CN108400297A - A kind of silicon substrate lithium ion battery negative material and preparation method thereof - Google Patents
A kind of silicon substrate lithium ion battery negative material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of silicon substrate lithium ion battery negative materials and preparation method thereof, belong to technical field of lithium ion, solve the problems, such as that poorly conductive, cycle life existing for existing silicon based anode material are low.This method does template with nano zine oxide first, and the ZnO/SiO of nucleocapsid is prepared by the hydrolysis of organosilicon2；By ZnO/SiO2Progress high-temperature process, which is mixed, with Zn powder obtains ZnO/SiOx(0≤X<2)；It with acid carries out that hollow H SiO are obtained by the reaction againx；Again in H SiOxSurface cladding polyaniline obtains H SiOx/PANI；Finally polyaniline adsorption graphite oxide alkene and restore obtain H SiOx/ PANI/RGO, as silicon substrate lithium ion battery negative material.The manufacturing technique requirement of the present invention is low, and silicon based anode material structural stability is good, and electric conductivity is high, and cycle life greatly promotes.
Description
Technical field
The present invention relates to a kind of silicon substrate lithium ion battery negative materials and preparation method thereof, belong to lithium ion battery technology neck
Domain.
Background technology
Lithium ion battery is high with energy density, have extended cycle life, using it is pollution-free the advantages that, become current new energy and grind
The theme studied carefully is widely used in notebook, mobile phone, on electric vehicle.Lithium ion battery is usually using graphite as negative at present
Pole material still since the theoretical capacity of graphite is low, limits the energy density of lithium ion battery entirety.The theoretical capacity of silicon
Up to 4200mAhg-1, it is far above graphite, and rich reserves on earth, is a kind of excellent lithium ion battery negative material；But
The poorly conductive of silicon, in charge and discharge process volume expansion up to 3 times or more, be easy to happen material granule is broken, material from
The problems such as falling off on collector causes battery capacity to decay rapidly, and battery life is short, the bad result such as high rate performance difference.
In order to improve the activity of silicon and in the application of field of batteries, have received in silicon by chemical vapor deposition in the prior art
The surface deposition last layer carbon-coating or graphene of rice grain improve the performance of battery to increase the electrical conductance of silicon.But it should
Requirement of the method to equipment is high, high energy consumption, and the condition of deposition requires height.Also have and nano silicon particles be doped by boric acid,
Then silicon particle is performed etching with silver nitrate solution, to form porous silicon, alleviates volume expansion, promotes battery life.
The doping of boron is not high in this mode, and silver nitrate is of high cost, and the hole amount of gained is less and smaller, little to performance boost.Also
Be that the high conductivity materials such as silica-base material and graphene, activated carbon, carbon nanotube are carried out by the modes such as ball milling by Physical,
Increase the electric conductivity of silica-base material, improves battery performance.But Physical is there are the structural stability of material is bad, and each group point it
Between the low disadvantage of binding ability.
Invention content
The present invention is directed to the above defect existing in the prior art, propose a kind of silicon substrate lithium ion battery negative material and its
Preparation method, poorly conductive when which solves silica-base material as lithium ion battery negative material, structural stability is low, follows
Ring service life low problem.
An object of the present invention technical scheme is that, a kind of silicon substrate negative electrode of lithium ion battery material
The preparation method of material, this approach includes the following steps：
A, organic silicon source, ammonium hydroxide are added into nano zinc oxide fluid dispersion, after reaction, precipitation are obtained by filtration, and will sink
Shallow lake is heated, and the ZnO/SiO with nucleocapsid is obtained2；
B, under the protection of inert gas, by the ZnO/SiO with nucleocapsid2It is blended in hot conditions with active Zn powder
Under be heat-treated, obtain that there is storage lithium active silica-base material ZnO/SiOx, the SiOxThe numerical value of middle X is 0≤X<2；
C, by ZnO/SiOxIt carries out reacting the ZnO for removing internal layer and extra zinc powder with dilute acid soln, centrifugation, washing obtain
To hollow silica-base material H-SiOx；
D, by hollow silica-base material H-SiOXIt is added to aniline monomer in the mixed liquor of water and ethyl alcohol, regulation system
PH value is 1~2, adds ammonium persulfate solution, carries out polymerisation and is centrifuged, washed, obtain polyphenyl after reaction
Amine PANI coats hollow silica-base material H-SiOxBinary composite H-SiOx/PANI；
E, by above-mentioned binary composite H-SiOx/ PANI and graphene oxide dispersion are added to the water, and pass through electrostatic
Absorption, makes graphene oxide be adsorbed on binary composite H-SiOxThe surface of/PANI adds reducing agent, and controls temperature
It is reacted under conditions of 70~90 DEG C, obtains the tri compound material in polyaniline adsorption redox graphene RGO
Expect H-SiOx/PANI/RGO。
The present invention, as template, using organosilicon as silicon source, obtains the ZnO/ of nucleocapsid by using nano zine oxide
SiO2Material, and using active Zn powder as reducing agent, under the high temperature conditions by reducing silica at the storage active SiO of lithiumx
