CN109437311B - Dumbbell-shaped MnO @ C composite microsphere and preparation method thereof - Google Patents
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Abstract
The invention relates to a dumbbell MnO @ C composite microsphere and a preparation method thereof, wherein the microsphere is characterized by being of a dumbbell shape and a bell-shaped core-shell structure, and manganese oxide is wrapped inside a carbon shell in a particle form; the composition is manganese oxide and carbon. The preparation process comprises the following steps: dumbbell manganese carbonate (MnCO)3) Preparation of dumbbell-shaped MnCO3Synthesis of @ RF composite microspheres and preparation of dumbbell-shaped MnO @ C composite microspheres. Reasonable proportion of a system, reasonable control of reaction time and limited vacuum carbonization reaction are the keys for preparing the dumbbell MnO @ C composite microspheres. The microspheres have large specific surface area, uniform carbon layer thickness and regular appearance. The dumbbell MnO @ C composite microsphere is simple in preparation process, easily available in raw materials, capable of realizing industrial amplification and potentially having application value in the fields of lithium ion battery cathode materials, catalysis, environmentality, biomedicine and the like.
Description
Technical Field
The invention belongs to the field of porous carbon composite materials, and relates to a dumbbell-shaped MnO @ C composite microsphere and a preparation method thereof.
Background
Since the commercialization of lithium ion batteries in the 90 s of the 20 th century, the research on electrode materials of lithium ion batteries has been in depth. The electrodes of the lithium ion battery are respectively composed of different intercalation compounds, and the positive electrode is different types of lithium-containing compounds, such as LiCoO2、LiMn2O4And the performance is excellent; however, commercial negative electrode materials mainly comprise carbon materials such as graphite and the like which are easy to enter lithium ions, and the capacity of the commercial negative electrode materials is low and is only 372mAh g-1And poor cycle performance. In contrast, manganese monoxide (MnO) has a higher theoretical capacity (756mAh g)-1) Low open circuit voltage (1.032V, VS. Li/Li)+) Rich natural reserves, low cost and environmentThe lithium ion battery cathode material is more suitable for being used as a lithium ion battery cathode material. However, the volume change of MnO is large due to lithium intercalation and lithium deintercalation reactions in the charging and discharging processes of the lithium ion battery, so that the material structure is damaged, and meanwhile, the MnO has poor conductivity, so that the energy loss of the lithium battery is increased, and the battery performance is seriously influenced. The effective way to solve the problems is to combine MnO-based materials with carbon materials with better conductivity, so that the conductivity of the MnO-based materials is improved, and the expansion and contraction of the MnO volume can be effectively buffered, so that the electrochemical performance of MnO is improved.
Yanmin Qin et al (electrochemical Acta 282(2018)719) prepare spherical MnO @ NC composite microspheres with manganese carbonate as precursor and dopamine as carbon source and nitrogen source, and the capacity of the microspheres is 880mAh g after the microspheres are circulated for 1000 times under the current density of 1.0A/g-1Higher than the theoretical capacity of MnO and better cycle performance. This strongly proves that carbon-coated MnO materials can be used as good electrode materials, and based on this, extensive attention has been paid to the preparation of carbon-coated MnO. Zhuihua Xiao et al (Carbon 139(2018)750) prepare cubic MnCO by one-step method3The @ C particles are calcined at high temperature in an argon environment to obtain cubic MnO @ C composite particles; shimei Guo et al (Nano Energy 9(2014)41) and the like use manganese carbonate as a precursor, and the spherical MnO @ C composite microspheres are obtained by coating polypyrrole and then calcining at high temperature; manganese sulfate is used as a manganese source (CN201610051974.1), manganese carbonate microspheres with a plurality of polystyrene microspheres embedded inside are prepared by a liquid phase deposition method, the manganese carbonate microspheres are used as a precursor, a carbon layer is coated, and then high-temperature calcination is carried out to prepare the spherical porous MnO @ C composite microspheres. Although the shapes of the MnO @ C composite material are rich at present, reports of dumbbell-shaped Mn @ C composite microspheres are not found yet.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a dumbbell-shaped MnO @ C composite microsphere and a preparation method thereof.
