratio of manganese nitrate to cerium nitrate hexahydrate is 19:1.
  5. 5. The method for preparing the cerium doped MnCO 3 -Mn 2 O 3 composite material according to claim 2, wherein in the second step, the constant temperature reaction temperature is 160 ℃ and the reaction time is 6 hours.
  6. 6. The method for preparing the cerium-doped MnCO 3 -Mn 2 O 3 composite material according to claim 2, wherein in the third step, the reaction product is washed by purified water, the reaction product is placed in the purified water to form a suspension, the suspension is subjected to ultrasonic treatment in an ultrasonic cleaner for 3 minutes, and the suspension is subjected to suction filtration for a total of 5 times.
  7. 7. The method for preparing the cerium doped MnCO 3 -Mn 2 O 3 composite material according to claim 2, wherein in the third step, the drying temperature is 80 ℃ and the drying time is 1.5 hours.
  8. 8. The method for preparing the cerium doped MnCO 3 -Mn 2 O 3 composite material according to claim 2, wherein in the fourth step, the calcination temperature is 450 ℃, the constant-temperature calcination time is 5 hours, and the temperature raising program is set to 2 hours, and the temperature is reduced to below 200 ℃ for 2 hours.
  9. 9. Use of the cerium doped MnCO 3 -Mn 2 O 3 composite according to claim 1 in aqueous zinc ion batteries.

Description

Preparation method of cerium doped MnCO 3-Mn2O3 composite material Technical Field The invention discloses a preparation method of a cerium doped MnCO 3-Mn2O3 composite material, and belongs to the technical field of water-based zinc ion batteries. Background With the transformation of global energy structures to sustainable directions, the development of efficient, safe, and low-cost electrochemical energy storage systems has become one of the core challenges in the energy technology field today. Among the many energy storage technologies, lithium ion batteries have led to consumer electronics and electric automobile markets, but they face inherent limitations such as limited lithium resources, rising cost, flammability of organic electrolytes, and explosiveness. In contrast, the water-based zinc ion battery has the outstanding advantages of high safety, low cost, environmental friendliness and the like, and is considered to have wide application prospect in the field of large-scale energy storage. However, the commercialization of aqueous zinc ion batteries is largely limited by the development of positive electrode materials. Among the numerous candidate materials, manganese-based oxides have been the main research object of the positive electrode materials of energy storage systems because of their advantages of multiple valence states, high theoretical capacity, abundant resources, no toxicity, and the like. However, they still face a serious challenge in practical applications, and the main problem is that the Jahn-Teller effect of Mn 3+ causes serious structural distortion and capacity degradation during charge and discharge. In order to overcome the bottleneck of manganese-based oxides in the application of the positive electrode of the water-based zinc ion battery, researchers have proposed various strategies, mainly including nanostructure design, material compounding, ion doping and the like. In recent years, rare earth element doping has demonstrated unique advantages in the fields of electrocatalysis, energy storage batteries, and the like. The rare earth elements can introduce lattice strain, regulate and control energy band structure, promote oxygen vacancy formation and possibly enhance the redox activity and structural firmness of the material through the synergistic effect with host metals in the doping process. The rare earth element cerium has Ce 3+/Ce4+ reversible redox pair, and has great potential in improving the cycling stability and reaction kinetics of the electrode material. Disclosure of Invention In order to solve the problem of manganese-based materials in application of water-based zinc ion batteries, the invention provides a preparation method of a cerium-doped MnCO 3-Mn2O3 composite material. Dissolving manganese nitrate aqueous solution, urea and cerium nitrate hexahydrate in purified water, and performing hydrothermal reaction, filtering, drying and calcination treatment to obtain the cerium doped MnCO 3-Mn2O3 composite material. The synthesis method is simple, low in cost and suitable for large-scale industrial production. The cerium doped MnCO 3-Mn2O3 composite material is characterized in that XRD diffraction peaks are 24.5 degrees, 31.65 degrees, 33.14 degrees and 55.33 degrees, XPS peaks are 288.77 eV,529.02 eV, 530.98 eV, 641.72 eV, 653.10 eV, 884.46 eV and 916.3 eV, cerium is coexisting with +3 and +4, and manganese is coexisting with +2 and +3. The invention also provides a preparation method of the cerium doped MnCO 3-Mn2O3 composite material, which comprises the following steps: Firstly, dispersing a manganese nitrate aqueous solution in deionized water, sequentially adding urea and cerium nitrate hexahydrate, and uniformly stirring; secondly, placing the uniformly stirred solution in a hydrothermal reaction kettle, performing constant-temperature reaction in an oven, and then naturally cooling; Thirdly, taking out the product from the hydrothermal reaction kettle, cleaning, filtering, and drying in an oven; And fourthly, calcining in a muffle furnace, and cooling to obtain the cerium-doped MnCO 3-Mn2O3 composite material. Further, in the technical scheme, in the first step, the molar ratio of manganese nitrate to urea is 19:60. Further, in the technical scheme, in the first step, the molar ratio of manganese nitrate to cerium nitrate hexahydrate is 19:1. Further, in the above technical scheme, in the second step, the constant temperature reaction temperature is 160 ℃, and the constant temperature reaction time is 6 hours. Further, in the above technical scheme, in the third step, the reaction product is washed with purified water, the reaction product is placed in purified water to form a suspension, and ultrasonic treatment is performed in an ultrasonic cleaner for 3 minutes, and then the suspension is subjected to suction filtration for a total of 5 times. Further, in the above technical scheme, in the third step, the drying temperature is 80 ℃ and the drying