Material, the wherein numberical range of X are 0≤X<2.Silica, which does not have, stores up lithium activity, and the present invention is obtaining after reduction
The silica-base material SiO arrivedXHave storage lithium activity, in the negative material as lithium ion battery, can occur with lithium ion
Embedded and deintercalation reaction, realizes the effect for providing high power capacity.And it will not be introduced using Zn powder as reducing agent other unrelated
Element avoids the introducing of impurity, and excessively active reducing agent reduction-oxidation zinc is avoided to cause to influence active silica-base material SiOx
Be reduced.Extra zinc powder and silica-base material ZnO/SiO are removed under the action of diluted acid againXInternal ZnO templates, in obtaining
The silica-base material H-SiO of hollow structurex, the hollow structure of formation is conducive to alleviate volume expansion of the silica-base material in embedding lithium, real
Existing stabilizing material structure, promotes the effect of battery life and battery capacity.Since silica-base material conductivity itself is not high,
In H-SiOXExternal sheath polyaniline, polyaniline are a kind of excellent conducting polymer composites, can increase leading for material
Electrically and reduce material resistance, and be formed by conductive network to provide lithium ion transport channel；Meanwhile polyaniline has
Elasticity, when during charge and discharge volume expansion occurs for the silica-base material of its internal layer, polyaniline can fetter silica-base material,
Alleviate the stress that its volume expansion is brought, reduces the capacity attenuation caused by based particles are ruptured, fallen off from collector.Most
Afterwards, it in material outer layer adsorption and oxidation graphene and is restored, makes composite material that there is higher structural stability and electric conductivity,
Promote the capacity retention ratio of material.H-SiO in above-mentioned silicon substrate lithium ion battery negative material in the present inventionx, PANI, RGO tri-
The synergistic effect of component, so as to get trielement composite material H-SiOx/ PANI/RGO has both conductive height, structural stability
Height, the advantages of having extended cycle life.The manufacturing technique requirement of the present invention is low, and reaction is without in exacting terms such as high vacuum
Lower progress also has the advantages that at low cost, pollution-free and environmentally friendly.
In the preparation method of above-mentioned silicon substrate lithium ion battery negative material, preferably, organic silicon source described in step A
Selected from methyl orthosilicate, ethyl orthosilicate or butyl silicate.It is to be formed to introduce silicon source using the purpose of these organic silicon sources
ZnO/SiO with nucleocapsid2, have the advantages that raw material is easy to get.As a further preference, organosilicon described in step A
The mass ratio of source and zinc oxide is 3:1~1:3.
In the preparation method of above-mentioned silicon substrate lithium ion battery negative material, preferably, the temperature heated described in step A
Degree is 60~120 DEG C.Purpose is to improve stability to form stable silicon dioxide layer, avoids the occurrence of material granule rupture
Phenomena such as.
In the preparation method of above-mentioned silicon substrate lithium ion battery negative material, preferably, nano oxidized described in step A
Zinc pattern is spherical or rodlike, and the grain size of the nano zine oxide is 10~200nm.By introducing nano level zinc oxide template
Agent can control to obtain different-shape, grain size and the composite material in aperture.
In the preparation method of above-mentioned silicon substrate lithium ion battery negative material, preferably, high-temperature process described in step B
Temperature be 400~1000 DEG C.It is to make reducing silica at storage to restore silica by the purpose of high-temperature process
The active silica-base material SiO of lithiumx, high power capacity is provided.As further preferred, the temperature of the high-temperature process is 500~800
℃。
In the preparation method of above-mentioned silicon substrate lithium ion battery negative material, preferably, zinc powder described in step B and
ZnO/SiO2Mass ratio be 1:1~5:1.Purpose is the amount by regulating and controlling zinc powder, obtains the SiO of different oxygen contentx, and restore
Agent can prevent the reduction of internal layer zinc oxide from influencing outer layer silica using zinc powder rather than the more active metal such as magnesium powder
Reduction.The general best reaction time is 3~for 24 hours, silica can be enable more adequately to be restored, to be lived
Property silica-base material.In the preparation method of above-mentioned silicon substrate lithium ion battery negative material, preferably, diluted acid described in step C
For dilute hydrochloric acid or dilute sulfuric acid, a concentration of 1~6mol/L of the diluted acid.
In a kind of above-mentioned preparation method of silicon substrate lithium ion battery negative material, preferably, H-SiO in step DXWith
The mass ratio of aniline monomer is 1:3~3:1, the molar ratio of the aniline monomer and ammonium persulfate is 1:1.Purpose is to obtain difference
The polyaniline-coated layer of thickness makes material have preferable electric conductivity, and provides lithium ion transport channel.
In the preparation method of above-mentioned silicon substrate lithium ion battery negative material, preferably, in step E graphene oxide with
H-SiOxThe mass ratio of/PANI is 1:10~1:1, the reducing agent is hydroiodic acid, hydrogen peroxide or vitamin C.It can protect
Under conditions of card silica-base material is not dissolved and polyaniline do not gone doping, redox graphene makes material have high electricity
Pond activity.
