CN110459732A - A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece and preparation method thereof and lithium ion battery - Google Patents
A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece and preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN110459732A CN110459732A CN201910752748.XA CN201910752748A CN110459732A CN 110459732 A CN110459732 A CN 110459732A CN 201910752748 A CN201910752748 A CN 201910752748A CN 110459732 A CN110459732 A CN 110459732A
- Authority
- CN
- China
- Prior art keywords
- graphene
- silicon
- sio
- carbon composite
- pole piece
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation methods: the silicon/graphene/carbon composite cellulosic membrane cathode pole piece is with method of electrostatic spinning by SiOx/ graphene/carbon composite nano-fiber membrane is attached to SiO in situxThe surface of/graphene film is constituted, and the value range of the x is 0≤x < 2.The present invention overcomes silicon materials conductivity itself is lower and the larger problem of cubical expansivity and collector are corroded bring battery short circuits, degradation problem.The present invention not only increases the adhesive force between active material and collector, and the contact resistance between collector and active material is also reduced, therefore the silicon/graphene/carbon composite cellulosic membrane cathode pole piece can promote the chemical property and service life of lithium ion battery.
Description
Technical field
It is especially a kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece, right the invention belongs to technical field of lithium batteries
The silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method, and it is negative using the silicon/graphene/carbon composite cellulosic membrane
The lithium ion battery of pole pole piece.
Background technique
Silicon materials are currently a kind of negative as lithium ion battery because of its higher lithium storage content and lower discharge platform
The popular research object of pole material.But in charge and discharge process, the lower conductivity of silicon materials itself and biggish volume are swollen
Swollen rate limits its commercial applications.Meanwhile collecting in lithium ion battery through being used as frequently with metals such as copper foil and aluminium foils at present
Fluid, but this technical solution has the following disadvantages: that 1, density metal is larger, reduces the ratio of active material in the electrodes
Example, limits the raising of battery energy density.2, electrochemical stability is poor, and there are anodic attacks etc. in long-term cyclic process
Problem accelerates the capacity attenuation of battery, reduces its service life.3, the interface of the contact surface of metal collector and active material
Resistance is larger, and high rate performance under the conditions of high current charge-discharge is restricted.Therefore, how to develop a kind of novel lithium from
Sub- battery silicon/graphene/carbon composite cellulosic membrane cathode pole piece, can overcome the above-mentioned problems in the prior art, be ability
Field technique personnel need the direction studied.
Summary of the invention
The object of the present invention is to provide a kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation methods, overcome silicon
The problem of material conductivity itself is lower and the larger problem sum aggregate fluid of cubical expansivity is easily corroded.
The technical scheme adopted is as follows:
A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method: the silicon/graphene/carbon composite cellulosic membrane
Cathode pole piece is with method of electrostatic spinning by SiOx/ graphene/carbon composite nano-fiber membrane is attached to SiO in situxThe table of/graphene film
Face is constituted, and the value range of the x is 0≤x < 2.
Preferably, above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method includes the following steps: S1: will
Graphite oxide is scattered in deionized water, is uniformly dispersed with high pressure homogenizer, and graphene oxide slurry is obtained；S2: by silicide-comprising
It closes object to be dispersed in water, obtains silicon-containing compound solution；S3: S1 is added in silicon-containing compound solution obtained by S2 under agitation
In gained graphene oxide slurry, after mixing evenly, continues to be uniformly dispersed with high pressure homogenizer, obtain silicon-containing compound/oxidation
Graphene slurry；S4: silicon-containing compound/graphene oxide slurry obtained by S3 is coated in PET base or nonwoven fabric base bottom, into
Row is dried, and obtains silicon-containing compound/graphene oxide membrane；S5: silicon-containing compound/graphene oxide membrane obtained by S4 is placed in
High-temperature process is carried out in inert atmosphere, and is rolled after high-temperature process, and SiO is obtainedx/ graphene film；S6: by graphite oxide
It is scattered in solvent, obtains graphene oxide solution；S7: by silicon-containing compound, oxygen obtained by S6 is slowly put under agitation
In graphite alkene solution, silicon-containing compound/graphene oxide solution is obtained；S8: by silicon-containing compound/graphene oxide obtained by S7
Solution is added in polymer dispersion liquid, is uniformly dispersed, and silicon-containing compound/graphene oxide spinning solution is obtained；S9: with Static Spinning
Silicon-containing compound obtained by S8/graphene oxide spinning solution is carried out spinning processing, the SiO obtained by S5 by silk equipmentxOn/graphene film
Generate silicon-containing compound/graphene oxide/composite nano-polymers tunica fibrosa；S10: S7 products obtained therefrom is placed in high temperature furnace,
High-temperature process is carried out under inert gas protection, in SiOx/ graphene membrane surface forms SiOx/ graphene/carbon composite nano fiber
Film is formed by SiOx/ graphene/carbon composite nano-fiber membrane/SiOx/ graphene film is silicon/graphene/carbon composite fibre
Film cathode pole piece.
