CN106966426B - A kind of preparation method of nanoporous stannous oxide - Google Patents
A kind of preparation method of nanoporous stannous oxide Download PDFInfo
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Abstract
The invention belongs to chemicals preparation technical fields, and in particular to a kind of preparation method of nanoporous stannous oxide.The present invention is first by active carbon and liquor alumini chloridi mixing ultrasonic disperse, the aluminum hydroxide precipitation generated using activated carbon adsorption, recycle calcining removal active carbon kernel, the calcining material rich in porous aluminas is made, recycle dopamine solution modified, improve the absorption property of porous calcining material, and adsorbing chlorinated stannous and the sediment that oxalic acid generates are expected using modified porous calcining, it is roasted under argon gas guard mode, generate the presoma containing stannous oxide, utilize porous aluminas in sodium hydroxide solution removal presoma, nanoporous stannous oxide is made after being centrifuged and drying.It is the reunion that template avoids porous calcining material the invention firstly uses active carbon, then to make porous calcining material by oneself as template, in precipitating and roasting process, product is avoided to reunite, efficiently solve the problems, such as that Conventional nano stannous oxide is easy to reunite during the preparation process.
Description
Technical field
The invention belongs to chemicals preparation technical fields, and in particular to a kind of preparation method of nanoporous stannous oxide.
Background technique
Stannous oxide is a kind of dark gray or brown-black powder, not soluble in water and alcohol and odorless or slightly salt acid smell gold
Belong to oxide.More stable in air, when heating, is easily converted to tin oxide, is dissolved in hydrochloric acid or dilute sulfuric acid generates corresponding tin
Salt is dissolved in dense strong base solution and generates stannite.It is a kind of important metal oxide, can be used as the cathode material of lithium battery
Material, performance have higher energy density per unit volume and specific energy compared with carbon material is the battery of cathode, and theory is reversible
Discharge capacity is up to 880mAh/g.People are prepared by the methods of vapour deposition process, homogeneous precipitation method, laser radiation method
Stannous oxide, and its performance is studied, from the point of view of test result, it need further perfect.The SnO base of such as Courtney preparation
Lithium storage materials, initial reversible discharge capacity only have 400mAh/g or so；This kind of Lithium storage materials of the reports such as Mouhill were through 20 weeks
After circulation, capacity is only left 100mAh/g or so.
The preparation method of stannous oxide crystal continues to develop maturation, and sol-gal process and hydro-thermal method are that current application is most
Preparation method, technical maturity, sufficiently, method is simple and is suitble to the advantages of being mass produced for synthesis mechanism research.But with wet
Forensic chemistry, which synthesizes nano oxidized stannous, certain difficulty, in preparation process, often along with the reunion of nanocrystal, leads to product
Performance decline.The appearance of nanotechnology, the especially appearance of high-performance nano material provide for research high performance lithium ion battery
Good opportunity.Due to the small-size effect and skin effect of nano material, so that it shows unique photoelectric properties, use
Lithium ion battery is transformed in it, the specific energy of lithium battery can not only be greatly improved very much, but also can reduce embedding de- lithium
Current potential improves electrode structure and its cycle performance.The stannous oxide of different-shape is prepared by distinct methods, its shape
Looks and size directly affect its performance, have very big application prospect, therefore, grind in terms of lithium battery, plating and catalysis
Study carefully to develop and a kind of be not susceptible to reunite and have important practical significance with the stannous oxide of excellent chemical property.