The second object of the present invention is to what is be achieved by the following technical programs, a kind of silicon substrate negative electrode of lithium ion battery material
Material, the negative material include hollow active silica-base material H-SiOx, the SiOxThe numerical value of middle X is 0≤X<2；It is described hollow
Active silica-base material H-SiOxIt is coated with polyaniline PANI；The adsorption of the polyaniline has redox graphene RGO；
The negative material is H-SiOx/PANI/RGO.The hollow active silica-base material of internal layer has storage lithium activity, can be with lithium
Embedded and deintercalation reaction occurs for ion, provides high power capacity, and the hollow structure formed is conducive to alleviate silica-base material in embedding lithium
Volume expansion, realize stabilizing material structure effect, improve battery life；H-SiOxThe polyaniline of outer cladding can play
Increase electric conductivity and reduce the effect of internal resistance, and polyaniline has elasticity, can also play constraint silica-base material, and it is swollen to alleviate volume
Swollen and the stress of generation effect, avoids the capacity attenuation caused by based particles are broken or come off；The surface of polyaniline
The redox graphene of absorption can then play stabilizing material structure and improve the effect of electric conductivity.The collaboration of three components is made
Good conductivity is had both with enabling this negative material to realize, structural stability is high, the advantages of having extended cycle life.
In conclusion compared with prior art, the invention has the advantages that：
1. the manufacturing technique requirement of the present invention is low, reaction under the exacting terms such as high vacuum without carrying out, also
Have the advantages that at low cost, pollution-free and environmentally friendly.
2. in silicon substrate lithium ion battery negative material prepared by the present invention, H-SiOx, tri- component of PANI, RGO collaboration make
With, so as to get trielement composite material H-SiOxFor/PANI/RGO with good conductivity, structural stability is high, has extended cycle life
The advantages of.Silicon substrate lithium ion battery negative material prepared by the present invention is in 0.5Ag-1Current density under cycle 50 circle after capacity
Still there is 885mAhg-1, capacity retention ratio height.
Description of the drawings
Fig. 1 is the H-SiO in the embodiment of the present invention 1xThe transmission electron microscope picture of material.
Fig. 2 is the H-SiO in the embodiment of the present invention 2xThe transmission electron microscope picture of/PANI/RGO materials.
Fig. 3 is the H-SiO in the embodiment of the present invention 3xCycle performance of/PANI/RGO the materials under different current densities
Figure.
Fig. 4 is the H-SiO in the embodiment of the present invention 3x/ PANI/RGO materials are in 0.5Ag-1Current density under cyclicity
It can figure.
Specific implementation mode
Below by specific embodiments and the drawings, the technical solutions of the present invention will be further described, but this
Invention is not limited to these examples.
Embodiment 1
(1) it is the spherical Zinc oxide particles of nanometer of 200nm to take 1g grain sizes, is scattered in the mixed solution of 50mL water and ethyl alcohol
In, form nano zinc oxide fluid dispersion.Then 1g tetraethyl orthosilicates are slowly added into above-mentioned nano zinc oxide fluid dispersion,
It stirs while adding.After waiting for that tetraethyl orthosilicate all adds, 5mL concentrated ammonia liquors are added, after stirring 30 minutes, centrifugation, washing,
Obtained sediment is dried.Sediment is placed in Muffle furnace again, 120 DEG C of processing 1h is heated to, obtains with nucleocapsid knot
The ZnO/SiO of structure2；
(2) the above-mentioned ZnO/SiO with nucleocapsid is taken2With zinc powder according to mass ratio be 1：4 ratio mixing, in tubular type
In stove under the protection of nitrogen atmosphere, reduction reaction 3h is carried out with 650 DEG C of temperature heating.After reaction, obtain that there is storage lithium
Active silica-base material ZnO/SiOx(ZnO/SiO is used belowxIndicate), wherein SiOxTo have the storage active silicon base substance of lithium, and
The numberical range of X is 0≤X<2；
(3) ZnO/SiO that will be obtainedxPut into dilute hydrochloric acid solution and be stirred to react 1 hour, dilute hydrochloric acid it is a concentration of
1mol/L.After reaction, centrifugation and carrying out washing treatment are carried out, hollow active silicon base substance H-SiO is obtainedx；
(4) the silicon base substance H-SiO that 1g is hollow is takenx, it is scattered in the mixed solution of 200mL water and ethyl alcohol, stirs evenly
Afterwards, finely dispersed H-SiO is formedxDispersion liquid.1mL aniline monomers are added, after being sufficiently stirred, 2.45g ammonium persulfates are added,
And the pH value that hydrochloric acid regulation system is added is 2, and polymerisation 6h is carried out under conditions of ice bath.After polymerisation, carry out
Centrifugation, is washed 3 times with ethyl alcohol, obtains coating polyaniline (PANI) substance binary composite wood on hollow active silicon base substance surface
Expect H-SiOx/PANI；
(5) 0.3g binary composite H-SiO obtained above are takenx/ PANI substances are scattered in 30mL water, are added
The 2mg/mL graphene oxide dispersions of 30mL, are sufficiently stirred 1h.Then, 0.5g vitamin Cs are added into dispersion liquid, and will divide
Dispersion liquid heating water bath keeps thermotonus after ten minutes, is centrifuged, washed, dried, obtain polyaniline (PANI) table to 80 DEG C
The trielement composite material of face absorbing and reducing graphene oxide RGO, as final product H-SiOx/ PANI/RGO negative materials, should
Negative material is followed successively by hollow having and stores up the active silicon base substance (H-SiO of lithium from inside to outsidex), polyaniline (PANI) and reduction
Graphene oxide (RGO).