By using above-mentioned technical proposal: with SiOx/ graphene/carbon composite nano-fiber membrane is attached to SiO in situx/ graphite
The surface of alkene film constitutes silicon/graphene/carbon composite cellulosic membrane cathode pole piece, because without introducing conductive agent and binder.Graphite
Alkene has excellent electric conductivity, electrochemical stability, mechanical performance and lower density, is as novel carbon nanomaterial
Composite material provides preferable electron channel.Using graphene film replace metal be used as lithium ion battery collector, reduce and
Contact resistance between active material promotes the chemical property of battery.And metal collector is avoided to be corroded bring battery
The problem of internal short-circuit, performance decline.Pass through graphene and carbon duplicate protection SiO simultaneouslyxParticle prevents silicon materials in charge and discharge
Particle expansion in electric process improves the chemical property and service life of battery.
Preferably, in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method: the silicon-containing compound
Using Nano-meter SiO_2xAny one of powder, silane coupling agent, positive esters of silicon acis, sodium metasilicate, organosilicon and diatom.
It is further preferred that in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method: being done described in step S4
Dry processing carries out in 80 DEG C of temperature environments below；High-temperature process described in step S5 is within the temperature range of 1000~2600 DEG C
It carries out, heating rate is 0.5~10 DEG C/min, and the processing time is 2~6 hours.
It may further be preferable that in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method: step S9 institute
The operating voltage for stating spinning processing is 8~15kV；High-temperature process described in step S10 within the temperature range of 800~2600 DEG C into
Row, heating rate are 0.5~10 DEG C/min, and the processing time is 2~8 hours.
It is even furthermore preferable that in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method: step S6
The solvent is any one of water, n,N-Dimethylformamide (DMF), ethylene glycol, dimethylbenzene or several mixing, step
Polymer dispersion liquid described in S8 is polyvinyl alcohol (PVA), aqueous polyurethane (WPU), polyacrylonitrile (PAN), polyacrylic acid
(PAA), any one of polylactic acid (PLA), polyvinylpyrrolidone (PVP) or several mixing.
The invention also discloses a kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece, use above-mentioned silicon/graphene/
Carbon composite cellulosic membrane cathode pole piece preparation method is prepared.
Preferably, in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece: the SiOx: graphene: the matter of carbon
Amount is than being (5~60): (2~40): (38~55)；The SiOx/ graphene film with a thickness of 6~30 μm, conductivity is 0.2~
1.2×105S/m；The SiOxSiO in/graphene filmx: the mass ratio of graphene is (0~3): (100:97)；The SiOx/
Graphene/carbon composite nano-fiber membrane with a thickness of 0.5~100 μm；The SiOxIn/graphene/carbon composite nano-fiber membrane
SiOx: graphene: the mass ratio of carbon is (2~60): (0:20): (40~78).
It is further preferred that in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece: the SiOxPartial size be 10~
500nm；The SiOxIn/graphene/carbon composite nano-fiber membrane, SiOxThe diameter of/graphene/carbon composite nano fiber is 100
~1500nm.
The invention also discloses a kind of lithium ion batteries comprising: anode electrode piece, diaphragm, electrolyte and above scheme
In manufactured silicon/graphene/carbon composite cellulosic membrane cathode pole piece.
