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CN-115602806-B - Preparation and application of zinc oxide-based hydrated cerium oxide carbonate composite material

CN115602806BCN 115602806 BCN115602806 BCN 115602806BCN-115602806-B

Abstract

The invention discloses a preparation method and application of a zinc oxide-based hydrated cerium oxide carbonate composite material, in particular to a preparation method and application of a Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite material, wherein the preparation method comprises the steps of salt solution preparation, alkali solution preparation, ultrasonic mixing of the salt solution and the alkali solution, pH adjustment, aging, washing and drying of a product. Compared with the traditional ZnO, the Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite material prepared by the method has larger specific surface area and higher catalytic activity.

Inventors

  • YU XIAOHUA
  • LIN YAN
  • QIN WEI
  • LI RONGXING
  • SHEN QINGFENG
  • XIE GANG
  • ZHU YIMING
  • CAI WEISONG
  • WANG LU
  • HOU YUWEI

Assignees

  • 昆明理工大学

Dates

Publication Date
20260508
Application Date
20220907

Claims (5)

  1. The preparation method of the Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite material is characterized by comprising the following steps: S1, uniformly mixing zinc nitrate and cerium nitrate according to a molar ratio of zinc ions to cerium ions of 3:0.75, and then adding deionized water to prepare a salt solution; S2, uniformly mixing sodium hydroxide and anhydrous sodium carbonate according to the molar ratio of nNaOH =2 (nZn 2+ +nCe 3+ ),nNa 2 CO 3 ＝2nCe 3+ , and then adding deionized water to prepare alkali liquor; s3, respectively carrying out ultrasonic treatment on the salt solution and the alkali liquor obtained in the steps S1 and S2 for 10min, and then standing; S4, adding deionized water into a container to serve as base solution, slowly dripping salt solution and alkali solution subjected to ultrasonic standing into the base solution under a water bath condition, stirring while dripping, controlling the pH value to be 9.5-10.5, and continuing stirring for 1h after the reaction is completed; S5, aging the reaction product obtained in the step S4 in a hydrothermal kettle for 10-12 hours, taking out the reaction product after the aging is finished, and washing the reaction product with alcohol and deionized water for 3-5 times; S6, drying the reaction product obtained in the S5 in a drying box for 10-12 hours to obtain a Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite material; the ageing temperature in the hydrothermal kettle in the step S5 is 120 ℃, and the drying temperature of the drying box in the step S6 is 60 ℃.
  2. 2. The method for preparing the Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite according to claim 1, wherein the water bath temperature in S4 is 60 ℃, and the salt solution and the alkali solution are slowly dripped into the base solution by a peristaltic pump.
  3. 3. The method of preparing a Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite according to claim 1, wherein the zinc nitrate and cerium nitrate are Zn (NO 3 ) 2 ·6H 2 O and Ce (NO 3 ) 3 ·6H 2 O).
  4. 4. The preparation method of the Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite material according to any one of claims 1 to 3, characterized by disclosing the application of the prepared Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite material in a zinc-nickel battery electrode material.
  5. 5. The use of a Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite according to claim 4, characterized in that it is realized by: Mixing the Ce 2 O(CO 3 ) 2 H 2 O/ZnO composite material with good crystallinity with zinc powder, acetylene black, CMC and PTFE according to the mass ratio of 80:6:5:4:5 to be used as a negative electrode active material of a zinc-nickel battery, pressing the mixture into a working electrode with the size of 1cm multiplied by 1cm, taking sintered nickel as a positive electrode, and forming the zinc-nickel battery in an organic glass outer package by using an electrolyte which is a KOH solution of saturated zinc oxide with the size of 6 mol/L.