Summary of the invention
The present invention solves the technical problem of：Group easily occurs during the preparation process for Conventional nano stannous oxide
The problem of gathering, properties of product is caused to decline, provide a kind of preparation method of nanoporous stannous oxide.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that：
（1）150~200g active carbon is weighed, pours into and fills 800~1000mL mass fraction as the three of 20% liquor alumini chloridi
In mouthful flask, after 15~20min of sonic oscillation, three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, is used while stirring
Mass fraction is 20% sodium hydroxide solution, adjusts pH to 10.6~10.8, to the end of pH is adjusted, continues constant temperature and is stirred to react 60
~90min；
（2）To the end of constant temperature is stirred to react, by material filtering in three-necked flask, active carbon and aluminium hydroxide composite filter are obtained
Cake, then it is washed and dry, dry activated carbon and the compound filter cake of aluminium hydroxide are obtained, then calcined, obtains porous calcining material, weigh 30
The porous calcining material of~50g, pours into and fills in the beaker that 200~300mL mass concentration is 2g/L dopamine solution, stand after stirring
20~30min, then by material filtering in beaker, obtain modified porous calcining material；
（3）The modified porous calcining material of gained is poured into four-hole boiling flask, then 300~500mL of addition is dense into four-hole boiling flask
Degree be 0.10~0.15mol/L stannous chloride ethanol solution, under nitrogen protection state, in temperature be 45~50 DEG C, revolving speed
Under the conditions of 200~400r/min, the second that 300~500mL concentration is 0.15~0.18mol/L oxalic acid is added dropwise into four-hole boiling flask
Alcoholic solution continues constant temperature and is stirred to react 60~90min, then by material filtering in four-hole boiling flask, be filtered, washed wait be added dropwise
And it is dry to constant weight, dry mixed filter residue is obtained, then dry mixed filter residue is transferred to tube type resistance furnace, is protected under argon gas guard mode
3~5h of temperature reaction；
（4）To the end of above-mentioned insulation reaction, room temperature is cooled to the furnace, discharge, obtain presoma material, and by gained presoma
Material, which pours into, to be filled in the beaker that 600~800mL mass fraction is 10~15% sodium hydroxide solutions, after sonic oscillation, centrifugation
Separation removes upper liquid, obtains lower sediment thing, then washed, dry and encapsulation to get nanoporous stannous oxide.
Step（2）The calcination condition is：In Muffle furnace, 650 are warming up to 8~10 DEG C/min rate program~
700 DEG C, after 2~4h is calcined in heat preservation, cool to room temperature with the furnace.
Step（2）During the standing, moreover it is possible to be passed through air into dopamine solution with 3~5mL/min rate.
Step（3）The ethanol solution dripping quantity of the oxalic acid is 300~500mL, and time for adding is drop in 1.5~2.5h
It is complete.
Step（3）The insulation reaction condition under argon gas guard mode is：With 40~50mL/min rate into furnace
It is passed through argon gas, under argon gas guard mode, is warming up to 500~550 DEG C with 8~10 DEG C/min rate program.
The beneficial effects of the invention are as follows：
（1）The invention firstly uses the superior absorption property of active carbon and pore structure abundant, adsorbing chlorinated aluminum solutions
The aluminum hydroxide precipitation generated is reacted with sodium hydroxide, aluminum hydroxide precipitation is tightly held by activated carbon once being formed in solution, is filled out
It fills in activated carbon pore structure, aluminium hydroxide is avoided to reunite, then remove active carbon kernel through calcining, while in calcination process
In, aluminium hydroxide decomposes, and forms porous aluminas；
（2）The present invention impregnates modified self-control porous aluminas using dopamine solution, using dopamine catechol and
Amido functional group is established in porous oxidation aluminium surface and is covalently mentioned with non-covalent interaction, the super strongly attached composite layer of formation
The absorption property of high porous aluminas, adsorbing chlorinated stannous react the stannous oxalate crystal generated with oxalic acid, compound layer surface
The steric hindrance of organic group can effectively prevent the stannous oxalate crystal of absorption from further growing up and reunite, and drying and roasting
In the process, because of the presence of porous aluminas, stannous oxalate crystal can be effectively prevented to reunite in the process, finally through hydrogen-oxygen
Change sodium solution to impregnate, porous aluminas is enable to remove, and makes the nano oxidized stannous of product that there is pore structure abundant.