Compared with prior art, the present invention overcomes silicon materials conductivity itself is lower and the larger problem of cubical expansivity,
And collector is corroded bring battery short circuit, degradation problem.Invention increases between active material and collector
Adhesive force, while reducing the contact resistance between collector and active material, silicon/graphene/carbon in the present invention is compound
Tunica fibrosa cathode pole piece can promote the chemical property and service life of battery.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is 1 gained silicon of embodiment/graphene/carbon composite cellulosic membrane cathode pole piece, with 1M LiPF6(DMC:EC=1:
It is bent 1vol%) to be that electrolyte, polypropylene screen are that diaphragm constitutes charge and discharge of the fastening lithium ionic cell in the current density of 0.5C
Line chart；
Fig. 3 is 1 gained silicon of embodiment/graphene/carbon composite cellulosic membrane cathode pole piece, with 1M LiPF6(DMC:EC=1:
It 1vol%) be electrolyte, polypropylene screen is that diaphragm constitutes coulombic efficiency of the fastening lithium ionic cell in the current density of 0.5C
Figure.
Specific embodiment
In order to illustrate more clearly of technical solution of the present invention, it is further described below in conjunction with each embodiment.
It should be appreciated that implementation of the invention is not limited by the following examples, the present invention is done in any form
Accommodation and/or change fall within the scope of the present invention.In following embodiment, if not refering in particular to, all percentage is
Unit of weight, used equipment and raw material etc. are commercially available or commonly used in the art.Side in following embodiments
Method is unless otherwise instructed the conventional method of this field.
Embodiment 1 as shown in Figs. 1-3:
A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece, is prepared by following steps:
1, SiO is preparedx/ graphene film:
It disperses graphite oxide in deionized water, 3% graphite oxide is obtained after high pressure homogenizer is uniformly dispersed
Alkene slurry；It is simultaneously 20nmSiO by partial sizexPowder or silicon-containing compound are dispersed in water, and obtain 5% SiOxPowder or siliceous chemical combination
Object solution；Then SiOx powder or silicon-containing compound solution are added under agitation in graphene oxide slurry, are recycled
High pressure homogenizer continues to be uniformly dispersed, and obtains SiOxPowder or silicon-containing compound/graphene oxide slurry；Then by Nano-meter SiO_2xPowder
Or silicon-containing compound/graphene oxide slurry is coated on PET or nonwoven fabric base bottom, obtains SiO after 75 DEG C of dry 4hxOr it is siliceous
Compound/graphene oxide membrane；Finally by SiOxPowder or silicon-containing compound/graphene oxide membrane are placed in argon atmosphere 2600 DEG C
After handling 2h, and rolled to obtain the SiO of 10 μ m-thicksx/ graphene film.
2, SiO is preparedx/ graphene/carbon composite nano-fiber membrane:
The graphene oxide solution for preparing 0.5% after ultrasonic 0.5h, is delayed in the case where revolving speed is the stirring condition of 1500 turns/min
The slow SiO that 20nm is addedxThe silicon-containing compounds such as powder or esters of silicon acis are subsequently added in 10% PAN dispersion liquid, after mixing evenly
Obtain spinning solution；Then with SiOx/ graphene film is to receive medium, is spun above-mentioned spinning solution using electrospinning device
Silk, in SiOxThe nano fibrous membrane containing graphene oxide and Si is obtained on/graphene film in situ；Under nitrogen gas protection,
To the SiO of supporting nanofibres filmx/ graphene film carries out high-temperature process, and treatment temperature keeps the temperature 3h at 1200 degree.It finally obtains
Load the SiO of 20 μ m-thicksxThe SiO of/graphene/carbon composite nano-fiber membranex/ graphene film.
Detection data: in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece, SiOx: graphene: the quality of carbon
Than for 36:9:55.Under the conditions of current density is 0.5C (1C=2286mA/g (Si/C=1:1)), specific discharge capacity is
2700mAh/g, first charge discharge efficiency reach 95.5%, after 100 circulations, can keep 96% capacity, have preferable circulation
Stability.
Embodiment 2:
A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece, is prepared by following steps:
1, SiO is preparedx/ graphene film:
It disperses graphite oxide in deionized water, 5% graphite oxide is obtained after high pressure homogenizer is uniformly dispersed
Alkene slurry；The SiO for being simultaneously 300nm by partial sizexPowder or silicon-containing compound are dispersed in water, and obtain 8% SiOxPowder or silicide-comprising
Polymer solution；Then by SiOxPowder or silicon-containing compound solution are added under agitation in graphene oxide slurry, then benefit
Continue to be uniformly dispersed with high pressure homogenizer, obtains SiOxPowder or silicon-containing compound/graphene oxide slurry；Then by Nano-meter SiO_2x
Powder or silicon-containing compound/graphene oxide slurry are coated on PET or nonwoven fabric base bottom, obtain SiO after 60 DEG C of dry 6hxOr contain
Silicon compound/graphene oxide membrane；Finally by SiOxPowder or silicon-containing compound/graphene oxide membrane are placed in 2500 in argon atmosphere
After DEG C processing 2.5h, and rolled to obtain the SiO of 20 μ m-thicksx/ graphene film.
