CN109603699B - Preparation of MnCO by limited hydrothermal system3Method for @ RF hollow composite microspheres - Google Patents
Preparation of MnCO by limited hydrothermal system3Method for @ RF hollow composite microspheres Download PDFInfo
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Abstract
The invention relates to a method for preparing MnCO by a limited hydrothermal system3The preparation process of the @ RF hollow composite microsphere includes three steps: hydrothermal synthesis and phenolic coating of dumbbell-shaped manganese carbonate to prepare MnCO with core-shell structure3@ RF composite microsphere and synthesis of MnCO through conversion under limited hydrothermal condition3@ RF hollow composite microspheres. Wherein, the synthesis of a limited (phenolic aldehyde layer coated) hydrothermal system is key, the formation of the hollow structure of the composite microsphere is determined, and meanwhile, no chemical agent is added in the process, and only MnCO is added3The @ RF composite microspheres are dispersed in an aqueous solution. The existence of the phenolic aldehyde layer ensures the formation of a hollow structure, improves the conductivity of the manganese carbonate microsphere and inhibits the volume change of the manganese carbonate in the using process. The hollow structure may also buffer the volume change of the manganese carbonate. MnCO3The preparation process of the @ RF hollow composite microspheres is mature, substances which are harmful to the environment are not used in the process, the raw materials are easy to obtain, and the @ RF hollow composite microspheres have potential application values in the fields of environmental science, biomedicine and the like while serving as the negative electrode materials of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of core-shell composite microsphere materials, and relates to a method for preparing MnCO by using a limited hydrothermal system3A method of @ RF hollow composite microspheres.
Background
At present, due to the serious environmental pollution problem caused by the excessive use of the conventional fuel, the lithium ion battery, which is a secondary battery that can be recycled and has low environmental hazard, is receiving more and more attention. As an important component of lithium ion batteries, the negative electrode material has a crucial impact on the performance of the battery. However, the theoretical capacity of the commercial lithium ion battery cathode material is lower(372mAh/g) and poor cycling performance carbon-based materials such as graphene. In order to improve the performance of the lithium ion battery, manganese carbonate (MnCO) is used3) The research of the transition metal carbonate as a representative as a novel lithium ion battery cathode material is continuously and deeply carried out. Manganese carbonate has a high theoretical capacity (>1000mAh/g), and good cycle performance. However, manganese carbonate also has problems of poor conductivity, large volume change during charge/discharge, and the like. An effective way to address these problems is to compound manganese carbonate with other materials to improve the overall performance of manganese carbonate. Manganese carbonate composite microspheres doped with nickel carbonate are prepared by Wangjing and the like (CN201510621387.7), wherein the molar ratio of nickel carbonate to manganese carbonate is 1: 100-30: 100, the first discharge capacity reaches 1500mAh/g, and the capacity is still higher than 500mAh/g after 100 times of circulation. The manganese carbonate/ferroferric oxide/graphene ternary composite material is prepared by Xiaoxiao et al (CN 201710408312.X), and the capacity is 532mAh g after the ternary composite material is circulated for 1000 times under the current density of 1000mA/g-1. Zhang Jianxin et al (CN201610333350.9) prepares the carbon-coated manganese carbonate microsphere in situ by a one-step method, and the initial capacity is 998mAh g at the current density of 100mA/g-1Capacity of 430mAh g after 100 cycles-1. Although the composite form of the manganese carbonate composite material is various at present, the preparation of hollow MnCO under a limited (phenolic aldehyde layer coated) hydrothermal system is not seen3Report of @ RF composite microspheres.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a limited hydrothermal system for preparing MnCO3A method of @ RF hollow composite microspheres.