Specific embodiment
The active carbon that 150~200g is crushed to 300~500 mesh is weighed, is poured into and is filled 800~1000mL mass fraction and be
In the three-necked flask of 20% liquor alumini chloridi, and three-necked flask is moved into sonic oscillation instrument, under the conditions of supersonic frequency is 40kHz,
15~20min of ultrasonic disperse, then the three-necked flask after ultrasonic treatment is moved into digital display and is tested the speed constant temperature blender with magnetic force, it is in temperature
55~60 DEG C, under the conditions of revolving speed is 300~500r/min, quality point is added dropwise into three-necked flask by dropping funel while stirring
Number is 20% sodium hydroxide solution, adjusts pH to 10.6~10.8, to completion of dropwise addition, continues constant temperature and is stirred to react 60~90min；
To the end of constant temperature is stirred to react, by material filtering in three-necked flask, active carbon and the compound filter cake of aluminium hydroxide is obtained, deionized water is used
Detergent active charcoal and the compound filter cake of aluminium hydroxide until cleaning solution is in neutrality, and by after washing active carbon and aluminium hydroxide it is compound
Filter cake is transferred in baking oven, is dried under the conditions of being 105~110 DEG C in temperature to constant weight, is obtained dry activated carbon and aluminium hydroxide is compound
Filter cake, then dry activated carbon and the compound filter cake of aluminium hydroxide are transferred to Muffle furnace, it is warming up to 8~10 DEG C/min rate program
It 650~700 DEG C, after 2~4h is calcined in heat preservation, cools to room temperature with the furnace, discharges, obtain porous calcining material；Weigh 30~50g institute much
Hole calcining material, pours into and fills in the beaker that 200~300mL mass concentration is 2g/L dopamine solution, be stirred with glass bar
After 10~20min, stands 20~30min and sky is passed through into dopamine solution with 3~5mL/min rate during standing
Gas, then by material filtering in beaker, obtain modified porous calcining material；The modified porous calcining material of gained is poured into four-hole boiling flask, then
The ethanol solution that 300~500mL concentration is 0.10~0.15mol/L stannous chloride is added, and into four-hole boiling flask with 3~5mL/
Min rate is passed through nitrogen into four-hole boiling flask, then four-hole boiling flask immigration digital display is tested the speed constant temperature blender with magnetic force, in nitrogen protection
Under state, it is 45~50 DEG C in temperature, under the conditions of revolving speed is 200~400r/min, is dripped by dropping funel into four-hole boiling flask
Adding 300~500mL concentration is the ethanol solution of 0.15~0.18mol/L oxalic acid, and control drips off in 1.5~2.5h, wait be added dropwise
It finishes, continues constant temperature and be stirred to react 60~90min；To the end of constant temperature is stirred to react, material filtering in four-hole boiling flask must mix
Filter residue is washed with deionized mixed filter residue 3~5 times, and the mixed filter residue after washing is transferred to vacuum oven, is in temperature
It dries under the conditions of 105~110 DEG C to constant weight, then the mixed filter residue after drying is transferred to tube type resistance furnace, with 40~50mL/min
Rate is passed through argon gas into furnace, under argon gas guard mode, is warming up to 500~550 DEG C with 8~10 DEG C/min rate program, protects
3~5h of temperature reaction；To the end of insulation reaction, room temperature is cooled to the furnace, discharge, obtain presoma material, and by gained presoma object
Material, which pours into, to be filled in the beaker that 600~800mL mass fraction is 10~15% sodium hydroxide solutions, then beaker is moved into ultrasound vibration
Instrument is swung, under the conditions of supersonic frequency is 40kHz, is ultrasonically treated 45~60min；To the end of being ultrasonically treated, material in beaker is turned
Enter centrifuge, 10~15min is centrifugated with 6000~8000r/min revolving speed, upper liquid is removed, obtains lower sediment thing, be used in combination
Deionized water washing gained lower sediment thing, until cleaning solution is in neutrality, then is transferred to vacuum for the lower sediment thing after washing and does
Dry case is dried under the conditions of being 105~110 DEG C in temperature to constant weight, and discharging encapsulates to get nanoporous stannous oxide.