2, SiO is preparedx/ graphene/carbon composite nano-fiber membrane:
The graphene oxide solution for preparing 0.4% after ultrasonic 0.5h, is delayed in the case where revolving speed is the stirring condition of 1500 turns/min
The slow SiO that 300nm is addedxThe silicon-containing compounds such as powder or esters of silicon acis are subsequently added in 8% PVA dispersion liquid, after mixing evenly
Obtain spinning solution；Then with SiOx/ graphene film is to receive medium, is spun above-mentioned spinning solution using electrospinning device
Silk, in SiOxThe nano fibrous membrane containing graphene oxide and Si is obtained on/graphene film in situ；Under nitrogen gas protection,
To the SiO of supporting nanofibres filmx/ graphene film carries out high-temperature process, and treatment temperature keeps the temperature 2h at 1500 degree.It finally obtains
Load the SiO of 50 μ m-thicksxThe SiO of/graphene/carbon composite nano-fiber membranex/ graphene film.
Detection data: in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece, SiOx: graphene: the quality of carbon
Than for 10:15:75.Under the conditions of current density is 0.5C (1C=2286mA/g (Si/C=1:1)), specific discharge capacity can reach
To 2300mAh/g, first charge discharge efficiency 92% can keep 97% capacity after 100 circulations, have preferable stable circulation
Property.
Embodiment 3
A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece, is prepared by following steps:
1, SiO is preparedx/ graphene film:
It disperses graphite oxide in deionized water, 4% graphite oxide is obtained after high pressure homogenizer is uniformly dispersed
Alkene slurry；It is simultaneously 100nm SiO by partial sizexPowder or silicon-containing compound are dispersed in water, and obtain 5% SiOxPowder or silicide-comprising
Polymer solution；Then by SiOxPowder or silicon-containing compound solution are added under agitation in graphene oxide slurry, then benefit
Continue to be uniformly dispersed with high pressure homogenizer, obtains SiOxPowder or silicon-containing compound/graphene oxide slurry；Then by Nano-meter SiO_2x
Powder or silicon-containing compound/graphene oxide slurry are coated on PET or nonwoven fabric base bottom, obtain SiO after 80 DEG C of dry 3hxOr contain
Silicon compound/graphene oxide membrane；Finally by SiOxPowder or silicon-containing compound/graphene oxide membrane are placed in 2600 in argon atmosphere
After DEG C processing 2.5h, and rolled to obtain the SiO of 12 μ m-thicksx/ graphene film.
2, SiO is preparedx/ graphene/carbon composite nano-fiber membrane:
The graphene oxide solution for preparing 0.5%, after ultrasonic 1h, slowly in the case where revolving speed is the stirring condition of 1500 turns/min
The SiO of 100nm is addedxThe silicon-containing compounds such as powder or esters of silicon acis are subsequently added in 10% PVA dispersion liquid, after mixing evenly
Obtain spinning solution；Then with SiOx/ graphene film is to receive medium, is spun above-mentioned spinning solution using electrospinning device
Silk, in SiOxThe nano fibrous membrane containing graphene oxide and Si is obtained on/graphene film in situ；Under nitrogen gas protection,
To the SiO of supporting nanofibres filmx/ graphene film carries out high-temperature process, and treatment temperature keeps the temperature 2h at 1500 degree.It finally obtains
Load the SiO of 10 μ m-thicksxThe SiO of/graphene/carbon composite nano-fiber membranex/ graphene film.
Detection data: in above-mentioned silicon/graphene/carbon composite cellulosic membrane cathode pole piece, SiOx: graphene: the quality of carbon
Than for 58:2:40.Under the conditions of current density is 0.5C (1C=2286mA/g (Si/C=1:1)), specific discharge capacity can reach
To 2800mAh/g, first charge discharge efficiency 92% can still keep 95% capacity after 100 circulations, have preferable circulation steady
It is qualitative.