Technical scheme
A dumbbell MnO @ C composite microsphere is characterized in that: the appearance is characterized by being a dumbbell-shaped appearance and a bell-shaped core-shell structure, and the manganese oxide is wrapped inside the carbon shell in a particle form.
The preparation method of the dumbbell-shaped MnO @ C 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 7.6-8.0kg/m3；
Step 2: adding deionized water, placing on a magnetic stirrer, starting stirring, and heating to completely dissolve;
and step 3: then cooling the solution 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 ℃, keeping the temperature, reacting for 5-6 hours, and taking out; 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 mass ratio of the dumbbell-shaped manganese carbonate 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 0.9-1.0kg/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: mixing the dumbbell-shaped MnCO3And (3) putting the @ RF composite microspheres into a tube furnace, calcining for 8-12 h under a vacuum condition, wherein the calcining temperature is 550-700 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
The water is deionized water.
The ethanol adopts absolute ethanol.
Advantageous effects
The invention provides a dumbbell MnO @ C composite microsphere and a preparation method thereof, wherein the microsphere is characterized by being of a dumbbell shape and a bell-shaped core-shell structure, and manganese oxide is wrapped inside a carbon shell in a particle form; the composition is manganese oxide and carbon. The preparation process comprises the following steps: dumbbell manganese carbonate (MnCO)3) Preparation of dumbbell-shaped MnCO3Synthesis of @ RF composite microspheres and preparation of dumbbell-shaped MnO @ C composite microspheres. Reasonable proportion of a system, reasonable control of reaction time and limited vacuum carbonization reaction are the keys for preparing the dumbbell MnO @ C composite microspheres. The microspheres have large specific surface area, uniform carbon layer thickness and regular appearance. The dumbbell MnO @ C composite microsphere is simple in preparation process, easily available in raw materials, capable of realizing industrial amplification and potentially having application value in the fields of lithium ion battery cathode materials, catalysis, environmentality, biomedicine and the like.
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 TEM and SEM photograph of dumbbell MnO @ C composite microspheres
FIG. 4 is an XRD spectrum of dumbbell MnO @ C composite microsphere
FIG. 5 is a nitrogen adsorption curve and a pore size distribution curve of dumbbell MnO @ C composite microspheres
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1 method of dumbbell MnO @ C composite microspheres
Weighing anhydrous0.58g of manganese chloride, 0.98g of urea, 3.01g of trisodium citrate dihydrate and 0.58g of sodium polyacrylate (with the molecular weight of 800 plus 1000 ten thousand) are placed in a beaker, 75mL of deionized water is added into the beaker, the beaker is placed on a magnetic stirrer and is stirred, the beaker is heated to be completely dissolved, the solution is transferred into a stainless steel-polytetrafluoroethylene lined high-pressure reaction kettle after being cooled and is placed in an oven, the temperature is set to be 170 ℃, the solution is taken out after the heat preservation reaction is carried out for 5 hours, the solution is cooled to the room temperature, and the dumbbell-shaped manganese carbonate is obtained after the deionized water washing, the centrifugal separation and the freeze drying; weighing 0.38g of dumbbell-shaped manganese carbonate and 1.90g of resorcinol, fully dispersing in 420mL of ethanol water solution to form a suspension (the volume ratio of deionized water to absolute ethyl alcohol is 1:2), 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 2.28g of formaldehyde water solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 15.20g 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; mixing the dumbbell-shaped MnCO3And (3) putting the @ RF composite microspheres into a tube furnace, calcining for 8 hours under a vacuum condition, wherein the calcining temperature is 550 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
Example 2 method of dumbbell MnO @ C composite microspheres
