CN107369822B - A kind of tin oxide as negative electrode of lithium ion battery/C nano hollow ball material and preparation method thereof - Google Patents
A kind of tin oxide as negative electrode of lithium ion battery/C nano hollow ball material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano hollow ball material, comprising the following steps: A) it is modified to the nanometer titanium dioxide silicon ball progress surface prepared with stober method, obtain the nanometer titanium dioxide silicon ball modified by surface；B it) disperses phenyl tin compound, crosslinking agent and the nanometer titanium dioxide silicon ball modified by surface in solvent, and existing for catalyst under the conditions of carries out cross-linking reaction, obtains the nanometer medicine ball of surface grafting macromolecule layer；C removing template is removed after) the nanometer medicine ball of the surface grafting macromolecule layer is carbonized under the conditions of protective atmosphere, obtains SnO2/ C nano hollow ball material.Preparation method provided by the invention is simple, obtained SnO2Ultra-fine SnO in/C nano hollow ball material2Particle is embedded into porous carbon structure, which has good electric property when as lithium ion battery negative material.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of SnO as negative electrode of lithium ion battery2/ C receives
Rice hollow ball material and preparation method thereof.
Background technique
With the development of electronic equipment and electric car, lithium ion battery is because its energy density is high, has extended cycle life, in day
Often increasingly important role is played in life.In order to meet the needs of people are growing for lithium ion battery, people
It has done a large amount of work and has looked for the novel anode material with high capacity and outstanding cycle performance.Graphite is due to its special layer
Structure becomes a kind of most classic negative electrode material, but because its theoretical capacity only has 372mAh g-1, this works as far from satisfaction
Preceding needs.In order to solve this problem, many is for Si sill, metal alloy, metal oxide and metal chalcogenide chemical combination
Object, which has been carried out, to come.Because stannic oxide has theoretical capacity height (790mAh g-1), the advantages that storage resources are abundant, so
Stannic oxide sill is considered as one of most promising negative electrode material of lithium ion battery.
There are many schemes for improving SnO at present2The lithium ion battery negative material of base.For example, reducing insertion SnO2
The size of particle is to reduce its volume expansion ratio when as lithium ion battery negative material during charge and discharge removal lithium embedded
Example reduces the stress due to caused by volume expansion with this to reducing SnO2Dusting of the particle in charge and discharge process；
In addition there are one researchers by SnO2Particles coat protects SnO in porous carbon layer with this2Particle from charge and discharge process by
It is crushed caused by volume expansion, to improve SnO2The charge-discharge performance of/C composite.But above-mentioned SnO2/ C is compound
The preparation process of material complexity is always one and is difficult to the problem of breaking through.So far for simply preparing while having ultra-fine
SnO2The nanocomposite that particle is embedded into two big advantages of porous carbon structure is still a problem.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of SnO as negative electrode of lithium ion battery2/C
Nano hollow sphere material and preparation method thereof, preparation method provided by the invention is simple, obtained SnO2/ C nano hollow sphere material
Material has good electric property when as lithium ion battery negative material.
The present invention provides a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano hollow ball material, packet
Include following steps:
A surface) is carried out to the nanometer titanium dioxide silicon ball prepared with stober method to be modified, and obtains the nanometer modified by surface
Silica spheres；
B it) disperses phenyl tin compound, crosslinking agent and the nanometer titanium dioxide silicon ball modified by surface in molten
In agent, and existing for catalyst under the conditions of, carries out cross-linking reaction, obtains the nanometer medicine ball of surface grafting macromolecule layer；
C mould is removed after) the nanometer medicine ball of the surface grafting macromolecule layer is carbonized under the conditions of protective atmosphere
Plate obtains SnO2/ C nano hollow ball material.
Preferably, the stober method are as follows:
Water, dehydrated alcohol and ammonium hydroxide are mixed, mixed solution is obtained；
Dehydrated alcohol is added into the mixed solution and ethyl orthosilicate is mixed, is reacted, obtains suspension；
By the suspension centrifuge washing, nanometer titanium dioxide silicon ball is obtained.
Preferably, the nanometer titanium dioxide silicon ball modified by surface the preparation method comprises the following steps:
The dispersion liquid of nano silica and the solution containing modifying agent is respectively configured, it is halogenated that the modifying agent is selected from 2-
Methyl is to chlorobenzoyl chloride, 3- halogenated methyl to chlorobenzoyl chloride or 4- halogenated methyl to chlorobenzoyl chloride；
The solution containing modifying agent is added into the dispersion liquid of nano silica and is mixed, is reacted,
Obtain reaction solution；
The reaction solution is subjected to centrifuge washing, obtains the nanometer titanium dioxide silicon ball modified by surface.
Preferably, the phenyl tin compound is selected from triphenyltin, triphenyl phosphonium halides tin, stannous phenide, diphenyl halogen
Change tin or tetraphenyltin.