Description

Preparation and application of zinc oxide-based hydrated cerium oxide carbonate composite material Technical Field The invention belongs to the technical field of new energy batteries, and particularly relates to preparation of a Ce 2O(CO3)2Hּ2 O/ZnO (zinc oxide-based hydrated cerium oxide carbonate) composite material and application of the Ce 2O(CO3)2Hּ2 O/ZnO composite material in a zinc-nickel battery. Background Compared with a lead-acid battery, the zinc-nickel battery has the advantages of high working voltage, high specific energy, high safety, low cost, faster charge and discharge, better environmental protection performance and the like, has no memory effect, can meet the discharge requirement of large current, and is an ideal substitute for the lead-acid battery. The existing zinc-nickel battery cathode material mainly comprises ZnO, and the ZnO material obviously generates dendrite growth phenomenon after tens of times of cyclic charge and discharge, and dendrite can further grow and pierce a diaphragm to cause battery failure along with the increase of the cyclic times. Compared with ZnO, the addition of rare earth elements with high hydrogen evolution overpotential can inhibit dendrite growth to a certain extent (reference FanX,YangZ,LongW.ThepreparationandelectrochemicalperformancesofthecompositematerialsofCeO2andZnOasanodematerialforNi-Znsecondarybatteries[J].ElectrochimicaActa,2013,108:741-748). shows that the preparation period of the zinc oxide monocrystal taught by the prior patent (a method for growing zinc oxide monocrystal by a hydrothermal method) (patent No. CN 200410009367.6) is longer, the production cost is higher, and the electrochemical performance of the zinc oxide monocrystal is not researched and the zinc oxide monocrystal is applied to zinc-nickel batteries, the prior patent (a method for preparing uniform-particle nano cerium oxide carbonate hydrate) (patent No. CN 201811561803.9) needs to carry out secondary pH value callback when preparing cerium oxide carbonate hydrate, and the preparation process is more complex. Disclosure of Invention Compared with physical mixing, the hydrothermal method can effectively control reaction and crystal growth by changing temperature, pressure and reaction time, so that Ce can better grow on the surface of ZnO, and a Ce 2O(CO3)2Hּ2 O/ZnO composite material with better crystallinity is generated. Compared with the traditional ZnO, the Ce 2O(CO3)2Hּ2 O/ZnO composite material prepared by the method has larger specific surface area and higher catalytic activity, and the Ce 2O(CO3)2Hּ2 O/ZnO composite material with high purity and few defects for inhibiting negative zinc dendrite can be prepared, and the material has excellent electrochemical performance in a zinc-nickel battery. In order to achieve the technical purpose, the invention is realized by the following technical scheme: The preparation method of the Ce 2O(CO3)2Hּ2 O/ZnO composite material comprises the following steps: S1, uniformly mixing zinc nitrate and cerium nitrate according to a molar ratio of zinc ions to cerium ions of 3:0.75, and then adding deionized water to prepare a salt solution; S2, uniformly mixing sodium hydroxide and anhydrous sodium carbonate according to the molar ratio of nNaOH =2 (nZn 2++nCe3+),nNa2CO3=2nCe3+, and then adding deionized water to prepare alkali liquor; s3, respectively carrying out ultrasonic treatment on the salt solution and the alkali liquor obtained in the steps S1 and S2 for 10min, and then standing; S4, adding deionized water into a container to serve as base solution, slowly dripping salt solution and alkali solution subjected to ultrasonic standing into the base solution under a water bath condition, stirring while dripping, controlling the pH value to be 9.5-10.5, and continuing stirring for 1h after the reaction is completed; S5, aging the reaction product obtained in the step S4 in a hydrothermal kettle for 10-12 hours, taking out the reaction product after the aging is finished, and washing the reaction product with alcohol and deionized water for 3-5 times; s6, drying the reaction product obtained in the S5 in a drying box for 10-12 hours to obtain a Ce 2O(CO3)2Hּ2 O/ZnO composite material; preferably, the water bath temperature in the step S4 is 60 ℃, and a peristaltic pump is used for slowly dripping the salt solution and the alkali solution into the base solution; preferably, the ageing temperature in the hydrothermal kettle in the step S5 is 120 ℃, and the drying temperature of the drying box in the step S6 is 60 ℃; Preferably, the zinc nitrate and the cerium nitrate are Zn (NO 3)26H2 O and Ce (NO 3)36H2O;Ce2O(CO3)2Hּ2 O/ZnO composite material is applied to a zinc-nickel battery electrode material; another object of the invention is to provide a method for applying the Ce 2O(CO3)2Hּ2 O/ZnO composite material: Mixing Ce 2O(CO3)2Hּ2 O/ZnO composite material with better crystallinity with zinc powder, acetylene black, sodium carb