Example 1
The active carbon that 150g is crushed to 300 mesh is weighed, pours into and fills 800mL mass fraction as the three of 20% liquor alumini chloridi
In mouth flask, and three-necked flask is moved into sonic oscillation instrument, under the conditions of supersonic frequency is 40kHz, ultrasonic disperse 15min, then
Three-necked flask after ultrasonic treatment is moved into digital display to test the speed constant temperature blender with magnetic force, in temperature be 55 DEG C, revolving speed 300r/min
Under the conditions of, while stirring by dropping funel is added dropwise into three-necked flask mass fraction be 20% sodium hydroxide solution, adjusting pH to
10.6, to completion of dropwise addition, continues constant temperature and be stirred to react 60min；To the end of constant temperature is stirred to react, by material mistake in three-necked flask
Filter, obtains active carbon and the compound filter cake of aluminium hydroxide, and active carbon and the compound filter cake of aluminium hydroxide is washed with deionized until washing
Liquid is in neutrality, and by after washing active carbon and the compound filter cake of aluminium hydroxide be transferred in baking oven, in temperature be 105 DEG C under the conditions of do
It is dry to obtain dry activated carbon and the compound filter cake of aluminium hydroxide to constant weight, then dry activated carbon and the compound filter cake of aluminium hydroxide are transferred to
Muffle furnace is warming up to 650 DEG C with 8 DEG C/min rate program, after 2h is calcined in heat preservation, cools to room temperature with the furnace, discharge, obtain porous forge
Imitation frosted glass；Porous calcining material obtained by 30g is weighed, pours into and fills in the beaker that 200mL mass concentration is 2g/L dopamine solution, use glass
After glass stick is stirred 10min, stands 20min and sky is passed through into dopamine solution with 3mL/min rate during standing
Gas, then by material filtering in beaker, obtain modified porous calcining material；The modified porous calcining material of gained is poured into four-hole boiling flask, then
The ethanol solution that 300mL concentration is 0.10mol/L stannous chloride is added into four-hole boiling flask, and with 3mL/min rate to four mouthfuls
It is passed through nitrogen in flask, then four-hole boiling flask immigration digital display is tested the speed constant temperature blender with magnetic force, under nitrogen protection state, in temperature
It is 45 DEG C, under the conditions of revolving speed is 200r/min, it is 0.15mol/L that 300mL concentration is added dropwise into four-hole boiling flask by dropping funel
The ethanol solution of oxalic acid, control drips off in 1.5h, wait be added dropwise, continues constant temperature and is stirred to react 60min；It is anti-to constant temperature stirring
It should terminate, by material filtering in four-hole boiling flask, obtain mixed filter residue, be washed with deionized mixed filter residue 3 times, and will be after washing
Mixed filter residue is transferred to vacuum oven, dries under the conditions of being 105 DEG C in temperature to constant weight, then the mixed filter residue after drying is transferred to
Tube type resistance furnace is passed through argon gas into furnace with 40mL/min rate, under argon gas guard mode, with 8 DEG C/min rate program liter
Temperature is to 500 DEG C, insulation reaction 3h；To the end of insulation reaction, room temperature is cooled to the furnace, discharge, obtain presoma material, and by gained
Presoma material, which pours into, to be filled in the beaker that 600mL mass fraction is 10% sodium hydroxide solution, then beaker is moved into sonic oscillation
Instrument is ultrasonically treated 45min under the conditions of supersonic frequency is 40kHz；To the end of being ultrasonically treated, material in beaker is transferred to centrifugation
Machine is centrifugated 10min with 6000r/min revolving speed, removes upper liquid, obtain lower sediment thing, and gained is washed with deionized
Lower sediment thing, until cleaning solution is in neutrality, then is transferred to vacuum oven for the lower sediment thing after washing, in temperature be 105
It is dried under the conditions of DEG C to constant weight, discharging encapsulates to get nanoporous stannous oxide.