Technical scheme
Preparation of MnCO by limited hydrothermal system3The method for @ RF hollow composite microspheres is characterized by comprising the following steps:
step 1: mixing anhydrous manganese chloride, urea, trisodium citrate dihydrate and sodium polyacrylate;
the mass ratio of the anhydrous manganese chloride to the urea to the sodium citrate dihydrate to the sodium polyacrylate is 1: 1.6-1.7: 5-5.2: 0.9-1.0;
the molecular weight of the sodium polyacrylate is 800-1000 ten thousand;
the mass concentration of the anhydrous manganese chloride is 7.8-8.0kg/m3；
Step 2: adding deionized water, placing on a magnetic stirrer, starting stirring, and heating to completely dissolve;
and step 3: cooling to room temperature, transferring the solution into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle, putting the stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle into an oven, setting the temperature to be 170-180 ℃, and carrying out heat preservation reaction for 5-6 hours; cooling to room temperature, washing with deionized water, centrifuging, and freeze drying to obtain dumbbell-shaped manganese carbonate MnCO3；
And 4, step 4: dispersing and dissolving dumbbell-shaped manganese carbonate and resorcinol in a mixed solution of ethanol and water, and performing ultrasonic treatment for more than 5min to obtain a suspension;
the dumbbell-shaped MnCO3 andthe mass ratio of the resorcinol is 1: 5-6;
the volume ratio of water to ethanol in the mixed solution is 1: 1.8-2;
the mass concentration of the dumbbell-shaped manganese carbonate is 0.8-1.0kg/m3；
And 5: stirring the suspension at the temperature of 25-35 ℃, adding 37-40% by mass of formaldehyde water solution, stirring for 20-40 min, and adding 25% by mass of ammonia water; reacting for 8-12 h at constant temperature, washing the obtained product with absolute ethyl alcohol, performing centrifugal separation, and performing vacuum drying treatment to obtain the dumbbell-shaped MnCO3@ RF composite microspheres, wherein RF is phenolic;
the mass ratio of the dumbbell-shaped manganese carbonate to the formaldehyde aqueous solution is 1: 6-7;
the mass ratio of the dumbbell-shaped manganese carbonate to the ammonia water is 1: 35-40;
step 6: weighing the prepared dumbbell-shaped MnCO3Uniformly dispersing the @ RF composite microspheres in deionized water to obtain a suspension, transferring the suspension into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle, placing the reaction kettle in an oven, setting the temperature to be 200-220 ℃, and keeping the temperature for 24-36 hours; wherein MnCO3@ RF of 1.5-2.0kg/m3；
And 7:cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
The water is deionized water.
The ethanol adopts absolute ethanol.
And the stirring speed in the step 5 is 300-500 rpm.
Advantageous effects
The invention provides a method for preparing MnCO by using a limited hydrothermal system3The preparation process of the @ RF hollow composite microsphere includes three steps: hydrothermal synthesis and phenolic coating of dumbbell-shaped manganese carbonate to prepare MnCO with core-shell structure3@ RF composite microsphere and synthesis of MnCO through conversion under limited hydrothermal condition3@ RF hollow composite microspheres. Wherein, the synthesis of a limited (phenolic aldehyde layer coated) hydrothermal system is key, the formation of the hollow structure of the composite microsphere is determined, and meanwhile, no chemical agent is added in the process, and only MnCO is added3The @ RF composite microspheres are dispersed in an aqueous solution. The existence of the phenolic aldehyde layer ensures the formation of a hollow structure, improves the conductivity of the manganese carbonate microsphere and inhibits the volume change of the manganese carbonate in the using process. The hollow structure may also buffer the volume change of the manganese carbonate. MnCO3The preparation process of the @ RF hollow composite microspheres is mature, substances which are harmful to the environment are not used in the process, the raw materials are easy to obtain, and the @ RF hollow composite microspheres have potential application values in the fields of environmental science, biomedicine and the like while serving as the negative electrode materials of the lithium ion battery.