Preferably, the crosslinking agent be selected from dimethoxy alkane, dimethoxy alkene, alkylene dihalide, dihaloalkene,
Aliphatic dicarboxylic acid, aliphatic unsaturation diacid, dihalo alkanone or dihalo ketenes.
Preferably, the catalyst is selected from aluminium chloride, iron chloride, sulfuric acid, stannic chloride, zinc chloride or hydrofluoric acid.
Preferably, the solvent be selected from dichloroethanes, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitrobenzene, acetic acid,
Ethylene glycol, dimethylformamide, ethyl acetate or ethyl alcohol.
Preferably, the ratio of the phenyl tin compound and crosslinking agent is 1g:(0.5~20) mL.Phenyltin class chemical combination
Object and the mass ratio of the nanometer titanium dioxide silicon ball modified by surface are (0.5~10): 1.
Preferably, the method for the carbonization are as follows:
600~900 DEG C are warming up to the heating rate of 0.5~20 DEG C/min, keeps the temperature 30min~10h.
The present invention also provides a kind of SnO as negative electrode of lithium ion battery that above-mentioned preparation method is prepared2/ C receives
Rice hollow ball material, by indefinite form carbon-coating and the SnO that is scattered in the hole of the indefinite form carbon-coating2The nanometer that particle is formed
Hollow ball material, the SnO2The mass percent that particle accounts for the nano hollow sphere material is 10%~30%；The nanometer
The size of hollow sphere be 80~500nm, the indefinite form carbon-coating with a thickness of 5~20nm.
Compared with prior art, the present invention provides a kind of SnO as negative electrode of lithium ion battery2/ C nano hollow sphere material
The preparation method of material, comprising the following steps: A) it is modified to the nanometer titanium dioxide silicon ball progress surface prepared with stober method, it obtains
By the modified nanometer titanium dioxide silicon ball in surface；B) by phenyl tin compound, crosslinking agent and described modified by surface
Nanometer titanium dioxide silicon ball is scattered in solvent, and existing for catalyst under the conditions of carries out cross-linking reaction, obtains surface grafting height
The nanometer medicine ball of molecular layer；C the nanometer medicine ball of the surface grafting macromolecule layer) is subjected to carbon under the conditions of protective atmosphere
Removing template is removed after change, obtains SnO2/ C nano hollow ball material.Preparation method provided by the invention is simple, obtained SnO2/ C receives
Ultra-fine SnO in rice hollow ball material2Particle is embedded into porous carbon structure, which has when as lithium ion battery negative material
There is good electric property.
The result shows that SnO prepared by the present invention2/ C nano hollow ball material is in 200mA g-1Electric current under first electric discharge and first
The capacity of charging reaches 1378.5mAh g-1With 507.3mAh g-1Capacity still keeps 501mAh g after circulation 100 is enclosed-1Its
Capacity retention ratio reaches 98.8% (C100th/C2nd).High current 5000mA g in high rate performance-1Its capacity is down
162.5mAh g-1, and when electric current comes back to 200mA g after the testing current of multiple and different size of current-1Shi Qirong
Amount still preferably remains 536.6mAh g-1。
Detailed description of the invention
Fig. 1 is the SEM figure of the nanometer titanium dioxide silicon ball of stober method preparation；
Fig. 2 is that the SEM of grafting polymer nanometer medicine ball schemes；
Fig. 3 is the SEM figure of the engrafted nanometer medicine ball of carbonization；
Fig. 4 is SnO2The SEM of/C nano hollow sphere schemes；
Fig. 5 is the TEM figure of the nanometer titanium dioxide silicon ball of stober method preparation；
Fig. 6 is that the TEM of grafting polymer nanometer medicine ball schemes；
Fig. 7 is the TEM figure of the engrafted nanometer medicine ball of carbonization；
Fig. 8 is SnO2/ C nano hollow sphere TEM figure；
Fig. 9 is SnO2The circulating ratio figure of/C nano hollow sphere；
Figure 10 is SnO2/ C nano hollow sphere is in 200mA g-1Lower constant current charge-discharge diagram.
Specific embodiment
The present invention provides a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano hollow ball material, packet
Include following steps:
A surface) is carried out to the nanometer titanium dioxide silicon ball prepared with stober method to be modified, and obtains the nanometer modified by surface
Silica spheres；
B it) disperses phenyl tin compound, crosslinking agent and the nanometer titanium dioxide silicon ball modified by surface in molten
In agent, and existing for catalyst under the conditions of, carries out cross-linking reaction, obtains the nanometer medicine ball of surface grafting macromolecule layer；
C mould is removed after) the nanometer medicine ball of the surface grafting macromolecule layer is carbonized under the conditions of protective atmosphere
Plate obtains SnO2/ C nano hollow ball material.