Fig. 1 is the hollow silica-base material H-SiO in the present embodimentxTransmission electron microscope picture.Institute is can be seen that by the figure
The H-SiO obtainedxFor the silica-base material of hollow form, silicon substrate layer thickness is about 50nm, and pore size is about 200nm, meets nano oxygen
Change the grain size of zinc.
The final product H-SiO that will be obtainedx/ PANI/RGO carries out electrochemical property test, and test process is：With this implementation
H-SiO prepared by examplex/ PANI/RGO negative materials are as working electrode, using lithium piece as to electrode, using the LiPF of 1mol/L6
For electrolyte, (it is 1 that wherein, solvent, which is volume ratio,：2 ethylene carbonate：Dimethyl carbonate), diaphragm produces for Celgard companies
2400 type polypropylene screens, be assembled into CR2032 type button cells.At room temperature, it is tested in 0.001~2V voltage ranges.
Multiplying power test is first successively with 0.1Ag-1,0.3Ag-1,0.5Ag-1,1Ag-1Current density cycle 10 circle, return 0.1Ag-1's
10 circle of current density cycle, test result are shown in Table 1；The current density of charge and discharge cycles test is 0.5Ag-1, test result is shown in Table
2。
Embodiment 2
(1) it is the spherical Zinc oxide particles of nanometer of 10nm to take 1g grain sizes, is scattered in the mixed solution of 50mL water and ethyl alcohol,
Form nano zinc oxide fluid dispersion.Then the positive quanmethyl silicates of 3g are slowly added into above-mentioned nano zinc oxide fluid dispersion, side
Side stirring is added.After waiting for that positive quanmethyl silicate all adds, 5mL concentrated ammonia liquors are added, after stirring 30 minutes, centrifugation, washing will
Obtained sediment drying.Sediment is placed in Muffle furnace again, 100 DEG C of processing 1.5h is heated to, obtains with nucleocapsid knot
The ZnO/SiO of structure2；
(2) the above-mentioned ZnO/SiO with nucleocapsid is taken2With zinc powder according to mass ratio be 1：3 ratio mixing, in tubular type
In stove and under the protection of nitrogen atmosphere, reduction reaction 6h is carried out with 750 DEG C of temperature heating.After reaction, had
Store up the active silica-base material ZnO/SiO of lithiumx(ZnO/SiO is used belowxIndicate), wherein SiOxTo have the storage active silicon substrate object of lithium
Matter, and X numberical ranges are 0≤X<2；
(3) ZnO/SiO that will be obtainedxIt puts into dilution heat of sulfuric acid and is stirred to react 1 hour, wherein dilute sulfuric acid is a concentration of
2mol/L.After reaction, centrifugation and carrying out washing treatment are carried out, hollow active silicon base substance H-SiO is obtainedx；
(4) the silicon base substance H-SiO that 1g is hollow is takenx, it is scattered in the mixed solution of 200mL water and ethyl alcohol, stirs evenly
Afterwards, 1.5mL aniline monomers are added, after being sufficiently stirred, add 3.68g ammonium persulfates, and the pH value of hydrochloric acid regulation system is added
It is 1.5, polymerisation 6h is carried out under conditions of ice bath.It after polymerisation, is centrifuged, is used in combination ethyl alcohol to wash 3 times, obtains
To in hollow silicon base substance surface cladding polyaniline (PANI) substance binary composite H-SiOx/PANI；
(5) 0.3g binary composite H-SiO obtained above are takenx/ PANI substance substances are scattered in 30mL water, then are added
The 1mg/mL graphene oxide dispersions for entering 30mL, are sufficiently stirred 1h.Then 0.5mL hydroiodic acids are added into dispersion liquid, and will
Dispersion liquid heating water bath keeps thermotonus after ten minutes to 90 DEG C, and obtained solid product is dried, obtained by centrifugation, washing
The trielement composite material of polyaniline (PANI) adsorption redox graphene RGO, as final product H-SiOx/PANI/
RGO negative materials, the negative material are followed successively by hollow having and store up the active silicon base substance (H-SiO of lithium from inside to outsidex), polyphenyl
Amine (PANI) and redox graphene (RGO).