According to parts by weight, 70 parts of present invention gained nanoporous stannous oxides are successively taken, 10 parts of acetylene blacks, 10 parts poly- inclined
Vinyl fluoride, 180 parts of N-Methyl pyrrolidones, is coated on copper foil of affluxion body after mixing, then copper foil is placed in vacuum drying
In case, stannous oxide electrode is made in dry 8h under the conditions of 120 DEG C, then using stannous oxide electrode as cathode, and lithium metal is anode,
2025 type button cells are assembled under argon gas guard mode.Through detecting, stannous oxide electrode in use, reversible discharge
Capacity is up to 700mAh/g, and through 100 charge and discharge cycles, the average capacity attenuation recycled every time is 0.025%, has excellent
Chemical property.
Example 2
The active carbon that 200g is crushed to 500 mesh is weighed, pours into and fills 1000mL mass fraction as the three of 20% liquor alumini chloridi
In mouth flask, and three-necked flask is moved into sonic oscillation instrument, under the conditions of supersonic frequency is 40kHz, ultrasonic disperse 20min, then
Three-necked flask after ultrasonic treatment is moved into digital display to test the speed constant temperature blender with magnetic force, in temperature be 60 DEG C, revolving speed 500r/min
Under the conditions of, while stirring by dropping funel is added dropwise into three-necked flask mass fraction be 20% sodium hydroxide solution, adjusting pH to
10.8, to completion of dropwise addition, continues constant temperature and be stirred to react 90min；To the end of constant temperature is stirred to react, by material mistake in three-necked flask
Filter, obtains active carbon and the compound filter cake of aluminium hydroxide, and active carbon and the compound filter cake of aluminium hydroxide is washed with deionized until washing
Liquid is in neutrality, and by after washing active carbon and the compound filter cake of aluminium hydroxide be transferred in baking oven, in temperature be 110 DEG C under the conditions of do
It is dry to obtain dry activated carbon and the compound filter cake of aluminium hydroxide to constant weight, then dry activated carbon and the compound filter cake of aluminium hydroxide are transferred to
Muffle furnace is warming up to 700 DEG C with 10 DEG C/min rate program, after 4h is calcined in heat preservation, cools to room temperature with the furnace, discharge, obtain porous
Calcining material；Porous calcining material obtained by 50g is weighed, pours into and fills in the beaker that 300mL mass concentration is 2g/L dopamine solution, use
After glass bar is stirred 20min, stands 30min and be passed through with 5mL/min rate into dopamine solution during standing
Air, then by material filtering in beaker, obtain modified porous calcining material；The modified porous calcining material of gained is poured into four-hole boiling flask,
The ethanol solution that 500mL concentration is 0.15mol/L stannous chloride is added into four-hole boiling flask again, and with 5mL/min rate to four
It is passed through nitrogen in mouthful flask, then four-hole boiling flask immigration digital display is tested the speed constant temperature blender with magnetic force, under nitrogen protection state, Yu Wen
Degree is 50 DEG C, and under the conditions of revolving speed is 400r/min, it is 0.18mol/ that 500mL concentration is added dropwise into four-hole boiling flask by dropping funel
The ethanol solution of L oxalic acid, control drips off in 2.5h, wait be added dropwise, continues constant temperature and is stirred to react 90min；It is stirred to constant temperature
Reaction terminates, and by material filtering in four-hole boiling flask, obtains mixed filter residue, is washed with deionized mixed filter residue 5 times, and will be after washing
Mixed filter residue be transferred to vacuum oven, dry under the conditions of being 110 DEG C in temperature to constant weight, then the mixed filter residue after drying is turned
Enter tube type resistance furnace, argon gas is passed through into furnace with 50mL/min rate, under argon gas guard mode, with 10 DEG C/min rate program
550 DEG C are warming up to, insulation reaction 5h；To the end of insulation reaction, room temperature is cooled to the furnace, discharge, obtain presoma material, and by institute
Presoma material pour into fill 800mL mass fraction be 15% sodium hydroxide solution beaker in, then by beaker move into ultrasound vibration
Instrument is swung, under the conditions of supersonic frequency is 40kHz, is ultrasonically treated 60min；To the end of being ultrasonically treated, by material in beaker be transferred to from
Scheming is centrifugated 15min with 8000r/min revolving speed, removes upper liquid, obtain lower sediment thing, and institute is washed with deionized
Lower sediment thing is obtained, until cleaning solution is in neutrality, then the lower sediment thing after washing vacuum oven is transferred to, is in temperature
It is dried under the conditions of 110 DEG C to constant weight, discharging encapsulates to get nanoporous stannous oxide.