The above, only specific embodiments of the present invention, but scope of protection of the present invention is not limited thereto, it is any ripe
The technical staff of art technology is known in technical scope disclosed by the invention, any changes or substitutions that can be easily thought of, should all contain
Lid is within protection scope of the present invention.Protection scope of the present invention is subject to the scope of protection of the claims.
Claims (10)
1. a kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method, it is characterised in that: the silicon/graphene/carbon
Composite cellulosic membrane cathode pole piece is with method of electrostatic spinning by SiOx/ graphene/carbon composite nano-fiber membrane is attached to SiO in situx/ stone
The surface of black alkene film is constituted, and the value range of the x is 0≤x < 2.
2. silicon as described in claim 1/graphene/carbon composite cellulosic membrane cathode pole piece preparation method, it is characterised in that: including such as
Lower step:
S1: dispersing graphite oxide in deionized water, is uniformly dispersed with high pressure homogenizer, obtains graphene oxide slurry；
S2: silicon-containing compound is dispersed in water, and obtains silicon-containing compound solution；
S3: silicon-containing compound solution obtained by S2 is added under agitation in graphene oxide slurry obtained by S1, is stirred evenly
Afterwards, continue to be uniformly dispersed with high pressure homogenizer, obtain silicon-containing compound/graphene oxide slurry；
S4: silicon-containing compound/graphene oxide slurry obtained by S3 is coated in PET base or nonwoven fabric base bottom, is dried
Processing, obtains silicon-containing compound/graphene oxide membrane；
S5: silicon-containing compound/graphene oxide membrane obtained by S4 is placed in inert atmosphere and carries out high-temperature process, and in high-temperature process
After rolled, obtain SiOx/ graphene film；
S6: dispersing graphite oxide in solvent, obtains graphene oxide solution；
S7: by silicon-containing compound, siliceous chemical combination slowly is obtained in graphene oxide solution obtained by investment S6 under agitation
Object/graphene oxide solution；
S8: silicon-containing compound/graphene oxide solution obtained by S7 is added in polymer dispersion liquid, is uniformly dispersed, is contained
Silicon compound/graphene oxide spinning solution；
S9: silicon-containing compound obtained by S8/graphene oxide spinning solution is carried out by spinning processing with electrospinning device, obtained by S5
SiOxSilicon-containing compound/graphene oxide/composite nano-polymers tunica fibrosa is generated on/graphene film；
S10: S7 products obtained therefrom is placed in high temperature furnace, high-temperature process is carried out under inert gas protection, in SiOx/ graphene film
Surface forms SiOx/ graphene/carbon composite nano-fiber membrane, is formed by SiOx/ graphene/carbon composite nano-fiber membrane/
SiOx/ graphene film is silicon/graphene/carbon composite cellulosic membrane cathode pole piece.
3. silicon as claimed in claim 2/graphene/carbon composite cellulosic membrane cathode pole piece preparation method, it is characterised in that: described to contain
Silicon compound uses Nano-meter SiO_2xAny one of powder, silane coupling agent, positive esters of silicon acis, sodium metasilicate, organosilicon and diatom.
4. silicon as claimed in claim 2/graphene/carbon composite cellulosic membrane cathode pole piece preparation method, it is characterised in that: step S4
The drying process carries out in 80 DEG C of temperature environments below；Temperature of the high-temperature process described in step S5 at 1000~2600 DEG C
It is carried out in range, heating rate is 0.5~10 DEG C/min, and the processing time is 2~6 hours.
5. silicon as claimed in claim 2/graphene/carbon composite cellulosic membrane cathode pole piece preparation method, it is characterised in that: step S9
The operating voltage of the spinning processing is 8~15kV；High-temperature process described in step S10 is within the temperature range of 800~2600 DEG C
It carries out, heating rate is 0.5~10 DEG C/min, and the processing time is 2~8 hours.
6. silicon as claimed in claim 2/graphene/carbon composite cellulosic membrane cathode pole piece preparation method, it is characterised in that: step S6
The solvent is any one of water, n,N-Dimethylformamide, ethylene glycol, dimethylbenzene or several mixing；Step S8 institute
Polymer dispersion liquid is stated as in polyvinyl alcohol, aqueous polyurethane, polyacrylonitrile, polyacrylic acid, polylactic acid, polyvinylpyrrolidone
It is any or appoint several mixing.