Drawings
FIG. 1 is an SEM photograph of dumbbell-shaped manganese carbonate
FIG. 2 is a dumbbell-shaped MnCO3TEM photograph of @ RF composite microspheres
FIG. 3 is a dumbbell-shaped MnCO3TEM and SEM photograph of @ RF hollow composite microsphere
FIG. 4 is a dumbbell-shaped MnCO3XRD spectrogram of @ RF hollow composite microsphere
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1 dumbbell MnCO3@ RF hollow composite microsphere
Weighing 0.52g of anhydrous manganese chloride, 0.84g of urea, 2.60g of trisodium citrate dihydrate and 0.52g of sodium polyacrylate (molecular weight of 800-; weighing 0.32g of dumbbell-shaped manganese carbonate and 1.92g of resorcinol, dispersing and dissolving in 350mL of ethanol water solution (the volume ratio of absolute ethanol to deionized water is 2:1), performing ultrasonic treatment for more than 5min to obtain a suspension, adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotation speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 2.24g of formaldehyde water solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 11.20g of ammonia water with the mass fraction of 25% into the three-necked bottle, reacting at constant temperature for 8h, washing a product with absolute ethyl alcohol, performing centrifugal separation, and performing vacuum drying treatment to obtain the dumbbell-shaped MnCO3@ RF composite microspheres (RF is phenolic); weighing the prepared dumbbell-shaped MnCO30.13g of @ RF composite microspheres are uniformly dispersed in 65mL of deionized water to obtain suspension, the suspension is transferred into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle and placed in a drying oven, the temperature is set to be 200 ℃, and the temperature is kept for 24 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
Example 2 dumbbell MnCO3@ RF hollow composite microsphere
Weighing 0.56g of anhydrous manganese chloride, 0.90g of urea, 2.80g of trisodium citrate dihydrate and 0.56g of sodium polyacrylate (molecular weight of 800 plus one 1000 ten thousand) in a beaker, adding 70mL of deionized water into the beaker, placing the beaker on a magnetic stirrer, starting stirring, heating to completely dissolve the sodium polyacrylate, cooling, transferring the solution into a stainless steel-polytetrafluoroethylene-lined high-pressure reaction kettle, placing the kettle into an oven, setting the temperature to be 170 ℃, carrying out heat preservation reaction for 6 hours, taking out the solution, cooling to room temperature, washing with deionized water, carrying out centrifugal separation, and freeze-drying to obtain the dumbbell-shaped dumbbellManganese carbonate; weighing 0.36g of dumbbell-shaped manganese carbonate and 2.16g of resorcinol, dispersing and dissolving in 400mL of ethanol water solution (the volume ratio of absolute ethanol to deionized water is 2:1), performing ultrasonic treatment for more than 5min to obtain a suspension, adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotation speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 2.52g of formaldehyde water solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 12.60g of ammonia water with the mass fraction of 25% into the three-necked bottle, reacting at constant temperature for 8h, washing a product with absolute ethyl alcohol, performing centrifugal separation, and performing vacuum drying treatment to obtain the dumbbell-shaped MnCO3@ RF composite microspheres (RF is phenolic); weighing the prepared dumbbell-shaped MnCO30.14g of @ RF composite microspheres are uniformly dispersed in 70mL of deionized water to obtain suspension, the suspension is transferred into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle and placed in an oven, the temperature is set to be 200 ℃, and the temperature is kept for 24 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
Example 3 dumbbell MnCO3@ RF hollow composite microsphere
Weighing 0.60g of anhydrous manganese chloride, 0.96g of urea, 3.00g of trisodium citrate dihydrate and 0.60g of sodium polyacrylate (molecular weight of 800 plus 1000 ten thousand) in a beaker, adding 70mL of deionized water into the beaker, placing the beaker on a magnetic stirrer, starting stirring, heating to completely dissolve the sodium polyacrylate, cooling, transferring the solution into a stainless steel-polytetrafluoroethylene-lined high-pressure reaction kettle, placing the kettle into an oven, setting the temperature to be 180 ℃, keeping the temperature for reaction for 5 hours, taking out the solution, cooling the solution to room temperature, washing the solution with deionized water, performing centrifugal separation, and performing freeze drying to obtain dumbbell-shaped manganese carbonate; weighing 0.41g of dumbbell-shaped manganese carbonate and 2.46g of resorcinol, dispersing and dissolving in 450mL of ethanol water solution (the volume ratio of absolute ethanol to