In the present invention, the nanometer titanium dioxide silicon ball is prepared using stober method, wherein the stober method is preferred
Are as follows:
Water, dehydrated alcohol and ammonium hydroxide are mixed, mixed solution is obtained；
Dehydrated alcohol is added into the mixed solution and ethyl orthosilicate is mixed, is reacted, obtains suspension；
By the suspension centrifuge washing, nanometer titanium dioxide silicon ball is obtained.
Specifically, water, dehydrated alcohol and ammonium hydroxide are mixed first by the present invention, mixed solution is obtained, wherein described
The volume ratio of water, dehydrated alcohol and ammonium hydroxide is preferably 100:100:(6~80).The temperature of the mixing is preferably 10~80
DEG C, preferably 30~60 DEG C, the speed of the mixing is preferably 300rpm.
After obtaining mixed solution, 200mL dehydrated alcohol and 10~40mL ethyl orthosilicate are added in Xiang Suoshu mixed solution
It is mixed, is reacted, obtain suspension.
The mixing is reacted and is carried out as follows:
Mixed solution, dehydrated alcohol and ethyl orthosilicate are stirred under the conditions of 300rpm after mixing evenly, reaction 3 is small
When.
After obtaining suspension, the suspension is subjected to centrifuge washing, obtains nanometer titanium dioxide silicon ball.
Specifically, suspension is centrifuged under 8000rpm speed conditions, then successively respectively with dehydrated alcohol and
1,2- dichloroethanes washing centrifugation lower sediment thing, finally obtains nanometer titanium dioxide silicon ball.
In the present invention, the partial size for the nanometer titanium dioxide silicon ball being prepared according to above-mentioned preparation method is preferably 100~
600nm.Wherein, the present invention selects the nanometer titanium dioxide silicon ball that partial size is 100nm, 200nm and 400nm to carry out subsequent respectively
Surface is modified.
Then, surface is carried out to the above-mentioned nanometer titanium dioxide silicon ball being prepared to be modified, obtain receiving by surface is modified
Rice silica spheres.
In the present invention, the nanometer titanium dioxide silicon ball modified by surface the preparation method comprises the following steps:
The dispersion liquid of nano silica and the solution containing modifying agent is respectively configured；
The solution containing modifying agent is added into the dispersion liquid of nano silica and is mixed, is reacted,
Obtain reaction solution；
The reaction solution is subjected to centrifuge washing, obtains the nanometer titanium dioxide silicon ball modified by surface.
The dispersion liquid of nano silica and the solution containing modifying agent are configured first；
Wherein, the dispersion liquid of the nano silica is configured as follows:
The above-mentioned nanometer titanium dioxide silicon ball being prepared is dispersed in organic solvent and is placed in ice-water bath.
The organic solvent is selected from dichloroethanes, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitrobenzene, acetic acid, second two
Alcohol, dimethylformamide, ethyl acetate or ethyl alcohol, preferably dichloroethanes.
The solution containing modifying agent is configured as follows:
Modifying agent is mixed with organic solvent, obtains the solution of modifying agent.
The volume ratio of the modifying agent and organic solvent is preferably 2:40mL~2:100mL.The modifying agent is preferably 2-
Halogenated methyl is to chlorobenzoyl chloride, 3- halogenated methyl to chlorobenzoyl chloride or 4- halogenated methyl to chlorobenzoyl chloride, wherein described " halogenated "
For fluoro, bromo, chloro or iodo, more preferably chloro.The modifying agent is more preferably 4- chloromethyl to chlorobenzoyl chloride.
Wherein, the organic solvent is selected from dichloroethanes, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitrobenzene, second
Acid, ethylene glycol, dimethylformamide, ethyl acetate or ethyl alcohol, preferably dichloroethanes.
The solution containing modifying agent is added into the dispersion liquid of nano silica and is mixed, is reacted,
Obtain reaction solution；
In the present invention, it is preferably by the mode that the solution containing modifying agent is added into the dispersion liquid of nano silica
It is added dropwise.
The environment of above-mentioned solution reaction is ice-water bath, and after being added dropwise, continuation is reacted 1 hour under conditions of ice-water bath,
Then it is reacted 24 hours under the conditions of 20~35 DEG C again.
Reaction solution is obtained after reaction, the reaction solution is subjected to centrifuge washing, obtains the nanometer modified by surface
Silica spheres.
After reaction solution centrifugation, centrifuge washing is carried out three times using organic solvent, the organic solvent is preferably chlorine
Ethane, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitrobenzene, acetic acid, ethylene glycol, dimethylformamide, ethyl acetate or second
Alcohol, more preferably dichloroethanes.
It obtains after the modified nanometer titanium dioxide silicon ball in surface, by phenyl tin compound, crosslinking agent and the warp
It crosses the modified nanometer titanium dioxide silicon ball in surface to be scattered in solvent, and existing for catalyst under the conditions of carries out cross-linking reaction, obtains
To the nanometer medicine ball of surface grafting macromolecule layer.
Specifically, the following steps are included:
1) it will be scattered in solvent by the modified nanometer titanium dioxide silicon ball in surface, and obtain dispersion liquid, and by the dispersion
Liquid is placed under water bath condition；
2) phenyl tin compound and catalyst are added in Xiang Suoshu dispersion liquid；
3) solution that crosslinking agent is added into the dispersion liquid again takes out reaction solution after mixing carries out cross-linking reaction
Filter and drying, obtain the nanometer medicine ball of surface grafting macromolecule layer.
Wherein, the phenyl tin compound is selected from triphenyltin, triphenyl phosphonium halides tin, stannous phenide, diphenyl halogenation
Tin, tetraphenyltin, preferably triphenyltin.
The crosslinking agent is selected from dimethoxy alkane, dimethoxy alkene, alkylene dihalide, dihaloalkene, aliphatic
Dicarboxylic acids, aliphatic unsaturation diacid, dihalo alkanone or dihalo ketenes, preferably dimethoxymethane.
The catalyst is selected from aluminium chloride, iron chloride, sulfuric acid, stannic chloride, zinc chloride or hydrofluoric acid, preferably.
The solvent be selected from dichloroethanes, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitrobenzene, acetic acid, ethylene glycol,
Dimethylformamide, ethyl acetate or ethyl alcohol, preferably dichloroethanes.The solvent of crosslinking agent is dissolved in the solution of the crosslinking agent
Selected from dichloroethanes, methylene chloride, carbon tetrachloride, hexamethylene, benzene, nitrobenzene, acetic acid, ethylene glycol, dimethylformamide, acetic acid
Ethyl ester or ethyl alcohol, preferably dichloroethanes.
In the present invention, the ratio of the phenyl tin compound and crosslinking agent is 1g:(0.5~20) mL, preferably 1g:
(1~10) mL, more preferably 1g:1.5mL.Phenyl tin compound and the nanometer titanium dioxide silicon ball modified by surface
Mass ratio is (0.5~10): 1, preferably (1~8): 1, more preferably 1:1.
The temperature of the water bath condition is preferably 50~100 DEG C, and more preferably 60~80 DEG C.
The temperature of the cross-linking reaction is preferably 50~100 DEG C, and more preferably 60~80 DEG C；The time of the cross-linking reaction
Preferably 12 hours.
It when reaction solution is filtered, is filtered using deionized water and alcohol, by surface grafting during suction filtration
The nanometer medicine ball of macromolecule layer is washed.
The drying is preferably dried in vacuo, and the vacuum drying temperature is preferably 80 DEG C, when described vacuum drying
Between preferably 8 hours.
Removing template is removed after the nanometer medicine ball of the surface grafting macromolecule layer is carbonized under the conditions of protective atmosphere,
Obtain SnO2/ C nano hollow ball material.
The method of the carbonization are as follows:
600~900 DEG C are warming up to the heating rate of 0.5~20 DEG C/min, keeps the temperature 30min~10h.
Preferably, the heating rate is 1~15 DEG C/min, more preferably 5~10 DEG C/min.The temperature of the carbonization is excellent
700~800 DEG C, more preferably 720~780` DEG C are selected as, the time of the heat preservation is preferably 1~8h, more preferably 3~5h.
After carbonization, removing template is removed, obtains SnO2/ C nano hollow ball material.
In the present invention, the method for removing removing template is that the nanometer medicine ball after above-mentioned carbonization is placed in NaOH solution
In, and removing template is removed 2~12 hours under conditions of 30~90 DEG C.
The NaOH solution is the aqueous solution of NaOH, and the concentration of aqueous solution of the NaOH is preferably 2mol/L.The removal
The temperature of template is preferably 50~70 DEG C, and the time is preferably 4~10 hours.
Final removal nanometer titanium dioxide sol-gel, obtains the SnO as negative electrode of lithium ion battery2/ C nano hollow sphere material
Material.
The present invention also provides a kind of SnO as negative electrode of lithium ion battery that above-mentioned preparation method is prepared2/ C receives
Rice hollow ball material, the SnO2/ C nano hollow ball material is by indefinite form carbon-coating and to be scattered in the indefinite form carbon-coating
SnO in hole2The nano hollow sphere material that particle is formed, the SnO2Particle accounts for the quality hundred of the nano hollow sphere material
Divide than being 10%~30%, preferably 15%~25%；The size of the nano-hollow ball be 80~500nm, preferably 100~
400nm, more preferably 150~350nm, the indefinite form carbon-coating with a thickness of 5~20nm, preferably 8~15nm.The SnO2
Granular size is 4~20nm, preferably 5~10nm.
Preparation method provided by the invention is simple, obtained SnO2Ultra-fine SnO in/C nano hollow ball material2Particle insertion
To porous carbon structure, which has good electric property when as lithium ion battery negative material.
The result shows that SnO prepared by the present invention2/ C nano hollow ball material is in 200mA g-1Electric current under first electric discharge and first
The capacity of charging reaches 1378.5mAh g-1With 507.3mAh g-1Capacity still keeps 501mAh g after circulation 100 is enclosed-1Its
Capacity retention ratio reaches 98.8% (C100th/C2nd).High current 5000mA g in high rate performance-1Its capacity is down
162.5mAh g-1, and when electric current comes back to 200mA g after the testing current of multiple and different size of current-1Shi Qirong
Amount still preferably remains 536.6mAh g-1。
For a further understanding of the present invention, below with reference to embodiment to provided by the invention as negative electrode of lithium ion battery
SnO2/ C nano hollow ball material and preparation method thereof is illustrated, and protection scope of the present invention is not by the limit of following embodiment
System.
Embodiment 1
(1) 100mL deionized water, 100mL dehydrated alcohol and 64mL ammonium hydroxide are added in three-neck flask, and by flask
It is placed in 35 DEG C of warm water.Then using mechanical stirring and adjusting mixing speed is 300rpm/min, it is allowed to be sufficiently stirred
It is even；
(2) it takes 200mL dehydrated alcohol and 20mL ethyl orthosilicate to be added in beaker and is stirred evenly with glass bar；
(3) solution of step (2) is quickly poured into flask and is stirred to react 3h at 300rpm/min.
(4) the reaction suspension for obtaining step (3) is centrifuged in 8000rpm/min, and successively uses dehydrated alcohol respectively
Nanometer titanium dioxide silicon ball is obtained three times with the centrifugation of 1,2- dichloroethanes, and SEM and TEM figure are respectively as Fig. 1 and Fig. 5, Fig. 1 are
The SEM figure of the nanometer titanium dioxide silicon ball of stober method preparation, Fig. 5 are the TEM figure of the nanometer titanium dioxide silicon ball of stober method preparation.
(5) by step (4) preparation nano silica decompose equipped with 100mL1,2- dichloroethanes flask in and
Flask is placed in ice-water bath；
(6) it takes 5mL4- chloromethyl to be added in 40mL1,2- dichloroethanes chlorobenzoyl chloride slowly to instill after mixing evenly
Into the dispersion liquid of step (5).Allow it after dripping off the reaction was continued under ice-water bath 1h, then recession removes ice-water bath at room temperature
Reaction is for 24 hours；
(7) reaction solution for obtaining step (6) is centrifuged and is centrifuged three times with 1,2- dichloroethanes；
(8) improved silica for taking 3g step (7) to prepare is dispersed in the flask equipped with 100mL1,2- dichloroethanes,
And flask is placed in 80 DEG C of water-baths.And successively 3g triphenyl tin chloride and 2g anhydrous ferric chloride is taken to be added to flask respectively
In；
(9) 20mL dimethoxymethane and 40mL1,2- dichloroethanes is taken to be added dropwise to the flask of step (8) after mixing
In.Reaction solution is filtered into the nanometer medicine ball being grafted with a large amount of deionized waters after reaction 12h, then receives obtained grafting
Rice medicine ball is dried in vacuo 8h, SEM and TEM figure respectively if Fig. 2 and Fig. 6, Fig. 2 are that grafting polymer nanometer is solid at 80 DEG C
The SEM of ball schemes, and Fig. 6 is that the TEM of grafting polymer nanometer medicine ball schemes；
(10) step (9) dry engrafted nanometer medicine ball is placed in argon gas protection tube furnace, with 20 DEG C/min heating
Rate from 50 DEG C be warming up to 900 DEG C after the nanometer medicine ball that is carbonized of heat preservation 6hization, SEM and TEM figure are respectively such as Fig. 3 and figure
7, Fig. 3 be the SEM figure of the engrafted nanometer medicine ball of carbonization, and Fig. 7 is the TEM figure of the engrafted nanometer medicine ball of carbonization；
(11) step (10) carbonization nanometer medicine ball is obtained to be added in the plastic bottle of the NaOH equipped with 2mol/L, and
Plastic bottle is placed in reaction 12h in 80 DEG C of water-bath goes template to obtain SnO2/ C nano Hollow Sphere Composites, SEM and
TEM figure enters Fig. 4 and Fig. 8, Fig. 4 SnO respectively2The SEM of/C nano hollow sphere schemes, Fig. 5 SnO2The TEM of/C nano hollow sphere schemes；
Embodiment 2
(1) 100mL deionized water, 200mL dehydrated alcohol and 64mL ammonium hydroxide are added in three-neck flask, and by flask
It is placed in 35 DEG C of warm water.Then using mechanical stirring and adjusting mixing speed is 300rpm/min, it is allowed to be sufficiently stirred
It is even；
(2) it takes 200mL dehydrated alcohol and 10mL ethyl orthosilicate to be added in beaker and is stirred evenly with glass bar；
(3) solution of step (2) is quickly poured into flask and is stirred to react 3h at 300rpm/min.
(4) the reaction suspension for obtaining step (3) is centrifuged in 8000rpm/min, and successively uses dehydrated alcohol respectively
Nanometer titanium dioxide silicon ball is obtained three times with the centrifugation of 1,2- dichloroethanes.
(5) by step (4) preparation nano silica decompose equipped with 100mL1,2- dichloroethanes flask in and
Flask is placed in ice-water bath；
(6) it takes 5mL4- chloromethyl to be added in 40mL1,2- dichloroethanes chlorobenzoyl chloride slowly to instill after mixing evenly
Into the dispersion liquid of step (5).Allow it after dripping off the reaction was continued under ice-water bath 1h, then recession removes ice-water bath at room temperature
Reaction is for 24 hours；
(7) reaction solution for obtaining step (6) is centrifuged and is centrifuged three times with 1,2- dichloroethanes；
(8) improved silica for taking 3g step (7) to prepare is dispersed in the flask equipped with 100mL1,2- dichloroethanes,
And flask is placed in 80 DEG C of water-baths.And successively 0.5g triphenyl tin chloride and 2g anhydrous aluminum chloride is taken to be added to burning respectively
In bottle；
(9) 0.5mL dimethoxymethane and 40mL1,2- dichloroethanes is taken to be added dropwise to the flask of step (8) after mixing
In.Reaction solution is filtered into the nanometer medicine ball being grafted with a large amount of deionized waters after reaction 12h, then receives obtained grafting
Rice medicine ball is dried in vacuo 8h at 80 DEG C；
(10) step (9) dry engrafted nanometer medicine ball is placed in argon gas protection tube furnace, with 0.5 DEG C/min heating
Rate from 50 DEG C be warming up to 600 DEG C after the nanometer medicine ball that is carbonized of heat preservation 30minization；
(11) step (10) carbonization nanometer medicine ball is obtained to be added in the plastic bottle of the NaOH equipped with 2mol/L, and
Plastic bottle is placed in reaction 12h in 80 DEG C of water-bath goes template to obtain SnO2/ C nano Hollow Sphere Composites；
Embodiment 3
(1) 100mL deionized water, 200mL dehydrated alcohol and 64mL ammonium hydroxide are added in three-neck flask, and by flask
It is placed in 35 DEG C of warm water.Then using mechanical stirring and adjusting mixing speed is 300rpm/min, it is allowed to be sufficiently stirred
It is even；
(2) it takes 200mL dehydrated alcohol and 20mL ethyl orthosilicate to be added in beaker and is stirred evenly with glass bar；
(3) solution of step (2) is quickly poured into flask and is stirred to react 3h at 300rpm/min.
(4) the reaction suspension for obtaining step (3) is centrifuged in 8000rpm/min, and successively uses dehydrated alcohol respectively
Nanometer titanium dioxide silicon ball is obtained three times with carbon tetrachloride centrifugation.
(5) nano silica of step (4) preparation is decomposed in the flask equipped with 100mL carbon tetrachloride and will be burnt
Bottle is placed in ice-water bath；
(6) it takes 5mL4- chloromethyl to be added in 40mL carbon tetrachloride chlorobenzoyl chloride and is slowly added dropwise to step after mixing evenly
Suddenly in the dispersion liquid of (5).Allow it after dripping off the reaction was continued under ice-water bath 1h, then recession goes ice-water bath to react at room temperature
24h；
(7) reaction solution for obtaining step (6) is centrifuged and is centrifuged three times with carbon tetrachloride；
(8) improved silica for taking 1g step (7) to prepare is dispersed in the flask equipped with 100mL carbon tetrachloride, and will
Flask is placed in 80 DEG C of water-baths.And successively 1g diphenyl stannous chloride and 2g anhydrous ferric chloride is taken to be added to flask respectively
In；
(9) 1.5mL dimethoxy-ethane and 40mL carbon tetrachloride is taken to be added dropwise in the flask of step (8) after mixing.
Reaction solution is filtered into the nanometer medicine ball being grafted, the engrafted nanometer that then will be obtained with a large amount of deionized waters after reaction 12h
Medicine ball is dried in vacuo 8h at 80 DEG C；
(10) step (9) dry engrafted nanometer medicine ball is placed in argon gas protection tube furnace, is heated up with 5 DEG C/min fast
Rate from 50 DEG C be warming up to 700 DEG C after the nanometer medicine ball that is carbonized of heat preservation 3h；
(11) step (10) carbonization nanometer medicine ball is obtained to be added in the plastic bottle of the NaOH equipped with 2mol/L, and
Plastic bottle is placed in reaction 12h in 80 DEG C of water-bath goes template to obtain SnO2/ C nano Hollow Sphere Composites；
Embodiment 4
(1) 100mL deionized water, 200mL dehydrated alcohol and 64mL ammonium hydroxide are added in three-neck flask, and by flask
It is placed in 35 DEG C of warm water.Then using mechanical stirring and adjusting mixing speed is 300rpm/min, it is allowed to be sufficiently stirred
It is even；
(2) it takes 200mL dehydrated alcohol and 40mL ethyl orthosilicate to be added in beaker and is stirred evenly with glass bar；
(3) solution of step (2) is quickly poured into flask and is stirred to react 3h at 300rpm/min.
(4) the reaction suspension for obtaining step (3) is centrifuged in 8000rpm/min, and successively uses dehydrated alcohol respectively
Nanometer titanium dioxide silicon ball is obtained three times with nitrobenzene centrifugation.
(5) nano silica by step (4) preparation is decomposed in the flask equipped with 100mL nitrobenzene and by flask
It is placed in ice-water bath；
(6) it takes 5mL4- chloromethyl to be added in 40mL nitrobenzene chlorobenzoyl chloride and is slowly added dropwise to step after mixing evenly
(5) in dispersion liquid.Allow it after dripping off the reaction was continued under ice-water bath 1h, then recession goes ice-water bath to react at room temperature
24h；
(7) reaction solution for obtaining step (6) is centrifuged and is centrifuged three times with nitrobenzene；
(8) improved silica for taking 1g step (7) to prepare is dispersed in the flask equipped with 100mL nitrobenzene, and will be burnt
Bottle is placed in 80 DEG C of water-baths.And successively 1g tetraphenyltin and 2g anhydrous zinc chloride is taken to be added in flask respectively；
(9) 1.5mL1 is taken, 2 oxalic acid and 40mL nitrobenzene are added dropwise to after mixing in the flask of step (8).Reaction
Reaction solution is filtered to the nanometer medicine ball being grafted after 12h with a large amount of deionized waters, it is then that obtained engrafted nanometer is solid
Ball is dried in vacuo 8h at 80 DEG C；
(10) step (9) dry engrafted nanometer medicine ball is placed in argon gas protection tube furnace, is heated up with 5 DEG C/min fast
Rate from 50 DEG C be warming up to 700 DEG C after the nanometer medicine ball that is carbonized of heat preservation 3h；
(11) step (10) carbonization nanometer medicine ball is obtained to be added in the plastic bottle of the NaOH equipped with 2mol/L, and
Plastic bottle is placed in reaction 12h in 80 DEG C of water-bath goes template to obtain SnO2/ C nano Hollow Sphere Composites；
Embodiment 5
(1) SnO that Example 1 is prepared2/ C nano composite material, PVDF, conductive black powder are with 80:10:10
After mixing for ratio, it is added in beaker and is modulated into slurry using deionized water as solvent.
(2) slurry that step (1) is modulated into is uniformly coated on the copper foil of 9 μ m-thicks.It is dried in vacuo at 80 DEG C afterwards
24h。
(3) dried copper foil, roller pricks backlash into the disk of 10mm size under pressure.
(4) cathode is made with punching copper foil in the case where argon gas is protected, lithium piece is used as to electrode, 2032 size battery shells into
Row assembling.
(5) battery after being completed is placed to activation at room temperature to be tested for the property afterwards for 24 hours.The test of its high rate performance
For respectively in 200,500,1000,2000 and 5000mA g-16 circle of test, such as Fig. 9, Fig. 9 SnO under different size of electric current2/C
The circulating ratio figure of nano-hollow ball；Its constant current charge-discharge test is in 200mA g-1100 circle of circulation, such as schemes under the electric current of size
10, Figure 10 SnO2/ C nano hollow sphere is in 200mA g-1Lower constant current charge-discharge diagram.
The result shows that SnO prepared by the present invention2/ C nano hollow ball material is in 200mAg-1Electric current under first electric discharge and first
The capacity of charging reaches 1378.5mAh g-1With 507.3mAh g-1Capacity still keeps 501mAh g after circulation 100 is enclosed-1Its
Capacity retention ratio reaches 98.8% (C100th/C2nd).High current 5000mAg in high rate performance-1Its capacity is down
162.5mAh g-1, and when electric current comes back to 200mA g after the testing current of multiple and different size of current-1Shi Qirong
Amount still preferably remains 536.6mAh g-1。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of SnO as negative electrode of lithium ion battery2The preparation method of/C nano hollow ball material, which is characterized in that including with
Lower step:
A surface) is carried out to the nanometer titanium dioxide silicon ball prepared with stober method to be modified, and obtains the nano-silica modified by surface
SiClx ball；
The nanometer titanium dioxide silicon ball modified by surface the preparation method comprises the following steps:
The dispersion liquid of nano silica and the solution containing modifying agent is respectively configured, the modifying agent is selected from 2- halogenated methyl
To chlorobenzoyl chloride, 3- halogenated methyl to chlorobenzoyl chloride or 4- halogenated methyl to chlorobenzoyl chloride；
The solution containing modifying agent is added into the dispersion liquid of nano silica and is mixed, is reacted, is obtained
Reaction solution；
The reaction solution is subjected to centrifuge washing, obtains the nanometer titanium dioxide silicon ball modified by surface；
B) solvent is dispersed by phenyl tin compound, crosslinking agent and the nanometer titanium dioxide silicon ball modified by surface
In, and existing for catalyst under the conditions of, carries out cross-linking reaction, obtains the nanometer medicine ball of surface grafting macromolecule layer；
The crosslinking agent is selected from dimethoxy alkane, dimethoxy alkene, alkylene dihalide, dihaloalkene, binary aliphatic
Carboxylic acid, aliphatic unsaturation diacid, dihalo alkanone or dihalo ketenes；
The catalyst is selected from aluminium chloride, iron chloride, sulfuric acid, stannic chloride, zinc chloride or hydrofluoric acid；
C removing template is removed after) the nanometer medicine ball of the surface grafting macromolecule layer is carbonized under the conditions of protective atmosphere, is obtained
To SnO2/ C nano hollow ball material；
The method of the carbonization are as follows:
600~900 DEG C are warming up to the heating rate of 0.5~20 DEG C/min, keeps the temperature 30min~6h.
2. preparation method according to claim 1, which is characterized in that the stober method are as follows:
Water, dehydrated alcohol and ammonium hydroxide are mixed, mixed solution is obtained；
Dehydrated alcohol is added into the mixed solution and ethyl orthosilicate is mixed, is reacted, obtains suspension；
By the suspension centrifuge washing, nanometer titanium dioxide silicon ball is obtained.
3. preparation method according to claim 1, which is characterized in that the phenyl tin compound be selected from triphenyltin,
Triphenyl phosphonium halides tin, stannous phenide, diphenyl tin halides or tetraphenyltin.
4. preparation method according to claim 1, which is characterized in that the solvent is selected from dichloroethanes, methylene chloride, four
Chlorination carbon, hexamethylene, benzene, nitrobenzene, acetic acid, ethylene glycol, dimethylformamide, ethyl acetate or ethyl alcohol.
5. preparation method according to claim 1, which is characterized in that the ratio of the phenyl tin compound and crosslinking agent
For 1g:(0.5~20) mL, phenyl tin compound and the mass ratio of the nanometer titanium dioxide silicon ball modified by surface are
(0.5~10) g:1g.
6. a kind of preparation method as claimed in any one of claims 1 to 5, wherein be prepared as negative electrode of lithium ion battery
SnO2/ C nano hollow ball material, which is characterized in that by indefinite form carbon-coating and be scattered in the hole of the indefinite form carbon-coating
SnO2The nano hollow sphere material that particle is formed, the SnO2The mass percent that particle accounts for the nano hollow sphere material is
10%~30%；The size of the nano-hollow ball be 80~500nm, the indefinite form carbon-coating with a thickness of 5~20nm.
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| WO2006050638A1 (en) * | 2004-11-11 | 2006-05-18 | Institute Of Chemistry, Chinese Academy Of Science | The method for preparation of hollow spheres and composite hollow spheres with template |
| CN102282704A (en) * | 2008-11-18 | 2011-12-14 | 康奈尔大学 | Carbon coated anode materials |
| CN103193263A (en) * | 2013-03-27 | 2013-07-10 | 东北师范大学 | Preparation method and application of hollow SnO2@C nanosphere in lithium ion battery |
| CN106941176A (en) * | 2017-05-18 | 2017-07-11 | 广东工业大学 | A kind of SnO as lithium ion battery negative2/ C nano medicine ball and preparation method thereof |
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| WO2006050638A1 (en) * | 2004-11-11 | 2006-05-18 | Institute Of Chemistry, Chinese Academy Of Science | The method for preparation of hollow spheres and composite hollow spheres with template |
| CN102282704A (en) * | 2008-11-18 | 2011-12-14 | 康奈尔大学 | Carbon coated anode materials |
| CN103193263A (en) * | 2013-03-27 | 2013-07-10 | 东北师范大学 | Preparation method and application of hollow SnO2@C nanosphere in lithium ion battery |
| CN106941176A (en) * | 2017-05-18 | 2017-07-11 | 广东工业大学 | A kind of SnO as lithium ion battery negative2/ C nano medicine ball and preparation method thereof |
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