7. a kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece, it is characterised in that: using such as any one of claim 1-6 institute
Silicon/graphene/carbon composite cellulosic membrane cathode pole piece preparation method is stated to be prepared.
8. silicon as claimed in claim 7/graphene/carbon composite cellulosic membrane cathode pole piece, it is characterised in that: the SiOx: graphite
Alkene: the mass ratio of carbon is (5~60): (2~40): (38~55)；The SiOx/ graphene film with a thickness of 6~30 μm, conductance
Rate is 0.2~1.2 × 105S/m；The SiOxSiO in/graphene filmx: the mass ratio of graphene is (0~3): (100:97)；
The SiOx/ graphene/carbon composite nano-fiber membrane with a thickness of 0.5~100 μm；The SiOx/ graphene/carbon composite Nano
SiO in tunica fibrosax: graphene: the mass ratio of carbon is (2~60): (0:20): (40~78).
9. silicon as claimed in claim 8/graphene/carbon composite cellulosic membrane cathode pole piece, it is characterised in that: the SiOxPartial size is
10~500nm；The SiOxIn/graphene/carbon composite nano-fiber membrane, SiOxThe diameter of/graphene/carbon composite nano fiber
For 100~1500nm.
10. a kind of lithium ion battery, it is characterised in that: negative including silicon as claimed in claim 9/graphene/carbon composite cellulosic membrane
Pole pole piece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910752748.XA CN110459732B (en) | 2019-08-14 | 2019-08-14 | Silicon/graphene/carbon composite fiber membrane negative electrode plate, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910752748.XA CN110459732B (en) | 2019-08-14 | 2019-08-14 | Silicon/graphene/carbon composite fiber membrane negative electrode plate, preparation method thereof and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110459732A true CN110459732A (en) | 2019-11-15 |
| CN110459732B CN110459732B (en) | 2021-04-09 |
Family
ID=68486723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910752748.XA Active CN110459732B (en) | 2019-08-14 | 2019-08-14 | Silicon/graphene/carbon composite fiber membrane negative electrode plate, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110459732B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082006A (en) * | 2019-12-06 | 2020-04-28 | 深圳市比克动力电池有限公司 | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery |
| CN111769274A (en) * | 2020-07-17 | 2020-10-13 | 昆山宝创新能源科技有限公司 | SiOx-C composite fiber felt negative electrode material and preparation method and application 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014160174A1 (en) * | 2013-03-14 | 2014-10-02 | Cornell University | Carbon and carbon precursors in nanofibers |
| CN104269539A (en) * | 2014-09-30 | 2015-01-07 | 南京中储新能源有限公司 | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery |
| CN104810504A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院金属研究所 | Flexible graphene current collector and active material integrated electrode pole piece and preparation method thereof |
| CN105098160A (en) * | 2015-08-31 | 2015-11-25 | 中原工学院 | Hollow porous graphene-doped carbon/silicon nanofiber lithium battery anode material and preparation method thereof |
| CN105742572A (en) * | 2014-12-12 | 2016-07-06 | 国家纳米科学中心 | Three-dimensional conductive network-supported porous silicon nanomaterial and preparation method and application thereof |
| CN106450335A (en) * | 2016-12-05 | 2017-02-22 | 中国科学院化学研究所 | A silicon-containing graphene composite material and its preparation method and application in flexible lithium batteries |
| KR20170130786A (en) * | 2016-05-19 | 2017-11-29 | 숭실대학교산학협력단 | Preparing method for carbon nanofibers composites comprising silicon/ silicon nitride and silicon carbide core-shell composites |
| CN108417808A (en) * | 2018-03-21 | 2018-08-17 | 南京工业大学 | Carbon fiber-silicon-graphene oxide composite material and preparation method thereof |
-
2019
- 2019-08-14 CN CN201910752748.XA patent/CN110459732B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014160174A1 (en) * | 2013-03-14 | 2014-10-02 | Cornell University | Carbon and carbon precursors in nanofibers |
| CN104810504A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院金属研究所 | Flexible graphene current collector and active material integrated electrode pole piece and preparation method thereof |
| CN104269539A (en) * | 2014-09-30 | 2015-01-07 | 南京中储新能源有限公司 | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery |
| CN105742572A (en) * | 2014-12-12 | 2016-07-06 | 国家纳米科学中心 | Three-dimensional conductive network-supported porous silicon nanomaterial and preparation method and application thereof |