According to parts by weight, 75 parts of present invention gained nanoporous stannous oxides are successively taken, 15 parts of acetylene blacks, 15 parts poly- inclined
Vinyl fluoride, 200 parts of N-Methyl pyrrolidones, is coated on copper foil of affluxion body after mixing, then copper foil is placed in vacuum drying
In case, stannous oxide electrode is made in dry 10h under the conditions of 125 DEG C, then using stannous oxide electrode as cathode, lithium metal is positive
Pole is assembled into 2025 type button cells under argon gas guard mode.Through detecting, stannous oxide electrode is in use, reversible
Discharge capacity is up to 710mAh/g, and through 100 charge and discharge cycles, the average capacity attenuation recycled every time is 0.035%, has excellent
Different chemical property.
Example 3
The active carbon that 175g is crushed to 400 mesh is weighed, pours into and fills 900mL mass fraction as the three of 20% liquor alumini chloridi
In mouth flask, and three-necked flask is moved into sonic oscillation instrument, under the conditions of supersonic frequency is 40kHz, ultrasonic disperse 18min, then
Three-necked flask after ultrasonic treatment is moved into digital display to test the speed constant temperature blender with magnetic force, in temperature be 58 DEG C, revolving speed 400r/min
Under the conditions of, while stirring by dropping funel is added dropwise into three-necked flask mass fraction be 20% sodium hydroxide solution, adjusting pH to
10.7, to completion of dropwise addition, continues constant temperature and be stirred to react 75min；To the end of constant temperature is stirred to react, by material mistake in three-necked flask
Filter, obtains active carbon and the compound filter cake of aluminium hydroxide, and active carbon and the compound filter cake of aluminium hydroxide is washed with deionized until washing
Liquid is in neutrality, and by after washing active carbon and the compound filter cake of aluminium hydroxide be transferred in baking oven, in temperature be 108 DEG C under the conditions of do
It is dry to obtain dry activated carbon and the compound filter cake of aluminium hydroxide to constant weight, then dry activated carbon and the compound filter cake of aluminium hydroxide are transferred to
Muffle furnace is warming up to 675 DEG C with 9 DEG C/min rate program, after 3h is calcined in heat preservation, cools to room temperature with the furnace, discharge, obtain porous forge
Imitation frosted glass；Porous calcining material obtained by 40g is weighed, pours into and fills in the beaker that 250mL mass concentration is 2g/L dopamine solution, use glass
After glass stick is stirred 15min, stands 25min and sky is passed through into dopamine solution with 4mL/min rate during standing
Gas, then by material filtering in beaker, obtain modified porous calcining material；The modified porous calcining material of gained is poured into four-hole boiling flask, then
The ethanol solution that 400mL concentration is 0.12mol/L stannous chloride is added into four-hole boiling flask, and with 4mL/min rate to four mouthfuls
It is passed through nitrogen in flask, then four-hole boiling flask immigration digital display is tested the speed constant temperature blender with magnetic force, under nitrogen protection state, in temperature
It is 48 DEG C, under the conditions of revolving speed is 300r/min, it is 0.16mol/L that 400mL concentration is added dropwise into four-hole boiling flask by dropping funel
The ethanol solution of oxalic acid, control drips off in 2h, wait be added dropwise, continues constant temperature and is stirred to react 75min；It is stirred to react to constant temperature
Terminate, by material filtering in four-hole boiling flask, obtain mixed filter residue, be washed with deionized mixed filter residue 4 times, and will be mixed after washing
It closes filter residue and is transferred to vacuum oven, dry under the conditions of being 108 DEG C in temperature to constant weight, then the mixed filter residue after drying is transferred to pipe
Formula resistance furnace is passed through argon gas into furnace with 45mL/min rate, under argon gas guard mode, with the heating of 9 DEG C/min rate program