Weighing 0.60g of anhydrous manganese chloride, 1.02g of urea, 3.12g of trisodium citrate dihydrate and 0.60g of sodium polyacrylate (molecular weight of 800 plus 1000 ten thousand) in a beaker, adding 77mL 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 ℃, carrying out heat preservation reaction for 6 hours, taking out the solution, cooling the solution to room temperature, washing the solution with deionized water, carrying out centrifugal separation, and carrying out freeze drying to obtain dumbbell-shaped manganese carbonate; weighing 0.42g of dumbbell-shaped manganese carbonate and 2.10g of resorcinol, fully dispersing in 460mL of ethanol water solution to form suspension (the volume ratio of deionized water to absolute ethyl alcohol is 1:2), adding the suspension into a three-neck flask with stirring, starting stirring, setting the rotating speed at 400rpm, and setting the reaction temperatureSetting the temperature to be 35 ℃; adding 2.52g of formaldehyde water solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 25min, adding 16.80g 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; mixing the dumbbell-shaped MnCO3And (3) putting the @ RF composite microspheres into a tube furnace, calcining for 10 hours under a vacuum condition, wherein the calcining temperature is 600 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
Example 3 method of dumbbell MnO @ C composite microspheres
Weighing 0.63g of anhydrous manganese chloride, 1.00g of urea, 3.24g of trisodium citrate dihydrate and 0.63g of sodium polyacrylate (molecular weight of 800 plus 1000 ten thousand) 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 0.47g of dumbbell-shaped manganese carbonate and 2.35g of resorcinol, fully dispersing in 520mL of ethanol water solution to form a suspension (the volume ratio of deionized water to absolute ethyl alcohol is 1:2), adding the suspension into a three-neck flask containing a stirrer, starting stirring, setting the rotating speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 2.82g of formaldehyde water solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 18.80g 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; mixing the dumbbell-shaped MnCO3And (3) putting the @ RF composite microspheres into a tube furnace, calcining for 10 hours under a vacuum condition, wherein the calcining temperature is 650 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
Example 4 method of dumbbell MnO @ C composite microspheres
Weighing 0.64g of anhydrous manganese chloride, 1.08g of urea, 3.32g of trisodium citrate dihydrate and 0.64g of sodium polyacrylate (molecular weight of 800-Putting the L deionized water on a magnetic stirrer, starting stirring, heating to completely dissolve the L deionized water, cooling, 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 ℃, keeping the temperature for reaction for 6 hours, taking out the solution, cooling to room temperature, washing with deionized water, performing centrifugal separation, and performing freeze drying to obtain the dumbbell-shaped manganese carbonate; weighing 0.49g of dumbbell-shaped manganese carbonate and 2.45g of resorcinol, fully dispersing in 540mL of ethanol water solution to form a suspension (the volume ratio of deionized water to absolute ethyl alcohol is 1:2), 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 2.94g of formaldehyde aqueous solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 22.40g 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; mixing the dumbbell-shaped MnCO3And (3) putting the @ RF composite microspheres into a tube furnace, calcining for 11 hours under a vacuum condition, wherein the calcining temperature is 600 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
Example 5 method of dumbbell MnO @ C composite microspheres
Weighing 0.65g of anhydrous manganese chloride, 1.10g of urea, 3.38g of trisodium citrate dihydrate and 0.65g of sodium polyacrylate (molecular weight of 800-; weighing 0.56g of dumbbell-shaped manganese carbonate and 2.80g of resorcinol, fully dispersing in 620mL of ethanol water solution to form a suspension (the volume ratio of deionized water to absolute ethyl alcohol is 1:2), adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotating speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 3.36g of formaldehyde water solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, and adding 22.40g of ammonia water with the mass fraction of 25%Putting into a three-neck bottle, reacting at constant temperature for 10h, washing the product with absolute ethyl alcohol, centrifuging, and vacuum drying to obtain dumbbell-shaped MnCO3@ RF composite microspheres; mixing the dumbbell-shaped MnCO3And (3) putting the @ RF composite microspheres into a tube furnace, calcining for 12 hours under a vacuum condition, wherein the calcining temperature is 700 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
Example 6 method of dumbbell MnO @ C composite microspheres