deionized water is 2:1), performing ultrasonic treatment for more than 5min to obtain suspension, adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotation speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 2.87g of formaldehyde water solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 14.35g of ammonia water with the mass fraction of 25% into the three-necked bottle, reacting at constant temperature for 10h, and subjecting the product to absolute ethyl alcoholCleaning, centrifugally separating and vacuum drying to obtain the dumbbell-shaped MnCO3@ RF composite microspheres (RF is phenolic); weighing the prepared dumbbell-shaped MnCO30.15g of @ RF composite microspheres are uniformly dispersed in 75mL of deionized water to obtain suspension, the suspension is transferred into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle and placed in an oven, the temperature is set to be 210 ℃, and the temperature is kept for 28 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
Example 4 dumbbell MnCO3@ RF hollow composite microsphere
Weighing 0.64g of anhydrous manganese chloride, 1.03g of urea, 3.20g of trisodium citrate dihydrate and 0.64g of sodium polyacrylate (with the molecular weight of 800 plus one million) in a beaker, adding 80mL of deionized water into the beaker, placing the beaker on a magnetic stirrer, starting stirring, heating to completely dissolve the sodium polyacrylate, cooling, transferring the solution into a stainless steel-polytetrafluoroethylene-lined high-pressure reaction kettle, placing the kettle into an oven, setting the temperature to be 180 ℃, keeping the temperature for reaction for 6 hours, taking out the solution, cooling the solution to room temperature, washing the solution with deionized water, performing centrifugal separation, and performing freeze drying to obtain dumbbell-shaped manganese carbonate; weighing 0.45g of dumbbell-shaped manganese carbonate and 2.70g of resorcinol, dispersing and dissolving in 500mL of ethanol water solution (the volume ratio of absolute ethanol to deionized water is 2:1), performing ultrasonic treatment for more than 5min to obtain a suspension, adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotation speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 3.15g of formaldehyde aqueous solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 15.75g of ammonia water with the mass fraction of 25% into the three-necked bottle, reacting at constant temperature for 10h, washing the product with absolute ethyl alcohol, performing centrifugal separation, and performing vacuum drying treatment to obtain the dumbbell-shaped MnCO3@ RF composite microspheres (RF is phenolic); weighing the prepared dumbbell-shaped MnCO30.16g of @ RF composite microspheres are uniformly dispersed in 80mL of deionized water to obtain suspension, the suspension is transferred into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle and placed in an oven, the temperature is set to be 210 ℃, and the temperature is kept for 28 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
Example 5 dumbbell MnCO3@ RF hollow composite microsphere
Weighing 0.68g of anhydrous manganese chloride, 1.09g of urea, 3.40g of trisodium citrate dihydrate and 0.68g of sodium polyacrylate (molecular weight of 800 plus 1000 ten thousand) in a beaker, adding 85mL of deionized water into the beaker, placing the beaker on a magnetic stirrer, starting stirring, heating to completely dissolve the sodium polyacrylate, cooling, transferring the solution into a stainless steel-polytetrafluoroethylene-lined high-pressure reaction kettle, placing the kettle into an oven, setting the temperature to be 175 ℃, keeping the temperature for reaction for 5 hours, taking out the solution, cooling the solution to room temperature, washing the solution with deionized water, performing centrifugal separation, and performing freeze drying to obtain dumbbell-shaped manganese carbonate; weighing 0.50g of dumbbell-shaped manganese carbonate and 3.00g of resorcinol, dispersing and dissolving in 550mL of ethanol water solution (the volume ratio of absolute ethanol to deionized water is 2:1), performing ultrasonic treatment for more than 5min to obtain a suspension, adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotation speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 3.50g of formaldehyde aqueous solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 17.50g of ammonia water with the mass fraction of 25% into the three-necked bottle, reacting at constant temperature for 12h, washing the product with absolute ethyl alcohol, performing centrifugal separation, and performing vacuum drying treatment to obtain the dumbbell-shaped MnCO3@ RF composite microspheres (RF is phenolic); weighing the prepared dumbbell-shaped MnCO30.17g of @ RF composite microspheres are uniformly dispersed in 85mL of deionized water to obtain suspension, the suspension is transferred into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle and placed in an oven, the temperature is set to be 220 ℃, and the temperature is kept for 32 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