Fig. 2 is H-SiO in the present embodimentxThe transmission electron microscope picture of/PANI/RGO composite materials, can be seen that by the figure
The H-SiO of gainedxRedox graphene is adsorbed on H-SiO in/PANI/RGO composite materialsxThe surfaces /PANI；Polyaniline-coated
In H-SiOxSurface forms clad.It combines closely between each component, forms stable structure.
The final product H-SiO that will be obtainedx/ PANI/RGO carries out electrochemical property test, and test process is：With this implementation
H-SiO prepared by examplex/ PANI/RGO negative materials are as working electrode, using lithium piece as to electrode, using the LiPF of 1mol/L6
For electrolyte, (it is 1 that wherein, solvent, which is volume ratio,:2 ethylene carbonate：Dimethyl carbonate), diaphragm produces for Celgard companies
2400 type polypropylene screens, be assembled into CR2032 type button cells.At room temperature, it is tested in 0.001~2V voltage ranges.
Multiplying power test is first successively with 0.1Ag-1,0.3Ag-1,0.5Ag-1,1Ag-1Current density cycle 10 circle, return 0.1Ag-1's
10 circle of current density cycle, test result are shown in Table 1；The current density of charge and discharge cycles test is 0.5Ag-1, test result is shown in Table
2。
Embodiment 3
(1) it is the spherical Zinc oxide particles of nanometer of 30nm to take 1g grain sizes, is scattered in the mixed solution of 50mL water and ethyl alcohol,
Form nano zinc oxide fluid dispersion.Then the positive tetrabutyl silicates of 1.5g are slowly added into above-mentioned nano zinc oxide fluid dispersion,
It stirs while adding.After waiting for that positive tetrabutyl silicate all adds, 5mL concentrated ammonia liquors are added, after stirring 30 minutes, centrifugation, washing,
Obtained sediment is dried.Sediment is placed in Muffle furnace again, 60 DEG C of processing 1h is heated to, obtains with nucleocapsid
ZnO/SiO2；
(2) the above-mentioned ZnO/SiO with nucleocapsid is taken2With zinc powder according to mass ratio be 1：3 ratio mixing, in tubular type
In stove and under the atmosphere of nitrogen protection, reduction reaction 3h is carried out with 850 DEG C of temperature heating.After reaction, had
Store up the active silica-base material ZnO/SiO of lithiumx(ZnO/SiO is used belowxIndicate), wherein SiOxTo have the storage active silicon substrate object of lithium
Matter, and the numberical range of X is 0≤X<2；
(3) ZnO/SiO that will be obtainedxPut into dilute hydrochloric acid solution and be stirred to react 1 hour, dilute hydrochloric acid it is a concentration of
3mol/L.After reaction, centrifugation and carrying out washing treatment are carried out, hollow active silicon base substance H-SiO is obtainedx；
(4) the silicon base substance H-SiO that 1g is hollow is takenx, it is scattered in the mixed solution of 200mL water and ethyl alcohol, stirs evenly
Afterwards, 3mL aniline monomers are added, after being sufficiently stirred, add 7.35g ammonium persulfates, and the pH value that hydrochloric acid regulation system is added is
1, polymerisation 8h is carried out under conditions of ice bath.It after polymerisation, is centrifuged, with ethyl alcohol to washing of precipitate 3 times, is obtained
To in hollow active silicon base substance surface cladding polyaniline (PANI) substance binary composite H-SiOx/PANI；
(5) 0.3g binary composite H-SiO obtained above are takenx/ PANI substances are scattered in 30mL water, are added
The 3mg/mL graphene oxide dispersions of 30mL, are sufficiently stirred 1h.Then 0.5mL hydrogen peroxide is added into dispersion liquid, and will divide
Dispersion liquid heating water bath keeps thermotonus after ten minutes, is centrifuged, washed, dried, obtain polyaniline (PANI) table to 80 DEG C
The trielement composite material of face absorbing and reducing graphene oxide RGO, as final product H-SiOx/ PANI/RGO negative materials, should
Negative material is followed successively by hollow having and stores up the active silicon base substance (H-SiO of lithium from inside to outsidex), polyaniline (PANI) and reduction
Graphene oxide (RGO).
The final product H-SiO that will be obtainedx/ PANI/RGO carries out electrochemical property test, and test process is：With this implementation
H-SiO prepared by examplex/ PANI/RGO negative materials are as working electrode, using lithium piece as to electrode, using the LiPF of 1mol/L6
For electrolyte, (it is 1 that wherein, solvent, which is volume ratio,:2 ethylene carbonate：Dimethyl carbonate), diaphragm produces for Celgard companies
2400 type polypropylene screens, be assembled into CR2032 type button cells.At room temperature, it is tested in 0.001~2V voltage ranges.
Multiplying power test is first successively with 0.1Ag-1,0.3Ag-1,0.5Ag-1,1Ag-1Current density cycle 10 circle, return 0.1Ag-1's
10 circle of current density cycle, is as a result shown in Fig. 3 and table 1；The current density of charge and discharge cycles test is 0.5Ag-1, as a result see Fig. 4 and
Table 2.