To 525 DEG C, insulation reaction 4h；To the end of insulation reaction, room temperature is cooled to the furnace, discharge, obtain presoma material, and will be before gained
Drive body material, which pours into, to be filled in the beaker that 700mL mass fraction is 12% sodium hydroxide solution, then beaker is moved into sonic oscillation
Instrument is ultrasonically treated 52min under the conditions of supersonic frequency is 40kHz；To the end of being ultrasonically treated, material in beaker is transferred to centrifugation
Machine is centrifugated 13min with 7000r/min revolving speed, removes upper liquid, obtain lower sediment thing, and gained is washed with deionized
Lower sediment thing, until cleaning solution is in neutrality, then is transferred to vacuum oven for the lower sediment thing after washing, in temperature be 108
It is dried under the conditions of DEG C to constant weight, discharging encapsulates to get nanoporous stannous oxide.
According to parts by weight, 72 parts of present invention gained nanoporous stannous oxides are successively taken, 12 parts of acetylene blacks, 12 parts poly- inclined
Vinyl fluoride, 190 parts of N-Methyl pyrrolidones, is coated on copper foil of affluxion body after mixing, then copper foil is placed in vacuum drying
In case, stannous oxide electrode is made in dry 9h under the conditions of 122 DEG C, then using stannous oxide electrode as cathode, and lithium metal is anode,
2025 type button cells are assembled under argon gas guard mode.Through detecting, stannous oxide electrode in use, reversible discharge
Capacity is up to 705mAh/g, and through 100 charge and discharge cycles, the average capacity attenuation recycled every time is 0.03%, has excellent electricity
Chemical property.
Claims (5)
1. a kind of preparation method of nanoporous stannous oxide, it is characterised in that specifically preparation step is：
（1）150~200g active carbon is weighed, three mouthfuls of burnings for filling that 800~1000mL mass fraction is 20% liquor alumini chloridi are poured into
In bottle, after 15~20min of sonic oscillation, three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, uses quality while stirring
Score is 20% sodium hydroxide solution, adjusts pH to 10.6~10.8, to the end of pH is adjusted, continue constant temperature be stirred to react 60~
90min；
（2）To the end of constant temperature is stirred to react, by material filtering in three-necked flask, active carbon and the compound filter cake of aluminium hydroxide are obtained, then
It is washed and dry, dry activated carbon and the compound filter cake of aluminium hydroxide are obtained, then calcined, obtains porous aluminas, weigh 30~50g
Porous aluminas, pour into fill 200~300mL mass concentration be 2g/L dopamine solution beaker in, after stirring stand 20~
30min, then by material filtering in beaker, obtain modified porous aluminium oxide；
（3）The modified porous calcining material of gained is poured into four-hole boiling flask, then 300~500mL concentration is added into four-hole boiling flask and is
The ethanol solution of 0.10~0.15mol/L stannous chloride, under nitrogen protection state, in temperature be 45~50 DEG C, revolving speed 200
Under the conditions of~400r/min, it is molten that the ethyl alcohol that 300~500mL concentration is 0.15~0.18mol/L oxalic acid is added dropwise into four-hole boiling flask
Liquid continues constant temperature and is stirred to react 60~90min, then by material filtering in four-hole boiling flask, be filtered, washed and do wait be added dropwise
It is dry to obtain dry mixed filter residue to constant weight, then dry mixed filter residue is transferred to tube type resistance furnace, 500 under argon gas guard mode~
550 DEG C of 3~5h of insulation reaction；
（4）To the end of above-mentioned insulation reaction, room temperature is cooled to the furnace, discharge, obtain presoma material, and by gained presoma material
It pours into and fills in the beaker that 600~800mL mass fraction is 10~15% sodium hydroxide solutions, after sonic oscillation, centrifugation point
From removal upper liquid obtains lower sediment thing, then washed, dry and encapsulation to get nanoporous stannous oxide.
2. a kind of preparation method of nanoporous stannous oxide according to claim 1, it is characterised in that：Step（2）Institute
The calcination condition stated is：In Muffle furnace, 650~700 DEG C are warming up to 8~10 DEG C/min rate program, 2~4h of heat preservation calcining
Afterwards, room temperature is cooled to the furnace.
3. a kind of preparation method of nanoporous stannous oxide according to claim 1, it is characterised in that：Step（2）Institute
During the standing stated, moreover it is possible to be passed through air into dopamine solution with 3~5mL/min rate.
4. a kind of preparation method of nanoporous stannous oxide according to claim 1, it is characterised in that：Step（3）Institute
The ethanol solution dripping quantity for the oxalic acid stated is 300~500mL, and time for adding is to drip off in 1.5~2.5h.
5. a kind of preparation method of nanoporous stannous oxide according to claim 1, it is characterised in that：Step（3）Institute
The insulation reaction condition under argon gas guard mode stated is：It is passed through argon gas into furnace with 40~50mL/min rate, is protected in argon gas
Under shield state, 500~550 DEG C are warming up to 8~10 DEG C/min rate program.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323463A (en) * | 2007-06-12 | 2008-12-17 | 赣州瑞德化工有限公司 | Production process of high pure superfine tin oxide |
| CN102602986A (en) * | 2012-04-13 | 2012-07-25 | 山东大学 | Preparation method of micronano stannic oxide porous rod with controllable shape |
| CN103562134A (en) * | 2011-01-27 | 2014-02-05 | 霍尼韦尔国际公司 | Method for the preparation of high purity stannous oxide |
| CN105236473A (en) * | 2015-10-29 | 2016-01-13 | 陕西科技大学 | Method for preparing shell-structured stannous oxide material |
| CN105344342A (en) * | 2015-11-09 | 2016-02-24 | 复旦大学 | Photocatalyst environment purifying material based on active carbon and preparation method therefor |
-
2017
- 2017-04-21 CN CN201710267152.1A patent/CN106966426B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323463A (en) * | 2007-06-12 | 2008-12-17 | 赣州瑞德化工有限公司 | Production process of high pure superfine tin oxide |
| CN103562134A (en) * | 2011-01-27 | 2014-02-05 | 霍尼韦尔国际公司 | Method for the preparation of high purity stannous oxide |
| CN102602986A (en) * | 2012-04-13 | 2012-07-25 | 山东大学 | Preparation method of micronano stannic oxide porous rod with controllable shape |
| CN105236473A (en) * | 2015-10-29 | 2016-01-13 | 陕西科技大学 | Method for preparing shell-structured stannous oxide material |
| CN105344342A (en) * | 2015-11-09 | 2016-02-24 | 复旦大学 | Photocatalyst environment purifying material based on active carbon and preparation method therefor |
Non-Patent Citations (2)
| Title |
|---|
| 纳米SnO的溶胶-凝胶法制备与电化学性能;何则强等;《无机化学学报》;20060228(第2期);第253-257页 * |
| 草酸亚锡热分解反应动力学;唐万军等;《中南民族大学学报(自然科学版)》;20070331;第26卷(第1期);第16-19页 * |
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