| CN105098160A (en) * | 2015-08-31 | 2015-11-25 | 中原工学院 | Hollow porous graphene-doped carbon/silicon nanofiber lithium battery anode material and preparation method thereof |
| KR20170130786A (en) * | 2016-05-19 | 2017-11-29 | 숭실대학교산학협력단 | Preparing method for carbon nanofibers composites comprising silicon/ silicon nitride and silicon carbide core-shell composites |
| CN106450335A (en) * | 2016-12-05 | 2017-02-22 | 中国科学院化学研究所 | A silicon-containing graphene composite material and its preparation method and application in flexible lithium batteries |
| CN108417808A (en) * | 2018-03-21 | 2018-08-17 | 南京工业大学 | Carbon fiber-silicon-graphene oxide composite material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082006A (en) * | 2019-12-06 | 2020-04-28 | 深圳市比克动力电池有限公司 | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery |
| CN111082006B (en) * | 2019-12-06 | 2022-07-19 | 深圳市比克动力电池有限公司 | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery |
| CN111769274A (en) * | 2020-07-17 | 2020-10-13 | 昆山宝创新能源科技有限公司 | SiOx-C composite fiber felt negative electrode material and preparation method and application 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110459732B (en) | 2021-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113054165B (en) | A negative pole piece of a zinc secondary battery and its preparation method and application | |
| CN104835949B (en) | Si‑TiO2C nano fiber composite film and its preparation method and application | |
| CN109273680A (en) | A kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery | |
| CN106207124A (en) | The nano combined nano fibrous membrane of silicon/carbon of graphene coated and application thereof | |
| WO2022021933A1 (en) | Negative electrode material for nonaqueous electrolyte secondary battery, and preparation method therefor | |
| CN105226253B (en) | A kind of silicon nanoparticle-graphite flake-carbon nano tube compound material and the preparation method and application thereof | |
| CN106129367A (en) | A kind of silicon/carbon nano-composite fiber and application thereof | |
| CN108315834A (en) | A kind of preparation method of array magnetizing reduction graphene oxide-carbon nanofibers | |
| CN105226254B (en) | A kind of silicon nanoparticle graphite nano plate carbon fibre composite and preparation method and application | |
| CN113745490B (en) | Nano silicon-based composite fiber negative electrode material of lithium ion battery | |
| CN104319405B (en) | The preparation method of Nano graphite powder used for all-vanadium redox flow battery/carbon nano-fiber combination electrode | |
| CN108448080A (en) | A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof | |
| CN105118974A (en) | Silicon-based negative electrode material and preparation method thereof | |
| CN112467200B (en) | Lithium fluoride/lithium lanthanum titanate nanofiber solid electrolyte interface material and preparation method and application thereof | |
| CN110459732A (en) | A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece and preparation method thereof and lithium ion battery | |
| CN112635762B (en) | Lithium ion battery negative electrode material, preparation method and application thereof, and lithium ion battery | |
| CN112038541B (en) | A kind of composite diaphragm material and its preparation method and application | |
| CN110854379B (en) | Silicon-carbon composite negative electrode material and preparation method thereof, negative electrode plate and lithium ion battery | |
| CN113488607B (en) | Preparation and application of metal zinc cathode with functional nano material modification layer | |
| CN112563468B (en) | Lithium ion battery cathode nanofiber composite material and preparation method and application thereof | |
| TWI651882B (en) | Lithium ion battery | |
| CN108199020A (en) | Carbon-coated silicon anode material with micro-nano hierarchical structure and preparation method and application thereof | |
| CN112201848B (en) | Solid electrolyte, composite integrated positive electrode, integrated battery and preparation method thereof | |
| CN112838203A (en) | CNF-GeO2-Li composite electrode applied to lithium metal battery and preparation method thereof | |
| Liu et al. | Functional ionic liquid modified core-shell structured fibrous gel polymer electrolyte for safe and efficient fast charging lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221129 Address after: No. 10-1, Century Avenue, Huaiyuan Economic Development Zone, Bengbu, Anhui 233499 Patentee after: Anhui Yuling New Energy Technology Co.,Ltd. Address before: 201318 room c290, building 1, 1628 suzhao Road, Minhang District, Shanghai Patentee before: SHANGHAI YULING NEW ENERGY TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |