CN106856241A - A kind of multiphase composite nanostructure negative material and preparation method thereof - Google Patents
A kind of multiphase composite nanostructure negative material and preparation method thereof Download PDFInfo
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- CN106856241A CN106856241A CN201611244053.3A CN201611244053A CN106856241A CN 106856241 A CN106856241 A CN 106856241A CN 201611244053 A CN201611244053 A CN 201611244053A CN 106856241 A CN106856241 A CN 106856241A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
The invention discloses a kind of multiphase composite nanostructure negative material and preparation method thereof, belong to lithium ion battery negative material and preparation method thereof field.The multiphase composite nanostructure negative material is class " concrete " structure, using surfactant modified silicon nanoparticle as SiO2Source, using organic titanic compound as TiO2Source, using graphene oxide dispersion as dispersant, precipitating reagent, Si/SiO is once prepared with glucose, sucrose or polyvinylpyrrolidone as organic carbon source, then by hydro-thermal reaction2/TiO2/ Graphene/C multiphases complex class " concrete " nanostructured negative material.The material can effectively overcome silicon based anode material cyclical stability poor, the shortcoming of high rate performance difference, the ion battery prepared as negative pole has the advantages that high power capacity, long lifespan, it is prepared by the easy suitable industrialization of its preparation method simultaneously, and raw material are cheap and easy to get, it is worth with huge commercial application.
Description
Technical field
The invention belongs to lithium ion battery negative material and preparation method thereof field, more specifically to a kind of multiphase
Composite nanostructure negative material and preparation method thereof.
Background technology
As the fossil energies such as oil, natural gas are quickly exhausted, and a large amount of exploitations of shale gas also to the air of the earth and
Marine environment brings huge impact, therefore the environment friend such as mankind nowadays society solar energy, wind energy, biomass energy and tide energy
Good new energy technology receives much concern.But because solar energy, wind energy and tidal power amount change with the change of power generation settings,
It is extremely unstable, and cannot be ultimately resulted in big by being incorporated to national public supply network into huge numbers of families and each enterprises and institutions
Amount generation of electricity by new energy factory and relevant device and material manufacturer loss even close down.How to solve this key issue, with stabilization,
Inexpensively, conveniently mode that new energy electric power successfully is carried out into peak regulation is grid-connected and be applied to mobile electronic device and electronic
Means of transport etc., is always the focus and the focus of research of science and industrial circle concern.Lithium ion battery is because with volume energy
Density is high, and power density is high, safety, low cost, the characteristic such as environment-friendly, is considered high performance green energy-storing device, can have
Effect solves the problems, such as the grid-connected use of above new energy, and promotes the development of electric automobile and high-performance mobile electronic equipment and answer
With.
Lithium ion battery positive and negative electrode material is the important component of battery, the actual capacity of electrode material, multiplying power and heap
Product density governs the power and energy density of lithium ion battery always.With Large Copacity energy storage device and power-type lithium ion electricity
The development in pond, market proposes higher, tightened up requirement to high-performance negative material.At present, high performance lithium ion battery is born
The research application of pole material and it is concentrated mainly on the unitary of composition and two such as tin (Sn), silicon (Si) and its oxide, nickel, cobalt and manganese
System of unit [(NixCoyMnz) O2] etc. transition metal oxide.This is mainly above transition metal and transition metal oxide possesses
Larger theory and actual capacity.Wherein Si possesses highest theoretical capacity (4200mAhg-1), it is considered to be most rich prospect,
It is the lithium ion battery negative material most expected by industrial quarters at present.But the sheet in silicon substrate composite negative pole material charge and discharge process
The problems such as levying huge volumetric expansion and slow ion mobility in defect, i.e. charge and discharge process, significantly reduces it
Coulombic efficiency, energy and power density, constrain silicon substrate composite negative pole material in high capacity cell and large-sized power field of power supplies
Commercialization popularization and application.Although being made some progress in terms of high power capacity silicon substrate composite negative pole in recent years, silicon substrate
The bulk density and cyclical stability of negative pole still cannot meet the demand of practical application, also larger room for promotion, so
Also one of emphasis and focus of lithium battery experts and scholars research are turned into.
At this stage the approach of silicium cathode material lift cyclical stability and high rate performance mainly by following three big measures come
Realize, it is specific as follows：(1) by the nanosizing and the oriented growth of nano silicon particles of silicon primary particle, so as to shorten lithium ion
The distance of migration lifts the high rate performance of silicium cathode, and is drawn from charge and discharge process is alleviated to a certain degree using nanoscale effect
The Volume Changes for rising cause the decline of electrode performance, in addition can be by controlling the direction of growth of nano silicon particles also can be further
The cyclical stability of lifting silicon nanometer negative pole.But transition considers that nanosizing will substantially reduce the bulk density of material, reduces silicon
The energy density of negative pole；Although the orientation controllable preparation of other nano silicon particles contributes to lift the cyclical stability of material, but
It is complicated preparation technology, low yield, high cost is unfavorable for commercial application；(2) by the micro- of rationally design Si-based nanometer material
See structure, controllable preparation carbon coating, SiO2Or TiO2Etc. the nano silicon particles nucleocapsid and hollow-core construction of cladding, by giving silicon nanometer
Core applies certain compression, and the Volume Changes of the silicon core in charge and discharge process, stabilization of solid electricity are suppressed to a certain extent
Solution matter interface phase, so as to preferably lift the cyclical stability of silicon nano material；But such material preparation process is complicated, efficiency
It is relatively low and cost is of a relatively high, thus such material and its preparation technology are not suitable for following large-scale production and industrialization should
It is required that.(3) three-dimensional conductive network is built using CNT and Graphene, while using in three-dimensional conductive network frame
The Volume Changes produced in charge and discharge process are alleviated in space, so as to obtain high rate performance and the preferable silicon-carbon cathode of cyclical stability
Material.But the price of CNT and Graphene is still higher at this stage, be not suitable for being commercialized large-scale application.
The method for presently mainly being cooperateed with by multistep processes, many kinds of measures is designed and prepares high performance silicon-carbon cathode material.
Typical example such as prepares carbon nano-fiber hard template first with electrostatic spinning technique, recycles CVD method in fiber surface
Deposition nano silicon material, one layer of TiO is prepared followed by solwution method on silicon-carbon nucleocapsid surface2Nanometer layer, eventually passes heat treatment
After obtain C/Si/TiO2Multi-layer core-shell structure.Such material has preferable high rate performance and a cyclical stability, but such material
Material preparation technology is complicated, and the cycle is long, high cost, low yield, therefore is unfavorable for the commercial applications of material.Therefore development technology letter
List, cycle is short, low cost, the synthetic method for being adapted to business large-scale production prepare high performance silicon-carbon cathode material as research
Emphasis and one of focus.
The content of the invention
It is poor for silicon based anode material cyclical stability present in prior art, high rate performance is poor, preparation method is complicated,
The problems such as poorly efficient and high cost, the invention provides a kind of multiphase composite nanostructure negative material and preparation method thereof, it has
There is class " concrete " structure, can solve that lithium ion battery high-volume silicon-carbon negative electrode material cyclical stability is poor, high rate performance
The problems such as difference, preparation technology complexity and high cost.
The purpose of the present invention is achieved through the following technical solutions.
Multiphase composite nanostructure negative material, it is characterised in that the multiphase composite nanostructure negative material structure
It is Si/SiO2/TiO2/ Graphene/C multiphases are combined.
The preparation method of multiphase composite nanostructure negative material, preparation process is as follows：
The dispersion of S1 nano silicon particles and surface treatment；
S2 nano silicon particles it is co-modified；
The dispersion of the co-modified nano silicon particles suspension of S3；
S4 additions glucose, sucrose or polyvinylpyrrolidone organic carbon source；
The carbonizing reduction reaction of S5 glucose, sucrose or polyvinylpyrrolidone organic carbon source；
S6 process annealings.
Further, a diameter of 30~100nm of nano silicon particles in step S1.
Further, the dispersion of nano silicon particles is with the step of surface treatment in step S1：Weigh 1g nano silica fumes
Be placed in 50~150mL ethanol, by 15~30min ultrasonic disperses treatment after, under conditions of magnetic agitation add 0.2~
2mL tetraethyl orthosilicates (TEOS) as surfactant, by 15~30min ultrasonic disperses.
Further, the co-modified step of nano silicon particles is in step S2：The fourth fat of 0.1~1mL metatitanic acids four is existed
The nano silicon particles alcohol dispersion liquid by the TEOS surface modifications obtained by step S1 is added dropwise under the auxiliary of magnetic agitation
In, at the uniform velocity stir 0.5~1h.
Further, it is the step of the dispersion of co-modified nano silicon particles suspension in step S3：Step S2 is obtained
The co-modified nano silicon particles suspension for obtaining is added dropwise to 20~50mL graphene oxides (GO) in the case where at the uniform velocity stirring
In dispersion liquid, after at the uniform velocity stirring addition is finished, then 0.5~3h is persistently stirred.
Further, graphene oxide (GO) dispersion liquid concentration is 0.5~0.1mg/mL.
Further, the organic carbon source step such as step S4 additions glucose, sucrose or polyvinylpyrrolidone is：Will
0.05g~0.5g glucose, sucrose or polyvinylpyrrolidonepowder powder are added to the co-modified silicon nanometer that step S3 is obtained
In grain suspension, 0.5~3h is at the uniform velocity stirred.
Further, the carbonizing reduction reaction of the organic carbon source such as step S5 glucose, sucrose or polyvinylpyrrolidone
Step is：Step S4 resulting solutions are placed in hydrothermal reaction kettle, 2~10h of hydro-thermal reaction at 160~220 DEG C, then will be anti-
Answer product first to wash 3 times, rear ethanol is washed three times, dried at 80 DEG C.
Further, annealing temperature is 350~600 DEG C in step S6, and annealing time is 2~6h.
Compared to prior art, the advantage of the invention is that：
(1) SiO in the multiphase composite nanostructure negative material in the present invention2And TiO2Play the volume for effectively suppressing Si
The effect of expansion, and Graphene and porous carbon play a part of cement, while SiO2And TiO2The Si nano particles of cladding are bonded
Together, three-dimensional class " concrete " structure is formed, buffer that Volume Changes in Si nano particle charge and discharge process cause on one side is interior
Stress, further lifts the cycle performance of nano silicon particles；
(2) the multiphase composite nanostructure negative material Graphene and porous carbon materials in the present invention form three mutually together
The conductive network of connection effectively lifts the high rate performance of Si negative poles；
(3) the multiphase composite nanostructure negative material Si/SiO in the present invention2/TiO2/ Graphene/C multiphase complex class
" concrete " nanostructured negative material has a high power capacity (500~1000mAh/g), the long-life (through two circle charge and discharges it is electro-active after,
300 circle capacity keep more than 100%)；
(4) prepared by the easy suitable industrialization of the multiphase composite nanostructure cathode material preparation method in the present invention, and former
Material is cheap and easy to get, is worth with huge commercial application, is the important negative pole of following Large Copacity, high power lithium ion cell
One of material.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of SSTGC-1；
Fig. 2 is the X-ray diffracting spectrum of SSTGC-1 and presoma SSTGC-1-P；
Fig. 3 is first circle charging and discharging curves of the SSTGC-1 under the current density of 0.1C；
Fig. 4 is SSTGC-1 charge and discharge cycles curves under 0.1C and 0.5C.
Specific embodiment
With reference to Figure of description and specific embodiment, the present invention is described in detail.
Embodiment 1
The present invention is class " concrete " structure nano composite negative pole material and preparation method thereof, belongs to high power capacity, long-life
Power type and accumulation energy type lithium ion battery Si/SiO2/TiO2/ Graphene/C multiphases complex class " concrete " nanostructured negative pole material
Material and its preparation method of low-coat scaleization.
Technical scheme is surfactant modified silicon nanoparticle using siliceous type organic, with organic titanizing
Compound is used as TiO2Source, using graphene oxide dispersion as dispersant, precipitating reagent, then with glucose, sucrose or polyethylene pyrrole
Pyrrolidone etc. is organic carbon source, then once prepares Si/SiO by hydro-thermal reaction2/TiO2/ Graphene/C multiphase complex class concrete
Nanostructured negative material.Its preparation process is as follows：
(1) weigh 1g50 nano silica fumes to be placed in 100mL ethanol, by obtaining preliminary point after the treatment of 15min ultrasonic disperses
Scattered nano-silicon alcohol suspending liquid.
(2) under conditions of at the uniform velocity stirring, 2mL tetraethyl orthosilicates (TEOS) are added dropwise over step as surfactant
In 1 made nano-silicon alcohol suspending liquid, the nano silicon particles of TEOS surface modifications are obtained after being processed through 30min ultrasonic disperses after
Alcohol dispersion liquid.
(3) the fourth fat of 0.5mL metatitanic acids four is added dropwise to by the TEOS tables obtained by step (2) under at the uniform velocity stirring state
In the nano silicon particles alcohol dispersion liquid of face modification, after at the uniform velocity stirring 30min, co-modified nano silicon particles ethanol dispersion is obtained
Liquid.
(4) graphene oxide (GO) dispersion liquid of 50mL1mg/mL is taken, 50mL deionized waters are added, is obtained after shaking up
0.5mg/mL graphene oxide dilute solutions.
(5) the co-modified nano silicon particles suspension that will be obtained according to step (3) at the uniform velocity stir in the case of dropwise
It is added in the GO dispersion liquids that 40mL is obtained by step (4), at the uniform velocity stirs after addition finishes, then persistently stir 1h, treats metatitanic acid
Four fourth fat and tetraethyl orthosilicate are fully hydrolyzed, and form uniform and stable Si/SiO2/TiO2/ graphene oxide colloid mixture suspends and divides
Dispersion liquid.
(6) 0.2g glucose powder is added to the Si/SiO obtained by step 52/TiO2/ graphene oxide epoxy glue
In body suspended dispersed liquid, continue at the uniform velocity stirring 1h after obtain second alcohol and water mixed solvent in Si/SiO2/TiO2/ graphite oxide
Alkene/glucose mixed solution.
(7) step (6) is obtained into mixed solution to be placed in hydrothermal reaction kettle, the hydro-thermal reaction 6h at 200 DEG C.Then will be anti-
Answer product first to wash 3 times, rear ethanol is washed 3 times, Si/SiO is obtained after being dried at 80 DEG C2/TiO2/ redox graphene/porous
Carbon heterogeneous composite material precursor.
(8) step (7) is finally obtained into Si/SiO2/TiO2Body before/redox graphene/porous carbon heterogeneous composite material
Body, further to remove the oxygen-containing functional group in reduced graphene and hydro-thermal porous carbon, is finally obtained in process annealing 5h at 450 DEG C
Obtain the excellent Si/SiO of electric conductivity2/TiO2/ Graphene/porous carbon (SSTGC-1) heterogeneous composite material, as shown in figure 1, SiO2
And TiO2The multiphase composite Nano of class " concrete " structure that the nano silicon particles Dispersed precipitate of cladding is constituted in Graphene and carbon
Structural material.
It is prepared by SSTGC-1 electrodes：
By SSTGC-1 classes " concrete " structure multiphase nano composite material (80%) as shown in Figure 1 and conductive black
(10%) and binding agent (PVDF, 10%) is uniformly mixed to prepare homogeneous slurry, then gained colloid is coated on copper foil surface, 70
After drying 3h at DEG C, continuation is vacuum dried 5h at 90 DEG C, final to obtain SSTGC-1 electrodes.
Button cell is assembled：It is to electrode and reference electrode, with 1mol/L LiPF with lithium piece6EC+DEC solution for electricity
Solution liquid, by made SSTGC-1 electrodes for working electrode is assembled into buckle type lithium-ion half-cell in vacuum glove box.
Chemical property feature：The button cell that will be installed carries out electrochemical property test with blue electricity battery test system.
Fig. 3 is constant current charge-discharge curve of the SSTGC-1 electrodes under 0.1C (1C=4200mA/g) current density, and battery is first under 0.1C
Circle electric discharge and charging capacity can reach 2176 and 1250mAh/g.Especially by 100 circles under the current density of 0.1C and 0.5C
Specific capacity may remain in 881mAh/g and 760mAh/g respectively after charge and discharge cycles test, as shown in Figure 4.
Embodiment 2
(1) weigh 1g30 nano silica fumes to be placed in 100mL ethanol, by obtaining preliminary point after the treatment of 15min ultrasonic disperses
Scattered nano-silicon alcohol suspending liquid.
(2) under conditions of at the uniform velocity stirring, 1mL tetraethyl orthosilicates (TEOS) are added dropwise over step as surfactant
(1) in made nano-silicon alcohol suspending liquid, the silicon nanometer of TEOS surface modifications is obtained after being processed through 15min ultrasonic disperses after
Grain alcohol dispersion liquid.
(3) the fourth fat of 0.4mL metatitanic acids four is added dropwise to by the TEOS tables obtained by step (2) under at the uniform velocity stirring state
In the nano silicon particles alcohol dispersion liquid of face modification, after at the uniform velocity stirring 1h, co-modified nano silicon particles ethanol dispersion is obtained.
(4) graphene oxide (GO) dispersion liquid of 50mL1mg/mL is taken, 50mL deionized waters are added, is obtained after shaking up
0.5mg/mL graphene oxide dilute solutions.
(5) the co-modified nano silicon particles suspension that will be obtained according to step (3) at the uniform velocity stir in the case of dropwise
It is added in the GO dispersion liquids that 40mL is obtained by step (4), at the uniform velocity stirs after addition finishes, then persistently stir 1h, treats metatitanic acid
Four fourth fat and tetraethyl orthosilicate are fully hydrolyzed, and form uniform and stable Si/SiO2/TiO2/ graphene oxide colloid mixture suspends and divides
Dispersion liquid.
(6) 0.4g glucose powder is added to the Si/SiO obtained by step (5)2/TiO2/ graphene oxide mixes
In colloidal suspension dispersion liquid, continue at the uniform velocity stirring 2h after obtain second alcohol and water mixed solvent in Si/SiO2/TiO2/ oxidation stone
Black alkene/glucose mixed solution.
(7) step (6) is obtained into mixed solution to be placed in hydrothermal reaction kettle, the hydro-thermal reaction 10h at 180 DEG C.Then will
Product is first washed 3 times, and rear ethanol is washed 3 times, and Si/SiO is obtained after being dried at 80 DEG C2/TiO2/ redox graphene/many
Hole carbon heterogeneous composite material precursor.
(8) step (7) is finally obtained into Si/SiO2/TiO2/ redox graphene/porous carbon heterogeneous composite material in
Process annealing 3h is finally led with further removing the oxygen-containing functional group in reduced graphene and hydro-thermal porous carbon at 500 DEG C
The Si/SiO of excellent electrical properties2/TiO2/ Graphene/porous carbon (SSTGC-2) heterogeneous composite material.
It is prepared by SSTGC-2 electrodes：By SSTGC-2 multiphases nano composite material (80%) and conductive black (10%) and bonding
Agent (PVDF, 10%) is uniformly mixed to prepare homogeneous slurry, then gained colloid is coated on into copper foil surface, and 3h is dried at 70 DEG C
Afterwards, continue to be vacuum dried 5h at 90 DEG C, it is final to obtain SSTGC-2 electrodes.
Button cell is assembled：It is to electrode and reference electrode, with 1mol/L LiPF with lithium piece6EC+DEC solution for electricity
Solution liquid, obtained SSTGC-2 electrodes are assembled into buckle type lithium-ion half-cell for working electrode in vacuum glove box.
Chemical property feature：The button cell that will be installed carries out electrochemical property test with blue electricity battery test system,
Can be protected respectively by specific capacity after 100 circle charge and discharge cycles tests under the current density of 0.1C and 0.5C (1C=4200mA/g)
Hold in 863mAh/g and 752mAh/g.Under the current density of 0.1C, battery first circle specific discharge capacity can reach 2150mAh/g.
Embodiment 3
(1) weigh 1g90 nano silica fumes to be placed in 100mL ethanol, by obtaining preliminary point after the treatment of 15min ultrasonic disperses
Scattered nano-silicon alcohol suspending liquid.
(2) under conditions of at the uniform velocity stirring, step is added dropwise over using 0.4mL tetraethyl orthosilicates (TEOS) as surfactant
Suddenly in (1) made nano-silicon alcohol suspending liquid, the silicon nanometer of TEOS surface modifications is obtained after being processed through 30min ultrasonic disperses after
Particle alcohol dispersion liquid.
(3) the fourth fat of 0.2mL metatitanic acids four is added dropwise to by the TEOS tables obtained by step (2) under at the uniform velocity stirring state
In the nano silicon particles alcohol dispersion liquid of face modification, after at the uniform velocity stirring 30min, co-modified nano silicon particles ethanol dispersion is obtained
Liquid.
(4) graphene oxide (GO) dispersion liquid of 50mL1mg/mL is taken, 200mL deionized waters are added, is obtained after shaking up
0.2mg/mL graphene oxide dilute solutions.
(5) the co-modified nano silicon particles suspension that will be obtained according to step (3) at the uniform velocity stir in the case of dropwise
It is added in the GO dispersion liquids that 30mL is obtained by step (4), at the uniform velocity stirs after addition finishes, then persistently stir 2h, treats metatitanic acid
Four fourth fat and tetraethyl orthosilicate are fully hydrolyzed, and form uniform and stable Si/SiO2/TiO2/ graphene oxide colloid mixture suspends and divides
Dispersion liquid.
(6) 0.1g polyvinylpyrrolidonepowder powders are added to the Si/SiO obtained by step (5)2/TiO2/ oxidation stone
In black alkene colloid mixture suspended dispersed liquid, continue at the uniform velocity stirring 1h after obtain second alcohol and water mixed solvent in Si/SiO2/
TiO2/ graphene oxide/glucose mixed solution.
(7) step (6) is obtained into mixed solution to be placed in hydrothermal reaction kettle, the hydro-thermal reaction 2h at 220 DEG C.Then will be anti-
Answer product first to wash 3 times, rear ethanol is washed 3 times, Si/SiO is obtained after being dried at 80 DEG C2/TiO2/ redox graphene/porous
Carbon heterogeneous composite material precursor.
(8) step 7 is finally obtained into Si/SiO2/TiO2/ redox graphene/porous carbon heterogeneous composite material is in 600
Process annealing 3h finally obtains electric conductivity further to remove the oxygen-containing functional group in reduced graphene and hydro-thermal porous carbon at DEG C
The excellent Si/SiO of energy2/TiO2/ Graphene/porous carbon (SSTGC-3) heterogeneous composite material.
It is prepared by SSTGC-3 electrodes：By SSTGC-3 multiphases nano composite material (80%) and conductive black (10%) and bonding
Agent (PVDF, 10%) is uniformly mixed to prepare homogeneous slurry, then gained colloid is coated on into copper foil surface, and 3h is dried at 70 DEG C
Afterwards, continue to be vacuum dried 5h at 90 DEG C, it is final to obtain SSTGC-1 electrodes.
Button cell is assembled：It is to electrode and reference electrode, with 1mol/L LiPF with lithium piece6EC+DEC solution for electricity
Solution liquid, buckle type lithium-ion half-cell is assembled into as working electrode with above-mentioned obtained SSTGC-3 electrodes in vacuum glove box.
Chemical property feature：The button cell that will be installed carries out electrochemical property test with blue electricity battery test system,
Can be protected respectively by specific capacity after 100 circle charge and discharge cycles tests under the current density of 0.1C and 0.5C (1C=4200mA/g)
Hold in 842mAh/g and 714mAh/g.Under the current density of 0.1C, battery first circle specific discharge capacity can reach 2205mAh/g.
Embodiment 4
(1) weigh 1g50 nano silica fumes to be placed in 100mL ethanol, by obtaining preliminary point after the treatment of 15min ultrasonic disperses
Scattered nano-silicon alcohol suspending liquid.
(2) under conditions of at the uniform velocity stirring, step is added dropwise over using 0.5mL tetraethyl orthosilicates (TEOS) as surfactant
Suddenly in (1) made nano-silicon alcohol suspending liquid, the silicon nanometer of TEOS surface modifications is obtained after being processed through 30min ultrasonic disperses after
Particle alcohol dispersion liquid.
(3) the fourth fat of 1mL metatitanic acids four is added dropwise to by the TEOS surfaces obtained by step (2) under at the uniform velocity stirring state
In the nano silicon particles alcohol dispersion liquid of modification, after at the uniform velocity stirring 1.5 hours, co-modified nano silicon particles ethanol dispersion is obtained
Liquid.
(4) graphene oxide (GO) dispersion liquid of 50mL1mg/mL is taken, 50mL deionized waters are added, is obtained after shaking up
0.5mg/mL graphene oxide dilute solutions.
(5) the co-modified nano silicon particles suspension that will be obtained according to step (3) at the uniform velocity stir in the case of dropwise
It is added in the GO dispersion liquids that 40mL is obtained by step (4), at the uniform velocity stirs after addition is finished and persistently stir 1h again, treats metatitanic acid four
Fourth fat and tetraethyl orthosilicate are fully hydrolyzed, and form uniform and stable Si/SiO2/TiO2/ graphene oxide colloid mixture suspended dispersed
Liquid.
(6) 0.2g sucrose powder is added to the Si/SiO obtained by step (5)2/TiO2/ graphene oxide epoxy glue
In body suspended dispersed liquid, continue at the uniform velocity stirring 1h after obtain second alcohol and water mixed solvent in Si/SiO2/TiO2/ graphite oxide
Alkene/glucose mixed solution.
(7) step (6) is obtained into mixed solution to be placed in hydrothermal reaction kettle, the hydro-thermal reaction 6h at 200 DEG C.Then will be anti-
Answer product first to wash 3 times, rear ethanol is washed 3 times, Si/SiO is obtained after being dried at 80 DEG C2/TiO2/ redox graphene/porous
Carbon heterogeneous composite material precursor.
(8) step (7) is finally obtained into Si/SiO2/TiO2/ redox graphene/porous carbon heterogeneous composite material in
Process annealing 5h is finally led with further removing the oxygen-containing functional group in reduced graphene and hydro-thermal porous carbon at 450 DEG C
The Si/SiO of excellent electrical properties2/TiO2/ Graphene/porous carbon (SSTGC-4) heterogeneous composite material.
It is prepared by SSTGC-4 electrodes：By SSTGC-4 multiphases nano composite material (80%) and conductive black (10%) and bonding
Agent (PVDF, 10%) is uniformly mixed to prepare homogeneous slurry, then gained colloid is coated on into copper foil surface, and 3h is dried at 70 DEG C
Afterwards, continue to be vacuum dried 5h at 90 DEG C, it is final to obtain SSTGC-4 electrodes.
Button cell is assembled：It is to electrode and reference electrode, with 1mol/L LiPF with lithium piece6EC+DEC solution for electricity
Solution liquid, buckle type lithium-ion half-cell is assembled into as working electrode with obtained SSTGC-4 electrodes in vacuum glove box.
Chemical property feature：The button cell that will be installed carries out electrochemical property test with blue electricity battery test system,
Can be protected respectively by specific capacity after 100 circle charge and discharge cycles tests under the current density of 0.1C and 0.5C (1C=4200mA/g)
Hold in 821mAh/g and 752mAh/g.Under the current density of 0.1C, battery first circle specific discharge capacity can reach 2105mAh/g.
Embodiment 5
(1) weigh 1g30 nano silica fumes to be placed in 100mL ethanol, by obtaining preliminary point after the treatment of 15min ultrasonic disperses
Scattered nano-silicon alcohol suspending liquid.
(2) under conditions of at the uniform velocity stirring, step is added dropwise over using 0.2mL tetraethyl orthosilicates (TEOS) as surfactant
Suddenly in (1) made nano-silicon alcohol suspending liquid, the silicon nanometer of TEOS surface modifications is obtained after being processed through 30min ultrasonic disperses after
Particle alcohol dispersion liquid.
(3) the fourth fat of 0.1mL metatitanic acids four is added dropwise to by the TEOS tables obtained by step (2) under at the uniform velocity stirring state
In the nano silicon particles alcohol dispersion liquid of face modification, after at the uniform velocity stirring 30min, co-modified nano silicon particles ethanol dispersion is obtained
Liquid.
(4) graphene oxide (GO) dispersion liquid of 50mL1mg/mL is taken, 450mL deionized waters are added, is obtained after shaking up
0.1mg/mL graphene oxide dilute solutions.
(5) the co-modified nano silicon particles suspension that will be obtained according to step (3) at the uniform velocity stir in the case of dropwise
It is added in the GO dispersion liquids that 40mL is obtained by step (4), at the uniform velocity stirs after addition finishes, then persistently stir 1h, treats metatitanic acid
Four fourth fat and tetraethyl orthosilicate are fully hydrolyzed, and form uniform and stable Si/SiO2/TiO2/ graphene oxide colloid mixture suspends and divides
Dispersion liquid.
(6) 0.1g glucose powder is added to the Si/SiO obtained by step (5)2/TiO2/ graphene oxide mixes
In colloidal suspension dispersion liquid, continue at the uniform velocity stirring 1h after obtain second alcohol and water mixed solvent in Si/SiO2/TiO2/ oxidation stone
Black alkene/glucose mixed solution.
(7) step (6) is obtained into mixed solution to be placed in hydrothermal reaction kettle, the hydro-thermal reaction 12h at 160 DEG C.Then will
Product is first washed 3 times, and rear ethanol is washed 3 times, and Si/SiO is obtained after being dried at 80 DEG C2/TiO2/ redox graphene/many
Hole carbon heterogeneous composite material precursor.
(8) step (7) is finally obtained into Si/SiO2/TiO2/ redox graphene/porous carbon heterogeneous composite material in
Process annealing 3h is finally led with further removing the oxygen-containing functional group in reduced graphene and hydro-thermal porous carbon at 550 DEG C
The Si/SiO of excellent electrical properties2/TiO2/ Graphene/porous carbon (SSTGC-5) heterogeneous composite material.
It is prepared by SSTGC-5 electrodes：By SSTGC-5 multiphases nano composite material (80%) and conductive black (10%) and bonding
Agent (PVDF, 10%) is uniformly mixed to prepare homogeneous slurry, then gained colloid is coated on into copper foil surface, and 3h is dried at 70 DEG C
Afterwards, continue to be vacuum dried 5h at 90 DEG C, it is final to obtain SSTGC-5 electrodes.
Button cell is assembled：It is to electrode and reference electrode, with 1mol/L LiPF with lithium piece6EC+DEC solution for electricity
Solution liquid, fastening lithium ionic cell is assembled into obtained SSTGC-5 electrodes as working electrode in vacuum glove box.
Chemical property feature：The button cell that will be installed carries out electrochemical property test with blue electricity battery test system,
Can be protected respectively by specific capacity after 100 circle charge and discharge cycles tests under the current density of 0.1C and 0.5C (1C=4200mA/g)
Hold in 801mAh/g and 683mAh/g.Under the current density of 0.1C, battery first circle specific discharge capacity can reach 2355mAh/g.
Embodiment 6
(1) weigh 1g70 nano silica fumes to be placed in 100mL ethanol, by obtaining preliminary point after the treatment of 15min ultrasonic disperses
Scattered nano-silicon alcohol suspending liquid.
(2) under conditions of at the uniform velocity stirring, step is added dropwise over using 0.5mL tetraethyl orthosilicates (TEOS) as surfactant
Suddenly in (1) made nano-silicon alcohol suspending liquid, the silicon nanometer of TEOS surface modifications is obtained after being processed through 1h ultrasonic disperses after
Grain alcohol dispersion liquid.
(3) the fourth fat of 1mL metatitanic acids four is added dropwise to by the TEOS surfaces obtained by step (2) under at the uniform velocity stirring state
In the nano silicon particles alcohol dispersion liquid of modification, after at the uniform velocity stirring 1h, co-modified nano silicon particles alcohol dispersion liquid is obtained.
(4) graphene oxide (GO) dispersion liquid of 50mL1mg/mL is taken, 50mL deionized waters are added, is obtained after shaking up
0.5mg/mL graphene oxide dilute solutions.
(5) the co-modified nano silicon particles suspension that will be obtained according to step 3 dropwise adds in the case where at the uniform velocity stirring
It is added in the GO dispersion liquids that 40mL is obtained by step (4), at the uniform velocity stirs after addition finishes, then persistently stir 1h, treats metatitanic acid four
Fourth fat and tetraethyl orthosilicate are fully hydrolyzed, and form uniform and stable Si/SiO2/TiO2/ graphene oxide colloid mixture suspended dispersed
Liquid.
(6) 0.5g glucose powder is added to the Si/SiO obtained by step (5)2/TiO2/ graphene oxide mixes
In colloidal suspension dispersion liquid, continue at the uniform velocity stirring 1.5h after obtain second alcohol and water mixed solvent in Si/SiO2/TiO2/ oxidation
Graphene/glucose mixed solution.
(7) step (6) is obtained into mixed solution to be placed in hydrothermal reaction kettle, the hydro-thermal reaction 6h at 200 DEG C.Then will be anti-
Answer product first to wash 3 times, rear ethanol is washed 3 times, Si/SiO is obtained after being dried at 80 DEG C2/TiO2/ redox graphene/porous
Carbon heterogeneous composite material precursor.
(8) step (7) is finally obtained into Si/SiO2/TiO2/ redox graphene/porous carbon heterogeneous composite material in
Process annealing 6h is finally led with further removing the oxygen-containing functional group in reduced graphene and hydro-thermal porous carbon at 400 DEG C
The Si/SiO of excellent electrical properties2/TiO2/ Graphene/porous carbon (SSTGC-6) heterogeneous composite material.
It is prepared by SSTGC-6 electrodes：By SSTGC-1 multiphases nano composite material (80%) and conductive black (10%) and bonding
Agent (PVDF, 10%) is uniformly mixed to prepare homogeneous slurry, then gained colloid is coated on into copper foil surface, and 3h is dried at 70 DEG C
Afterwards, continue to be vacuum dried 5h at 90 DEG C, it is final to obtain SSTGC-6 electrodes.
Button cell is assembled：It is to electrode and reference electrode, with 1mol/L LiPF with lithium piece6EC+DEC solution for electricity
Solution liquid, buckle type lithium-ion half-cell is assembled into as working electrode with obtained SSTGC-6 electrodes in vacuum glove box.
Chemical property feature：The button cell that will be installed carries out electrochemical property test with blue electricity battery test system,
Can be protected respectively by specific capacity after 100 circle charge and discharge cycles tests under the current density of 0.1C and 0.5C (1C=4200mA/g)
Hold in 875mAh/g and 747mAh/g.Under the current density of 0.1C, battery first circle specific discharge capacity can reach 2143mAh/g.
Below schematically the invention and embodiments thereof are described, the description does not have restricted, accompanying drawing
Shown in be also the invention one of implementation method, actual structure is not limited thereto.So, if this area
Those of ordinary skill enlightened by it, in the case where this creation objective is not departed from, designed and the technology without creative
The similar frame mode of scheme and embodiment, all should belong to the protection domain of this patent.
Claims (10)
1. a kind of multiphase composite nanostructure negative material, it is characterised in that the multiphase composite nanostructure negative material knot
Structure is Si/SiO2/TiO2/ Graphene/C multiphase composite nanostructures.
2. a kind of preparation method of multiphase composite nanostructure negative material, preparation process is as follows：
The dispersion of S1 nano silicon particles and surface treatment；
S2 nano silicon particles it is co-modified；
The dispersion of the co-modified nano silicon particles suspension of S3；
S4 additions glucose, sucrose or polyvinylpyrrolidone organic carbon source；
The carbonizing reduction reaction of S5 glucose, sucrose or polyvinylpyrrolidone organic carbon source；
S6 process annealings.
3. a kind of preparation method of multiphase composite nanostructure negative material according to claim 2, it is characterised in that step
A diameter of 30~the 100nm of nano silicon particles in rapid S1.
4. a kind of preparation method of multiphase composite nanostructure negative material according to claim 2, it is characterised in that step
The dispersion of nano silicon particles is with the step of surface treatment in rapid S1：Weigh 1g nano silica fumes to be placed in 50~150mL ethanol, pass through
After crossing the treatment of 15~30min ultrasonic disperses, 0.2~2mL tetraethyl orthosilicate (TEOS) conduct is added under conditions of magnetic agitation
Surfactant, 15~30min of ultrasonic disperse.
5. a kind of preparation method of multiphase composite nanostructure negative material according to claim 2, it is characterised in that step
The co-modified step of nano silicon particles is in rapid S2：The fourth fat of 0.1~1mL metatitanic acids four is dropwise added under the auxiliary of magnetic agitation
Enter in the nano silicon particles alcohol dispersion liquid of the TEOS surface modifications to obtained by by step S1, at the uniform velocity stir 0.5~1h.
6. a kind of preparation method of multiphase composite nanostructure negative material according to claim 2, it is characterised in that step
It is the step of the dispersion of co-modified nano silicon particles suspension in rapid S3：The co-modified nano silicon particles that step S2 is obtained are hanged
Supernatant liquid in 20~50mL graphene oxides (GO) dispersion liquid is added dropwise in the case of at the uniform velocity stirring, added by the uniform velocity stirring
Bi Hou, then persistently stir 0.5~3h.
7. a kind of preparation method of multiphase composite nanostructure negative material according to claim 6, it is characterised in that institute
Graphene oxide (GO) dispersion liquid concentration is stated for 0.5~0.1mg/mL.
8. a kind of preparation method of multiphase composite nanostructure negative material according to claim 2, it is characterised in that step
Rapid S4 additions glucose, sucrose or polyvinylpyrrolidone organic carbon source step are：By 0.05g~0.5g glucose, sucrose or
Polyvinylpyrrolidonepowder powder is added in the co-modified nano silicon particles suspension that step S3 is obtained, at the uniform velocity stir 0.5~
3h。
9. a kind of preparation method of multiphase composite nanostructure negative material according to claim 2, it is characterised in that step
The step of rapid S5 glucose, sucrose or polyvinylpyrrolidone organic carbon source carbonizing reduction react be：By step S4 resulting solutions
It is placed in hydrothermal reaction kettle, 2~10h of hydro-thermal reaction at 160~220 DEG C then first washes product 3 times, and ethanol is washed
Three times, dried at 80 DEG C.
10. the preparation method of a kind of multiphase composite nanostructure negative material according to claim 2, it is characterised in that
Annealing temperature is 350~600 DEG C in step S6, and annealing time is 2~6h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569750A (en) * | 2012-03-21 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Cathode composite material of lithium ion battery and preparation method thereof |
| CN102903930A (en) * | 2012-10-23 | 2013-01-30 | 中国科学院过程工程研究所 | Lithium ion secondary battery and preparation method thereof |
| CN103031724A (en) * | 2013-01-17 | 2013-04-10 | 哈尔滨工业大学 | Preparation method for carbon fiber surface composite coating |
| CN103311506A (en) * | 2013-06-25 | 2013-09-18 | 蒋涛 | Preparation method of silicon graphene-coated lithium titanate composite negative electrode material |
| CN103346307A (en) * | 2013-07-09 | 2013-10-09 | 中山大学 | Lithium-ion battery negative material and preparation method thereof |
| CN103531754A (en) * | 2013-10-17 | 2014-01-22 | 宁波卡尔新材料科技有限公司 | Preparation method of graphene/silicon dioxide/copper/silicon/soft carbon laminated composite negative pole material |
| CN103833032A (en) * | 2014-03-11 | 2014-06-04 | 中国第一汽车股份有限公司 | Graphene-based composite cathode material |
| CN104900851A (en) * | 2015-06-24 | 2015-09-09 | 湖北骆驼蓄电池研究院有限公司 | Cathode for lead-carbon batteries, production method of cathode and battery made with cathode |
| CN105063556A (en) * | 2015-07-17 | 2015-11-18 | 中国科学院合肥物质科学研究院 | Method for preparing nano metal particle array on graphene |
| EP3047905A1 (en) * | 2015-01-21 | 2016-07-27 | Université de Strasbourg | Method for preparing highly nitrogen-doped mesoporous carbon composites |
-
2016
- 2016-12-29 CN CN201611244053.3A patent/CN106856241B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569750A (en) * | 2012-03-21 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Cathode composite material of lithium ion battery and preparation method thereof |
| CN102903930A (en) * | 2012-10-23 | 2013-01-30 | 中国科学院过程工程研究所 | Lithium ion secondary battery and preparation method thereof |
| CN103031724A (en) * | 2013-01-17 | 2013-04-10 | 哈尔滨工业大学 | Preparation method for carbon fiber surface composite coating |
| CN103311506A (en) * | 2013-06-25 | 2013-09-18 | 蒋涛 | Preparation method of silicon graphene-coated lithium titanate composite negative electrode material |
| CN103346307A (en) * | 2013-07-09 | 2013-10-09 | 中山大学 | Lithium-ion battery negative material and preparation method thereof |
| CN103531754A (en) * | 2013-10-17 | 2014-01-22 | 宁波卡尔新材料科技有限公司 | Preparation method of graphene/silicon dioxide/copper/silicon/soft carbon laminated composite negative pole material |
| CN103833032A (en) * | 2014-03-11 | 2014-06-04 | 中国第一汽车股份有限公司 | Graphene-based composite cathode material |
| EP3047905A1 (en) * | 2015-01-21 | 2016-07-27 | Université de Strasbourg | Method for preparing highly nitrogen-doped mesoporous carbon composites |
| CN104900851A (en) * | 2015-06-24 | 2015-09-09 | 湖北骆驼蓄电池研究院有限公司 | Cathode for lead-carbon batteries, production method of cathode and battery made with cathode |
| CN105063556A (en) * | 2015-07-17 | 2015-11-18 | 中国科学院合肥物质科学研究院 | Method for preparing nano metal particle array on graphene |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713242A (en) * | 2017-10-26 | 2019-05-03 | 银隆新能源股份有限公司 | Titanium silicon-carbon cathode material and preparation method thereof with nucleocapsid pomegranate structure |
| CN109713242B (en) * | 2017-10-26 | 2022-02-18 | 银隆新能源股份有限公司 | Titanium silicon carbon negative electrode material with core-shell pomegranate structure and preparation method thereof |
| CN107986380A (en) * | 2017-12-02 | 2018-05-04 | 延海平 | A kind of N doping coateds TiO2The technique of photocatalyst for degrading waste water |
| CN107986380B (en) * | 2017-12-02 | 2021-08-27 | 黄建勇 | N-doped wrapped TiO2Process for degrading wastewater by using photocatalyst |
| CN108923027A (en) * | 2018-06-26 | 2018-11-30 | 华南师范大学 | A kind of organic acid modified Si/TiO2/ rGO@C lithium ion battery negative material and the preparation method and application thereof |
| CN111441107A (en) * | 2020-03-23 | 2020-07-24 | 江苏师范大学 | Spinning solution for preparing carbon fiber material, flexible electrode material and preparation method |
| CN111646473A (en) * | 2020-06-04 | 2020-09-11 | 松山湖材料实验室 | Si-TiO2Preparation method of-C composite nanowire, product and application thereof |
| CN111646473B (en) * | 2020-06-04 | 2022-02-11 | 松山湖材料实验室 | Si-TiO2Preparation method of-C composite nanowire, product and application thereof |
| CN114039032A (en) * | 2021-11-08 | 2022-02-11 | 深圳市翔丰华科技股份有限公司 | Titanium dioxide (B) negative electrode material with improved performance and preparation method thereof |
| CN114284479A (en) * | 2021-12-22 | 2022-04-05 | 博路天成新能源科技有限公司 | Preparation method of novel carbon-silicon negative electrode material |
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