Example 6 dumbbell MnCO3@ RF hollow composite microsphere
Weighing 0.72g of anhydrous manganese chloride, 1.16g of urea, 3.60g of trisodium citrate dihydrate and 0.72g of sodium polyacrylate (molecular weight of 800-,cooling to room temperature, washing with deionized water, centrifuging, and freeze drying to obtain dumbbell-shaped manganese carbonate; weighing 0.54g of dumbbell-shaped manganese carbonate and 3.24g of resorcinol, dispersing and dissolving in 600mL of ethanol water solution (the volume ratio of absolute ethanol to deionized water is 2:1), performing ultrasonic treatment for more than 5min to obtain suspension, adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotation speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 3.78g of formaldehyde aqueous solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 18.90g of ammonia water with the mass fraction of 25% into the three-necked bottle, reacting at constant temperature for 12h, washing the product with absolute ethyl alcohol, performing centrifugal separation, and performing vacuum drying treatment to obtain the dumbbell-shaped MnCO3@ RF composite microspheres (RF is phenolic); weighing the prepared dumbbell-shaped MnCO30.18g of @ RF composite microspheres are uniformly dispersed in 90mL of deionized water to obtain suspension, the suspension is transferred into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle and placed in an oven, the temperature is set to be 220 ℃, and the temperature is kept for 32 hours; cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
Claims (4)
1. Preparation of MnCO by limited hydrothermal system3The method for @ RF hollow composite microspheres is characterized by comprising the following steps:
step 1: mixing anhydrous manganese chloride, urea, trisodium citrate dihydrate and sodium polyacrylate;
the mass ratio of the anhydrous manganese chloride to the urea to the trisodium citrate dihydrate to the sodium polyacrylate is 1: 1.6-1.7: 5-5.2: 0.9-1.0;
the molecular weight of the sodium polyacrylate is 800-1000 ten thousand;
the mass concentration of the anhydrous manganese chloride is 7.8-8.0kg/m3；
Step 2: adding deionized water, placing on a magnetic stirrer, starting stirring, and heating to completely dissolve;
and step 3: cooling to room temperature, transferring the solution into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle, putting the stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle into an oven, setting the temperature to be 170-180 ℃, and carrying out heat preservation reaction for 5-6 hours; cooling downCooling to room temperature, washing with deionized water, centrifuging, and freeze-drying to obtain dumbbell-shaped manganese carbonate MnCO3；
And 4, step 4: dispersing and dissolving dumbbell-shaped manganese carbonate and resorcinol in a mixed solution of ethanol and water, and performing ultrasonic treatment for more than 5min to obtain a suspension;
the dumbbell-shaped MnCO3The mass ratio of the resorcinol to the resorcinol is 1: 5-6;
the volume ratio of water to ethanol in the mixed solution is 1: 1.8-2;
the mass concentration of the dumbbell-shaped manganese carbonate is 0.8-1.0kg/m3；
And 5: stirring the suspension at the temperature of 25-35 ℃, adding 37-40% by mass of formaldehyde water solution, stirring for 20-40 min, and adding 25% by mass of ammonia water; reacting for 8-12 h at constant temperature, washing the obtained product with absolute ethyl alcohol, performing centrifugal separation, and performing vacuum drying treatment to obtain the dumbbell-shaped MnCO3@ RF composite microspheres, wherein RF is phenolic;
the mass ratio of the dumbbell-shaped manganese carbonate to the formaldehyde aqueous solution is 1: 6-7;
the mass ratio of the dumbbell-shaped manganese carbonate to the ammonia water is 1: 35-40;
step 6: weighing the prepared dumbbell-shaped MnCO3Uniformly dispersing the @ RF composite microspheres in deionized water to obtain a suspension, transferring the suspension into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle, placing the reaction kettle in an oven, setting the temperature to be 200-220 ℃, and keeping the temperature for 24-36 hours; wherein MnCO3@ RF of 1.5-2.0kg/m3；
And 7: cooling the high-pressure reaction kettle to room temperature, and centrifugally separating and freeze-drying a product to obtain MnCO3@ RF hollow composite microspheres.
2. The method of claim 1, wherein: the water is deionized water.
3. The method of claim 1, wherein: the ethanol adopts absolute ethanol.
4. The method of claim 1, wherein: and the stirring speed in the step 5 is 300-500 rpm.
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