Weighing 0.67g of anhydrous manganese chloride, 1.13g of urea, 3.48g of trisodium citrate dihydrate and 0.67g 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 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 0.60g of dumbbell-shaped manganese carbonate and 3.00g of resorcinol, fully dispersing in 660mL of ethanol water solution to form a suspension (the volume ratio of deionized water to absolute ethyl alcohol is 1:2), adding the suspension into a three-neck flask containing stirring, starting stirring, setting the rotating speed at 400rpm, and setting the reaction temperature at 30 ℃; adding 3.60g of formaldehyde aqueous solution with the mass fraction of 37-40% into a three-necked bottle, stirring for 30min, adding 24.00g 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 to obtain the dumbbell-shaped MnCO3@ RF composite microspheres; mixing the dumbbell-shaped MnCO3And (3) putting the @ RF composite microspheres into a tube furnace, calcining for 10 hours under a vacuum condition, wherein the calcining temperature is 600 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
Claims (4)
1. A preparation method of dumbbell MnO @ C composite microspheres is characterized by comprising the following steps: the dumbbell MnO @ C composite microsphere is characterized by being of a dumbbell shape and a bell-shaped core-shell structure, and manganese oxide is wrapped inside a carbon shell in a particle form;
the preparation method comprises the following specific 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 7.6-8.0kg/m3；
Step 2: adding deionized water, placing on a magnetic stirrer, starting stirring, and heating to completely dissolve;
and step 3: then cooling the solution 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 ℃, keeping the temperature, reacting for 5-6 hours, and taking out; 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 mass ratio of the dumbbell-shaped manganese carbonate 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 0.9-1.0kg/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: mixing the dumbbell-shaped MnCO3The @ RF composite microspheres are put into a tube furnace and calcined under the vacuum conditionAnd (3) burning for 8-12 h at the calcining temperature of 550-700 ℃, and cooling along with the furnace to obtain the dumbbell-shaped MnO @ C composite microspheres.
2. The method for preparing the dumbbell-shaped MnO @ C composite microspheres of claim 1, wherein the method comprises the following steps: the water is deionized water.
3. The method for preparing the dumbbell-shaped MnO @ C composite microspheres of claim 1, wherein the method comprises the following steps: the ethanol adopts absolute ethanol.
4. The method for preparing the dumbbell-shaped MnO @ C composite microspheres of claim 1, wherein the method comprises the following steps: and the stirring speed in the step 5 is 300-500 rpm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07257928A (en) * | 1994-03-22 | 1995-10-09 | Masayuki Yoshio | Electrolytic production of manganese dioxide from carbon-manganese oxide composite dispersed bath and application to active material for positive electrode of alkali cell |
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN105633373A (en) * | 2015-11-06 | 2016-06-01 | 北京化工大学 | Carbon-coated porous manganese monoxide composite material and preparation method and application thereof |
| CN108269983A (en) * | 2018-01-16 | 2018-07-10 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating manganese oxide negative material and preparation method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07257928A (en) * | 1994-03-22 | 1995-10-09 | Masayuki Yoshio | Electrolytic production of manganese dioxide from carbon-manganese oxide composite dispersed bath and application to active material for positive electrode of alkali cell |
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN105633373A (en) * | 2015-11-06 | 2016-06-01 | 北京化工大学 | Carbon-coated porous manganese monoxide composite material and preparation method and application thereof |
| CN108269983A (en) * | 2018-01-16 | 2018-07-10 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating manganese oxide negative material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Carbon-coated MnO microparticulate porous nanocomposites serving as anode materials with enhanced electrochemical performances;Shimei Guo et al.;《Nano Energy》;20140702;第9卷;41-49 * |
| Glucose-based carbon coated MnOx hierarchical architectures with enhanced photostability and photocatalytic activity;Junli Zhou et al.;《Microporous and Mesoporous Materials》;20141125;第204卷;115-122 * |
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