CN106966426A - 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 preparing technical field, and in particular to a kind of preparation method of nanoporous stannous oxide.The present invention is first by activated carbon and liquor alumini chloridi mixing ultrasonic disperse, the aluminum hydroxide precipitation produced using charcoal absorption, calcining is recycled to remove activated carbon kernel, the calcining material rich in Woelm Alumina is made, dopamine solution is recycled to be modified, improve the absorption property of porous calcining material, and the sediment produced using the adsorbing chlorinated stannous of modified porous calcining material with oxalic acid, it is calcined under argon gas guard mode, generate the presoma containing stannous oxide, Woelm Alumina in presoma is removed using sodium hydroxide solution, it is centrifuged and nanoporous stannous oxide is made after drying.The present invention in precipitation and roasting process, it is to avoid product is reunited, efficiently solves the problem of Conventional nano stannous oxide is easily reunited in preparation process first with the reunion that activated carbon is that template avoids porous calcining material, then to make porous calcining material by oneself for template.
Description
Technical field
The invention belongs to chemicals preparing technical field, and in particular to a kind of preparation method of nanoporous stannous oxide.
Background technology
Stannous oxide is a kind of dark gray or brown-black powder, water insoluble and alcohol and odorless or the slightly gold of salt acid smell
Belong to oxide.It is more stable in atmosphere, tin oxide is easily converted to during heating, hydrochloric acid is dissolved in or dilute sulfuric acid generates corresponding tin
Salt, is dissolved in dense strong base solution generation stannite.It is a kind of important metal oxide, can as lithium battery negative pole material
Material, its performance is compared with battery of the carbon material for negative pole, and with higher energy density per unit volume and specific energy, its theory is reversible
Discharge capacity is up to 880mAh/g.People are prepared by methods such as vapour deposition process, homogeneous precipitation method, laser radiation methods
Stannous oxide, and its performance is studied, from the point of view of test result, it need further perfect.The SnO bases of such as Courtney preparations
Lithium storage materials, its initial reversible discharge capacity only has 400mAh/g or so；This kind of Lithium storage materials of the reports such as Mouhill were through 20 weeks
After circulation, its 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, synthesis mechanism research is abundant, and method is simple and is adapted to the advantage of large-scale production.But with wet
Forensic chemistry, which synthesizes nano oxidized stannous, to be had in certain difficulty, preparation process, often along with the reunion of nanocrystal, causes product
Hydraulic performance decline.The appearance of the appearance of nanometer technology, particularly high-performance nano material, is provided 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 the photoelectric properties of uniqueness, use
It transforms lithium ion battery, the specific energy of lithium battery not only can be greatly improved very much, and can also 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 affects its performance, and it has very big application prospect, therefore, grind in terms of lithium battery, plating and catalysis
Study carefully a kind of stannous oxide for being not susceptible to reunite and there is excellent chemical property of exploitation to have important practical significance.
The content of the invention
The present invention solves the technical problem of：Group easily occurs in preparation process for Conventional nano stannous oxide
Poly-, causing the problem of properties of product decline, there is provided a kind of preparation method of nanoporous stannous oxide.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）150~200g activated carbons are weighed, three mouthfuls of burnings for filling that 800~1000mL mass fractions are 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, quality is used while stirring
Fraction is 20% sodium hydroxide solution, and pH is to 10.6~10.8 for regulation, treats that pH regulations terminate, continuation constant temperature stirring reaction 60~
90min；
（2）Treat that constant temperature stirring reaction terminates, by material filtering in three-necked flask, obtain activated carbon and aluminium hydroxide is combined filter cake, then
It is scrubbed and dry, obtain dry activated carbon and aluminium hydroxide is combined filter cake, then through calcining, obtain porous calcining material, weigh 30~50g
It is porous calcining material, pour into fill 200~300mL mass concentrations be 2g/L dopamine solutions beaker in, after stirring stand 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 concentration is added into four-hole boiling flask and is
The ethanol solution of 0.10~0.15mol/L stannous chlorides, is 45~50 DEG C in temperature, rotating speed is 200 under nitrogen guard mode
Under the conditions of~400r/min, 300~500mL concentration is added dropwise into four-hole boiling flask molten for the ethanol of 0.15~0.18mol/L oxalic acid
Liquid, treats completion of dropping, continues constant temperature 60~90min of stirring reaction, then by material filtering in four-hole boiling flask, filter, wash and do
It is dry to obtain dry mixed filter residue to constant weight, then dry mixed filter residue is transferred to tube type resistance furnace, it is incubated under argon gas guard mode anti-
Answer 3~5h；
（4）Treat that above-mentioned insulation reaction terminates, cool to room temperature with the furnace, discharge, obtain presoma material, and by gained presoma material
Pour into and fill in the beaker that 600~800mL mass fractions are 10~15% sodium hydroxide solutions, after sonic oscillation, centrifugation point
From removal upper liquid obtains lower sediment thing, then scrubbed, dry and encapsulation, produces nanoporous stannous oxide.
Step（2）Described calcination condition is：In Muffle furnace, 650 are warming up to 8~10 DEG C/min rate programs~
700 DEG C, insulation is calcined after 2~4h, cools to room temperature with the furnace.
Step（2）During described standing, moreover it is possible to air is passed through into dopamine solution with 3~5mL/min speed.
Step（3）The ethanol solution dripping quantity of described oxalic acid is 300~500mL, and time for adding is to be dripped in 1.5~2.5h
It is complete.
Step（3）The described insulation reaction condition under argon gas guard mode is：With 40~50mL/min speed into stove
Argon gas is passed through, under argon gas guard mode, 500~550 DEG C are warming up to 8~10 DEG C/min rate programs.
The beneficial effects of the invention are as follows：
（1）The present invention is first with the superior absorption property of activated carbon and abundant pore structure, adsorbing chlorinated aluminum solutions and hydrogen
Once it is to be tightly held by activated carbon to form aluminum hydroxide precipitation in the aluminum hydroxide precipitation that sodium oxide molybdena reaction is produced, solution, it is filled in
In activated carbon pore structure, it is to avoid aluminium hydroxide is reunited, then activated carbon kernel is removed through calcining, while in calcination process, hydrogen
Alumina decomposition, forms Woelm Alumina；
（2）The present invention utilizes the catechol and amino of dopamine using the modified self-control Woelm Alumina of dopamine solution immersion
Functional group, covalent and non-covalent interaction is set up in porous oxidation aluminium surface, forms the composite bed of superpower attachment, is improved many
The absorption property of porous aluminum oxide, adsorbing chlorinated stannous reacts the stannous oxalate crystal produced with oxalic acid, is combined the organic of layer surface
The steric hindrance of group can effectively prevent the stannous oxalate crystal of absorption from further growing up and reunite, and in drying and roasting process
In, because of the presence of Woelm Alumina, it can effectively prevent stannous oxalate crystal to reunite in the process, finally through sodium hydroxide
Solution soaks, and Woelm Alumina is removed, and the nano oxidized stannous of product is had abundant pore structure.
Embodiment
The activated carbon that 150~200g is crushed to 300~500 mesh is weighed, is poured into and is filled 800~1000mL mass fractions 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 will be ultrasonically treated after three-necked flask move into digital display and test the speed constant temperature blender with magnetic force, be in temperature
55~60 DEG C, rotating speed divides for quality under the conditions of 300~500r/min, is added dropwise into three-necked flask by dropping funel while stirring
Number is 20% sodium hydroxide solution, and pH is to 10.6~10.8 for regulation, treats completion of dropwise addition, continues 60~90min of constant temperature stirring reaction；
Treat that constant temperature stirring reaction terminates, by material filtering in three-necked flask, obtain activated carbon and aluminium hydroxide is combined filter cake, use deionized water
Detergent active charcoal and aluminium hydroxide are combined filter cake until cleaning solution is in neutrality, and the activated carbon and aluminium hydroxide after washing are combined
Filter cake is transferred in baking oven, is dried under the conditions of temperature is 105~110 DEG C to constant weight, obtains 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 programs
650~700 DEG C, insulation is calcined after 2~4h, cools to room temperature with the furnace, is discharged, and obtains porous calcining material；Weigh 30~50g institutes much
Hole calcining material, pours into and fills in the beaker that 200~300mL mass concentrations are 2g/L dopamine solutions, stirred and mixed with glass bar
After 10~20min, 20~30min is stood, during standing, sky is passed through into dopamine solution with 3~5mL/min speed
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 chlorides is added into four-hole boiling flask, and with 3~5mL/
Min speed 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, in temperature be 45~50 DEG C, rotating speed be 200~400r/min under the conditions of, dripped by dropping funel into four-hole boiling flask
Plus 300~500mL concentration be 0.15~0.18mol/L oxalic acid ethanol solution, control dripped off in 1.5~2.5h, wait to be added dropwise
Finish, continue 60~90min of constant temperature stirring reaction；Treat that constant temperature stirring reaction terminates, material filtering in four-hole boiling flask must be mixed
Filter residue, is washed with deionized mixing filter residue 3~5 times, and the mixing filter residue after washing is transferred into vacuum drying chamber, is in temperature
Dried under the conditions of 105~110 DEG C to constant weight, then dried mixing filter residue is transferred to tube type resistance furnace, with 40~50mL/min
Speed is passed through argon gas into stove, under argon gas guard mode, and 500~550 DEG C, guarantor are warming up to 8~10 DEG C/min rate programs
3~5h of temperature reaction；Treat that insulation reaction terminates, cool to room temperature with the furnace, discharge, obtain presoma material, and by gained presoma thing
Material, which is poured into, to be filled in the beaker that 600~800mL mass fractions are 10~15% sodium hydroxide solutions, then beaker immigration ultrasound is shaken
Instrument is swung, under the conditions of supersonic frequency is 40kHz, ultrasonically treated 45~60min；Ultrasonically treated end is treated, material in beaker is turned
Enter centrifuge, 10~15min is centrifuged with 6000~8000r/min rotating speeds, remove upper liquid, obtain 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 by the lower sediment thing after washing and does
Dry case, dries to constant weight under the conditions of temperature is 105~110 DEG C, discharges, and encapsulation produces nanoporous stannous oxide.
Example 1
The activated carbon that 150g is crushed to 300 mesh is weighed, three mouthfuls of burnings for filling that 800mL mass fractions are 20% liquor alumini chloridi are poured into
In bottle, and three-necked flask is moved into sonic oscillation instrument, under the conditions of supersonic frequency is 40kHz, ultrasonic disperse 15min, then will be super
Three-necked flask after sonication moves into digital display and tested the speed constant temperature blender with magnetic force, is 55 DEG C in temperature, rotating speed is 300r/min conditions
Under, mass fraction is added dropwise into three-necked flask by dropping funel while stirring for 20% sodium hydroxide solution, regulation pH to
10.6, completion of dropwise addition is treated, continues constant temperature stirring reaction 60min；Treat that constant temperature stirring reaction terminates, by material mistake in three-necked flask
Filter, obtains activated carbon and aluminium hydroxide is combined filter cake, and activated carbon is washed with deionized and aluminium hydroxide is combined filter cake until washing
Liquid is transferred in baking oven in neutrality, and by the compound filter cake of activated carbon and aluminium hydroxide after washing, is done under the conditions of temperature is 105 DEG C
It is dry to constant weight, obtain dry activated carbon and aluminium hydroxide and be combined filter cake, then dry activated carbon and aluminium hydroxide are combined filter cake and be transferred to
Muffle furnace, is warming up to after 650 DEG C, insulation calcining 2h with 8 DEG C/min rate programs, 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 concentrations are 2g/L dopamine solutions, use glass
After glass rod stirring mixing 10min, 20min is stood, during standing, sky is passed through into dopamine solution with 3mL/min speed
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 chlorides is added into four-hole boiling flask, and with 3mL/min speed 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 guard mode, in temperature
For 45 DEG C, rotating speed is under the conditions of 200r/min, it is 0.15mol/L that 300mL concentration, which is added dropwise, into four-hole boiling flask by dropping funel
The ethanol solution of oxalic acid, control is dripped off in 1.5h, treats completion of dropping, continues constant temperature stirring reaction 60min；Treat that constant temperature stirring is anti-
It should terminate, by material filtering in four-hole boiling flask, obtain mixing filter residue, mixing filter residue be washed with deionized 3 times, and by after washing
Mixing filter residue is transferred to vacuum drying chamber, is dried under the conditions of temperature is 105 DEG C to constant weight, then dried mixing filter residue is transferred to
Tube type resistance furnace, argon gas is passed through into stove with 40mL/min speed, under argon gas guard mode, with 8 DEG C/min rate program liters
Temperature is to 500 DEG C, insulation reaction 3h；Treat that insulation reaction terminates, cool to room temperature with the furnace, discharge, obtain presoma material, and by gained
Presoma material, which is poured into, to be filled in the beaker that 600mL mass fractions are 10% sodium hydroxide solution, then beaker is moved into sonic oscillation
Instrument, under the conditions of supersonic frequency is 40kHz, ultrasonically treated 45min；Ultrasonically treated end is treated, material in beaker is transferred to centrifugation
Machine, 10min is centrifuged with 6000r/min rotating speeds, removes upper liquid, obtains lower sediment thing, and gained is washed with deionized
Lower sediment thing, until the lower sediment thing after washing then is transferred to vacuum drying chamber by cleaning solution in neutrality, in temperature be 105
Dry to constant weight, discharge under the conditions of DEG C, encapsulation produces nanoporous stannous oxide.
Count by weight, take 70 parts of present invention gained nanoporous stannous oxides successively, 10 parts of acetylene blacks, 10 parts are poly- inclined
PVF, 180 parts of 1-METHYLPYRROLIDONEs are coated on copper foil of affluxion body, then copper foil is placed in into vacuum drying after being well mixed
In case, stannous oxide electrode is made in dry 8h under the conditions of 120 DEG C, then using stannous oxide electrode as negative pole, lithium metal is positive pole,
2025 type button cells are assembled under argon gas guard mode.After testing, stannous oxide electrode in use, reversible discharge
Capacity is up to 700mAh/g, through 100 charge and discharge cycles, and the average capacity attenuation circulated every time is 0.025%, with excellent
Chemical property.
Example 2
The activated carbon that 200g is crushed to 500 mesh is weighed, three mouthfuls of burnings for filling that 1000mL mass fractions are 20% liquor alumini chloridi are poured into
In bottle, and three-necked flask is moved into sonic oscillation instrument, under the conditions of supersonic frequency is 40kHz, ultrasonic disperse 20min, then will be super
Three-necked flask after sonication moves into digital display and tested the speed constant temperature blender with magnetic force, is 60 DEG C in temperature, rotating speed is 500r/min conditions
Under, mass fraction is added dropwise into three-necked flask by dropping funel while stirring for 20% sodium hydroxide solution, regulation pH to
10.8, completion of dropwise addition is treated, continues constant temperature stirring reaction 90min；Treat that constant temperature stirring reaction terminates, by material mistake in three-necked flask
Filter, obtains activated carbon and aluminium hydroxide is combined filter cake, and activated carbon is washed with deionized and aluminium hydroxide is combined filter cake until washing
Liquid is transferred in baking oven in neutrality, and by the compound filter cake of activated carbon and aluminium hydroxide after washing, is done under the conditions of temperature is 110 DEG C
It is dry to constant weight, obtain dry activated carbon and aluminium hydroxide and be combined filter cake, then dry activated carbon and aluminium hydroxide are combined filter cake and be transferred to
Muffle furnace, is warming up to after 700 DEG C, insulation calcining 4h with 10 DEG C/min rate programs, 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 concentrations are 2g/L dopamine solutions, use
After glass bar stirring mixing 20min, 30min is stood, during standing, is passed through with 5mL/min speed into dopamine solution
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,
Add the ethanol solution that 500mL concentration is 0.15mol/L stannous chlorides into four-hole boiling flask again, and with 5mL/min speed 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 guard mode, Yu Wen
Spend for 50 DEG C, rotating speed is under the conditions of 400r/min, it is 0.18mol/ that 500mL concentration, which is added dropwise, into four-hole boiling flask by dropping funel
The ethanol solution of L oxalic acid, control is dripped off in 2.5h, treats completion of dropping, continues constant temperature stirring reaction 90min；Treat that constant temperature is stirred
Reaction terminates, by material filtering in four-hole boiling flask, obtains mixing filter residue, mixing filter residue is washed with deionized 5 times, and by after washing
Mixing filter residue be transferred to vacuum drying chamber, in temperature be 110 DEG C under the conditions of dry to constant weight, then by it is dried mixing filter residue turn
Enter tube type resistance furnace, argon gas is passed through into stove with 50mL/min speed, under argon gas guard mode, with 10 DEG C/min rate programs
It is warming up to 550 DEG C, insulation reaction 5h；Treat that insulation reaction terminates, cool to room temperature with the furnace, discharge, obtain presoma material, and by institute
Presoma material pour into fill 800mL mass fractions be 15% sodium hydroxide solution beaker in, then by beaker immigration ultrasound shake
Instrument is swung, under the conditions of supersonic frequency is 40kHz, ultrasonically treated 60min；Treat ultrasonically treated end, by material in beaker be transferred to from
Scheming, 15min is centrifuged with 8000r/min rotating speeds, is removed upper liquid, is obtained 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 drying chamber is transferred to, is in temperature
Dry to constant weight, discharge under the conditions of 110 DEG C, encapsulation produces nanoporous stannous oxide.
Count by weight, take 75 parts of present invention gained nanoporous stannous oxides successively, 15 parts of acetylene blacks, 15 parts are poly- inclined
PVF, 200 parts of 1-METHYLPYRROLIDONEs are coated on copper foil of affluxion body, then copper foil is placed in into vacuum drying after being well mixed
In case, stannous oxide electrode is made in dry 10h under the conditions of 125 DEG C, then using stannous oxide electrode as negative pole, lithium metal is just
Pole, is assembled into 2025 type button cells under argon gas guard mode.After testing, stannous oxide electrode is in use, reversible
Discharge capacity is up to 710mAh/g, through 100 charge and discharge cycles, and the average capacity attenuation circulated every time is 0.035%, with excellent
Different chemical property.
Example 3
The activated carbon that 175g is crushed to 400 mesh is weighed, three mouthfuls of burnings for filling that 900mL mass fractions are 20% liquor alumini chloridi are poured into
In bottle, and three-necked flask is moved into sonic oscillation instrument, under the conditions of supersonic frequency is 40kHz, ultrasonic disperse 18min, then will be super
Three-necked flask after sonication moves into digital display and tested the speed constant temperature blender with magnetic force, is 58 DEG C in temperature, rotating speed is 400r/min conditions
Under, mass fraction is added dropwise into three-necked flask by dropping funel while stirring for 20% sodium hydroxide solution, regulation pH to
10.7, completion of dropwise addition is treated, continues constant temperature stirring reaction 75min；Treat that constant temperature stirring reaction terminates, by material mistake in three-necked flask
Filter, obtains activated carbon and aluminium hydroxide is combined filter cake, and activated carbon is washed with deionized and aluminium hydroxide is combined filter cake until washing
Liquid is transferred in baking oven in neutrality, and by the compound filter cake of activated carbon and aluminium hydroxide after washing, is done under the conditions of temperature is 108 DEG C
It is dry to constant weight, obtain dry activated carbon and aluminium hydroxide and be combined filter cake, then dry activated carbon and aluminium hydroxide are combined filter cake and be transferred to
Muffle furnace, is warming up to after 675 DEG C, insulation calcining 3h with 9 DEG C/min rate programs, 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 concentrations are 2g/L dopamine solutions, use glass
After glass rod stirring mixing 15min, 25min is stood, during standing, sky is passed through into dopamine solution with 4mL/min speed
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 chlorides is added into four-hole boiling flask, and with 4mL/min speed 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 guard mode, in temperature
For 48 DEG C, rotating speed is under the conditions of 300r/min, it is 0.16mol/L that 400mL concentration, which is added dropwise, into four-hole boiling flask by dropping funel
The ethanol solution of oxalic acid, control is dripped off in 2h, treats completion of dropping, continues constant temperature stirring reaction 75min；Treat constant temperature stirring reaction
Terminate, by material filtering in four-hole boiling flask, obtain mixing filter residue, mixing filter residue is washed with deionized 4 times, and will be mixed after washing
Close filter residue and be transferred to vacuum drying chamber, dried under the conditions of temperature is 108 DEG C to constant weight, then dried mixing filter residue is transferred to pipe
Formula resistance furnace, argon gas is passed through into stove with 45mL/min speed, under argon gas guard mode, is heated up with 9 DEG C/min rate programs
To 525 DEG C, insulation reaction 4h；Treat that insulation reaction terminates, cool to room temperature with the furnace, discharge, obtain presoma material, and by before gained
Drive body material, which is poured into, to be filled in the beaker that 700mL mass fractions are 12% sodium hydroxide solution, then beaker is moved into sonic oscillation
Instrument, under the conditions of supersonic frequency is 40kHz, ultrasonically treated 52min；Ultrasonically treated end is treated, material in beaker is transferred to centrifugation
Machine, 13min is centrifuged with 7000r/min rotating speeds, removes upper liquid, obtains lower sediment thing, and gained is washed with deionized
Lower sediment thing, until the lower sediment thing after washing then is transferred to vacuum drying chamber by cleaning solution in neutrality, in temperature be 108
Dry to constant weight, discharge under the conditions of DEG C, encapsulation produces nanoporous stannous oxide.
Count by weight, take 72 parts of present invention gained nanoporous stannous oxides successively, 12 parts of acetylene blacks, 12 parts are poly- inclined
PVF, 190 parts of 1-METHYLPYRROLIDONEs are coated on copper foil of affluxion body, then copper foil is placed in into vacuum drying after being well mixed
In case, stannous oxide electrode is made in dry 9h under the conditions of 122 DEG C, then using stannous oxide electrode as negative pole, lithium metal is positive pole,
2025 type button cells are assembled under argon gas guard mode.After testing, stannous oxide electrode in use, reversible discharge
Capacity is up to 705mAh/g, through 100 charge and discharge cycles, and the average capacity attenuation circulated every time is 0.03%, with excellent electricity
Chemical property.
Claims (5)
1. a kind of preparation method of nanoporous stannous oxide, it is characterised in that specifically preparation process is：
（1）150~200g activated carbons are weighed, three mouthfuls of burnings for filling that 800~1000mL mass fractions are 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, quality is used while stirring
Fraction is 20% sodium hydroxide solution, and pH is to 10.6~10.8 for regulation, treats that pH regulations terminate, continuation constant temperature stirring reaction 60~
90min；
（2）Treat that constant temperature stirring reaction terminates, by material filtering in three-necked flask, obtain activated carbon and aluminium hydroxide is combined filter cake, then
It is scrubbed and dry, obtain dry activated carbon and aluminium hydroxide is combined filter cake, then through calcining, obtain porous calcining material, weigh 30~50g
It is porous calcining material, pour into fill 200~300mL mass concentrations be 2g/L dopamine solutions beaker in, after stirring stand 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 concentration is added into four-hole boiling flask and is
The ethanol solution of 0.10~0.15mol/L stannous chlorides, is 45~50 DEG C in temperature, rotating speed is 200 under nitrogen guard mode
Under the conditions of~400r/min, 300~500mL concentration is added dropwise into four-hole boiling flask molten for the ethanol of 0.15~0.18mol/L oxalic acid
Liquid, treats completion of dropping, continues constant temperature 60~90min of stirring reaction, then by material filtering in four-hole boiling flask, filter, wash and do
It is dry to obtain dry mixed filter residue to constant weight, then dry mixed filter residue is transferred to tube type resistance furnace, it is incubated under argon gas guard mode anti-
Answer 3~5h；
（4）Treat that above-mentioned insulation reaction terminates, cool to room temperature with the furnace, discharge, obtain presoma material, and by gained presoma material
Pour into and fill in the beaker that 600~800mL mass fractions are 10~15% sodium hydroxide solutions, after sonic oscillation, centrifugation point
From removal upper liquid obtains lower sediment thing, then scrubbed, dry and encapsulation, produces 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, 2~4h of insulation calcining are warming up to 8~10 DEG C/min rate programs
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 air is passed through into dopamine solution with 3~5mL/min speed.
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 be dripped 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：Argon gas is passed through into stove with 40~50mL/min speed, protected in argon gas
Under shield state, 500~550 DEG C are warming up to 8~10 DEG C/min rate programs.
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