Wherein, Fig. 3 is H-SiO in the present embodimentxCycle of/PANI/RGO the composite materials under different current densities is bent
Line.From figure 3, it can be seen that trielement composite material H-SiOx/ PANI/RGO negative materials are in 0.1Ag-1,0.3Ag-1,
0.5Ag-1,1Ag-1Current density under, capacity 1188mAhg-1,1102mAhg-1,887mAhg-1,732mAhg-1；Work as electric current
Density is from 1Ag-1Return to 0.1Ag-1When, the capacity of material can be restored to 1152mAhg-1, illustrate excellent forthright again of material
Energy and good cycle performance.
Wherein, Fig. 4 is H-SiO in the present embodimentx/ PANI/RGO composite materials are in 0.5Ag-1Current density under cycle
Curve, it can be seen from the figure that the capacity for the first time of material is up to 987mAhg-1, the capacity of the second circle is 947mAhg-1, cycle 50
Capacity still has 885mAhg after circle-1, it is higher by the theoretical capacity of graphite significantly, capacity retention ratio 89.6% illustrates the silicon substrate
Material has very high cyclical stability.
Embodiment 4
(1) it is the Nanometer-sized Rods ZnO particle of 100nm to take 1g grain sizes, is scattered in the mixed solution of 50mL water and ethyl alcohol
In, form nano zinc oxide fluid dispersion.Then 2g tetraethyl orthosilicates are slowly added into above-mentioned nano zinc oxide fluid dispersion,
It stirs while adding.After waiting for that tetraethyl orthosilicate all adds, be added 5mL concentrated ammonia liquors, stirring 30 minutes after, carry out centrifugation and
Washing, and obtained sediment is dried.Sediment is placed in Muffle furnace again, 110 DEG C of processing 2h is heated to, is had
The ZnO/SiO of nucleocapsid2；
(2) the above-mentioned ZnO/SiO with nucleocapsid is taken2With zinc powder according to mass ratio be 1：5 ratio mixing, in tubular type
In stove and under nitrogen atmosphere protection, reduction reaction 6h is carried out with 700 DEG C of temperature heating.After reaction, obtain that there is storage
The active silica-base material ZnO/SiO of lithiumx(ZnO/SiO is used belowxIndicate), wherein SiOxTo have the storage active silicon base substance of lithium,
And the numberical range of X is 0≤X<2；
(3) ZnO/SiO that will be obtainedxPut into dilute hydrochloric acid solution and be stirred to react 1 hour, dilute hydrochloric acid it is a concentration of
6mol/L.After reaction, it is centrifuged and is washed, obtain hollow active silicon base substance H-SiOx；
(4) the silicon base substance H-SiO that 1g is hollow is takenx, it is scattered in the mixed solution of 200mL water and ethyl alcohol, stirs evenly
Afterwards, finely dispersed H-SiO is formedxDispersion liquid.1mL aniline monomers are added, after being sufficiently stirred, 2.45g ammonium persulfates are added,
And the pH value that hydrochloric acid regulation system is added is 1.0, and polymerisation 6h is carried out under conditions of ice bath.After polymerisation, into
Row centrifugation, is used in combination ethyl alcohol to wash 3 times, obtains multiple in hollow active silicon base substance surface cladding polyaniline (PANI) substance binary
Condensation material H-SiOx/PANI；
(5) 0.3g binary composite H-SiO obtained above are takenx/ PANI substances are scattered in 30mL water, are added
30mL 1.5mg/mL graphene oxide dispersions stir 1h.Then 0.5g hydroiodic acids are added into dispersion liquid, by dispersion liquid water
Bath is heated to 80 DEG C, keeps thermotonus after ten minutes, is centrifuged, washed, dried, obtain polyaniline (PANI) adsorption
The trielement composite material of redox graphene RGO, as final product H-SiOx/ PANI/RGO negative materials, the cathode material
Material is followed successively by hollow having and stores up the active silicon base substance (H-SiO of lithium from inside to outsidex), polyaniline (PANI) and oxygen reduction fossil
Black alkene (RGO).
Obtained product is subjected to correlated performance test, specific test is：At room temperature, in 0.001~2V voltage ranges
It is tested.Multiplying power test is first successively with 0.1Ag-1,0.3Ag-1,0.5Ag-1,1Ag-1Current density cycle 10 circle, return
0.1Ag-110 circle of current density cycle, test result is shown in Table 1；The current density of charge and discharge cycles test is 0.5Ag-1, test
It the results are shown in Table 2.
Embodiment 5
(1) it is the Nanometer-sized Rods ZnO particle of 120nm to take 3g grain sizes, is scattered in the mixed solution of 50mL water and ethyl alcohol
In, form nano zinc oxide fluid dispersion.Then the positive quanmethyl silicates of 1g are slowly added into above-mentioned nano zinc oxide fluid dispersion,
It stirs while adding.After waiting for that positive quanmethyl silicate all adds, be added 5mL concentrated ammonia liquors, stirring 30 minutes after, carry out centrifugation and
Washing, obtained sediment is dried.Sediment is placed in Muffle furnace again, 60 DEG C of processing 3h is heated to, is had
There is the ZnO/SiO of nucleocapsid2；
(2) the above-mentioned ZnO/SiO with nucleocapsid is taken2With zinc powder according to mass ratio be 5：1 ratio mixing, in tubular type
In stove and under nitrogen atmosphere protection, reduction reaction 3h is carried out with 1000 DEG C of temperature heating.After reaction, obtain that there is storage
The active silica-base material ZnO/SiO of lithiumx(ZnO/SiO is used belowxIndicate), wherein SiOxTo have the storage active silicon base substance of lithium,
And the numberical range of X is 0≤X<2；
(3) ZnO/SiO that will be obtainedxPut into dilute hydrochloric acid solution and be stirred to react 1 hour, dilute hydrochloric acid it is a concentration of
4.0mol/L.After reaction, it is centrifuged and is washed, obtain hollow active silicon base substance H-SiOx；
(4) the silicon base substance H-SiO that 1g is hollow is takenx, it is scattered in the mixed solution of 200mL water and ethyl alcohol, stirs evenly
Afterwards, finely dispersed H-SiO is formedxDispersion liquid.0.5mL aniline monomers are added, after being sufficiently stirred, 1.23g persulfuric acid is added
Ammonium, and the pH value that hydrochloric acid regulation system is added is 1.5, and polymerisation 6h is carried out under conditions of ice bath.After polymerisation,
It is centrifuged, ethyl alcohol is used in combination to wash 3 times, obtain coating polyaniline (PANI) substance binary on hollow active silicon base substance surface
Composite material H-SiOx/PANI；
(5) 0.3g binary composite H-SiO obtained above are takenx/ PANI substances are scattered in 30mL water, are added
The 1.5mg/mL graphene oxide dispersions of 200mL, are sufficiently stirred 1h.Then 0.5g hydroiodic acids are added into dispersion liquid, will divide
Dispersion liquid heating water bath keeps thermotonus after twenty minutes, is centrifuged, washed, dried, obtain polyaniline (PANI) table to 80 DEG C
The trielement composite material of face absorbing and reducing graphene oxide RGO, as final product H-SiOx/ PANI/RGO negative materials, should
Negative material is followed successively by hollow having and stores up the active silicon base substance (H-SiO of lithium from inside to outsidex), polyaniline (PANI) and reduction
Graphene oxide (RGO).
Obtained product is subjected to correlated performance test, specific test is：At room temperature, in 0.001~2V voltage ranges
Inside tested.Multiplying power test is first successively with 0.1Ag-1,0.3Ag-1,0.5Ag-1,1Ag-110 circle of current density cycle, then return
To 0.1Ag-110 circle of current density cycle, test result is shown in Table 1；The current density of charge and discharge cycles test is 0.5Ag-1, survey
Test result is shown in Table 2.
Comparative example 1
It is the spherical nano-silicon powder of 200nm to take commercially available grain size, carries out correlated performance test.It specifically tests and is：In room
Under temperature, tested in 0.001~2V voltage ranges.Multiplying power test is first successively with 0.1Ag-1,0.3Ag-1,0.5Ag-1,1Ag-1
Current density cycle 10 circle, return 0.1Ag-1Current density cycle 10 circle.Above-mentioned corresponding spherical nano-silicon powder
Test result is shown in Table 1；And it is 0.5Ag to carry out the current density of corresponding charge and discharge cycles test-1, specific test result
It is shown in Table 2.
Following table 1 is the final product H-SiO obtained to corresponding embodimentxCommercially available in/PANI/RGO and comparative example receives
Rice Si powder carries out multiplying power and tests acquired results.It is specific that test result is as follows shown in table 1：
Table 1
Following table 2 is the final product H-SiO obtained to corresponding embodimentxCommercially available in/PANI/RGO and comparative example receives
Rice Si powder carries out charge and discharge cycles and tests acquired results.It is specific that test result is as follows shown in table 2：
Table 2
It can be seen that from the test result of above-mentioned table 1 and use commercially available nano-silicon powder in current density for 0.1Ag-1When
Capacity is up to 3210mAhg-1, and when current density is 1Ag-1Shi Rongliang is only 124mAhg-1, when current density returns to 0.1Ag-1
Shi Rongliang only restores to 345mAhg-1, high rate performance is poor.And silica-base material prepared by the method in the present invention is in 1Ag-1When still
There is 760mAhg-1Above capacity, when current density returns to 0.1Ag-1Shi Rongliang can be restored to 930mAhg-1More than, have compared with
Good high rate performance.
From the test result in table 2 can be seen that using commercially available nano-silicon powder cycle 50 circle after capacity retention ratio only
Have 6.5%；And the silica-base material capacity retention ratio prepared by the method in the present invention is 80% or more.Therefore, in the present invention
Silica-base material prepared by method improves significantly compared to commercially available nano-silicon on high rate performance and cycle performance.
Specific embodiment described in the present invention is only an illustration of the spirit of the invention.Technology belonging to the present invention is led
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious that can make various changes or correct without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon substrate lithium ion battery negative material, which is characterized in that this approach includes the following steps：
A, organic silicon source, ammonium hydroxide are added into nano zinc oxide fluid dispersion, after reaction, precipitation are obtained by filtration, and will precipitate into
Row heat treatment, obtains the ZnO/SiO with nucleocapsid2；
B, under the protection of inert gas, by the ZnO/SiO with nucleocapsid2With active Zn powder mixing under the high temperature conditions into
Row heat treatment obtains having the active silica-base material ZnO/SiO of storage lithiumx, the SiOxThe numerical value of middle X is 0≤X<2；
C, by ZnO/SiOxIt carries out reacting the ZnO for removing internal layer and extra zinc powder with dilute acid soln, centrifugation, washing obtain hollow
Silica-base material H-SiOx；
D, by hollow silica-base material H-SiOXIt is added to aniline monomer in the mixed liquor of water and ethyl alcohol, the pH value of regulation system
It is 1~2, adds ammonium persulfate solution, carries out polymerisation and centrifuged, washed, obtain polyaniline after reaction
PANI coats hollow silica-base material H-SiOxBinary composite H-SiOx/PANI；
E, by above-mentioned binary composite H-SiOx/ PANI and graphene oxide dispersion are added to the water, and graphene oxide is made to inhale
It is attached to binary composite H-SiOxThe surfaces /PANI, add reducing agent, and control temperature and carried out under conditions of 70~90 DEG C
Reaction, obtains the trielement composite material H-SiO of polyaniline adsorption redox graphene RGOx/PANI/RGO。
2. the preparation method of silicon substrate lithium ion battery negative material according to claim 1, which is characterized in that institute in step A
It states organic silicon source and is selected from methyl orthosilicate, ethyl orthosilicate or butyl silicate.
3. the preparation method of silicon substrate lithium ion battery negative material according to claim 1, which is characterized in that institute in step A
The mass ratio for stating organic silicon source and zinc oxide is 3:1~1:3.
4. according to claims 1 or 2 or the preparation method of the 3 silicon substrate lithium ion battery negative materials, which is characterized in that step
The temperature heated described in A is 60~120 DEG C.
5. according to claims 1 or 2 or the preparation method of the 3 silicon substrate lithium ion battery negative materials, which is characterized in that step
Nano zine oxide pattern described in A is spherical or rodlike, and the grain size of the nano zine oxide is 10~200nm.
6. according to claims 1 or 2 or the preparation method of the 3 silicon substrate lithium ion battery negative materials, which is characterized in that step
Zinc powder described in B and ZnO/SiO2Mass ratio be 1:5~5:1；The temperature of high-temperature process described in step B is 400~1000
℃。
7. according to claims 1 or 2 or the preparation method of the 3 silicon substrate lithium ion battery negative materials, which is characterized in that step
Diluted acid described in C is dilute hydrochloric acid or dilute sulfuric acid, a concentration of 1~6mol/L of the diluted acid.
8. according to claims 1 or 2 or the preparation method of the 3 silicon substrate lithium ion battery negative materials, which is characterized in that step
H-SiO in DXMass ratio with aniline monomer is 1:3~3:1, the molar ratio of the aniline monomer and ammonium persulfate is 1:1.
9. according to claims 1 or 2 or the preparation method of the 3 silicon substrate lithium ion battery negative materials, which is characterized in that step
Graphene oxide described in E and H-SiOxThe mass ratio of/PANI is 1:10~1:1, the reducing agent is hydroiodic acid, hydrogen peroxide
Or vitamin C.
10. a kind of silicon substrate lithium ion battery negative material, which is characterized in that the negative material includes hollow active silica-base material
H-SiOx, the SiOxThe numerical value of middle X is 0≤X<2；The hollow active silica-base material H-SiOxIt is coated with polyaniline PANI,
The adsorption of the polyaniline has redox graphene RGO.
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| CN108987724A (en) * | 2018-08-16 | 2018-12-11 | 浙江衡远新能源科技有限公司 | A kind of hollow Si/C composite negative pole material of lithium ion battery and preparation method thereof |
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| CN110931753A (en) * | 2019-12-09 | 2020-03-27 | 华南师范大学 | Silicon negative electrode material and preparation method thereof |
| CN111146427A (en) * | 2019-12-31 | 2020-05-12 | 北京化工大学 | Method for preparing hollow core-shell structure nano silicon-carbon composite material by using polyaniline as carbon source and secondary battery using material |
| CN116014144A (en) * | 2023-03-27 | 2023-04-25 | 河南锂动电源有限公司 | Silicon oxide composite material and preparation method thereof |
| CN116014144B (en) * | 2023-03-27 | 2023-08-15 | 河南锂动电源有限公司 | Silicon oxide composite material and preparation method thereof |
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