CN106058209A - Lithium ion battery self-supporting silicon-based anode material with multilayered film and preparation method of anode material - Google Patents
Lithium ion battery self-supporting silicon-based anode material with multilayered film and preparation method of anode material Download PDFInfo
- Publication number
- CN106058209A CN106058209A CN201610628026.XA CN201610628026A CN106058209A CN 106058209 A CN106058209 A CN 106058209A CN 201610628026 A CN201610628026 A CN 201610628026A CN 106058209 A CN106058209 A CN 106058209A
- Authority
- CN
- China
- Prior art keywords
- anode material
- plural layers
- lithium ion
- ion battery
- carbon
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- 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
- H01M4/1395—Processes of manufacture of 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery self-supporting silicon-based anode material with a multilayered film and a preparation method of the anode material. The anode material is made from silicon nano-particles and carbon nano-fibers through compounding, wherein the mass ratio of silicon to carbon is 1:0.5-1:6 and the thickness ratio of a carbon fiber layer to a silicon-carbon compound fiber layer is 1:1-1:5. The preparation method comprises the following steps: dispersing a mixture formed from silicon nano-particles/an organic high-molecular polymer and an organic high-molecular polymer in an organic agent, respectively, and performing fully stirring to obtain an uniform suspension and solution; through control of the injection volume and time of electrostatic spinning, obtaining a multilayered periodic structure of carbon-carbon silicon compound-carbon-carbon silicon compound...-carbon; and performing carbonization treatment in the protective atmosphere to obtain the lithium ion battery self-supporting silicon-based anode material with a multilayered film. The anode material has characteristics of self-supporting, high capacity, good cyclic stability and simple preparation.
Description
Technical field
Lithium ion battery self-supporting silicon based anode material that the present invention relates to a kind of plural layers and preparation method thereof, belongs to the energy
Material Field.
Background technology
Along with the extensive application of electric automobile, hybrid vehicle and solar energy, wind power generation etc., high-performance storage device becomes
Become more and more important.It is high that lithium ion battery has energy density, good cycle, and specific energy is high, the advantages such as environmental pollution is little, thus
It it is one of currently the most important ones energy storage device.
Lithium ion battery refers to that Li+ embeds and a kind of of abjection positive and negative pole material can the high-energy battery of discharge and recharge.At present its
Positive electrode typically uses slotting lithium compound, such as LiCoO2、LiNiO2、LiMnO2Deng；Its negative material uses stratiform material with carbon element such as
Graphite；Electrolyte is for having dissolved lithium salts (such as LiPF6、LiAsF6、LiClO4Deng) organic solvent (such as ethylene carbonate EC, carbonic acid
Dimethyl ester DMC etc.).In charging process, Li+Coming and going between two electrodes and insert abjection, battery chemistries expression is as follows:
(-) Cn│LiPF6 - EC+DMC│LiMxOy (+)
Its cell reaction is:
LiMxOy + nC ↔ Li1-xMxOy + LixCn
Lithium ion battery is a kind of lithium concentration difference battery, Li during charging+Being embedded into negative pole by electrolyte, electronics is by outward
Circuit compensation is to negative pole, it is ensured that charge balance.During electric discharge then on the contrary, Li+Being embedded into positive pole by electrolyte, electronics passes through dispatch from foreign news agency
Road compensates positive pole and guarantees charge balance.
From above-mentioned lithium ion battery operation principle, negative material carries the effect of embedding and removing, negative material
Performance quality the performance of lithium ion battery is had strong influence.The lithium ion battery negative material of existing market is stone
Ink, its specific capacity relatively low (only 372mAh/g), energy density is relatively low, it is difficult to meet the field such as electric automobile, mobile electronic device
Requirement to heavy-duty battery, the most how to obtain have the negative material of height ratio capacity and good circulation performance be lithium from
The important research direction of sub-battery material.
Silicon can react with lithium, reversibly forms multiple alloy, as、Li15Si4、Deng, it is used as negative
Theoretical Mass specific capacity up to (4200mAh/g, the Li during material of pole22Si5), it is the highest in the negative material being currently known, and
Relatively low to lithium current potential (0.4V), is therefore one of the most promising negative material.
But, silicon can experience the change in volume more than 400% during charge and discharge cycles, is easily caused active material efflorescence
And depart from from collector and cause poor electric contact, and cause SEI film unstable and constantly consume active material, so that its
Cycle performance is very poor.How to improve the cycle performance of silicon and don't too much affect its capacity, being grinding of current silicon based anode material
Study carefully emphasis.
In order to improve the cycle performance of silicon based anode material, recent domestic researcher has done substantial amounts of work
Make, devise the structure of multiple silicon, such as silicon nanowire array, carbon-coated nano silicone tube, the carbon silicon microsphere of nucleocapsid structure, three-dimensional
Porous silicon carbon complex etc..These work achieve the best achievement, specific capacity and the cyclicity to silicon based anode material
Can all serve bigger improvement.But its preparation process is the most complicated, and area ratio capacity is the most relatively low；And current research
It is all to be optimized structure design, also nobody in microstructure aspect to do macroscopic aspect and microcosmic point collaborative optimization material
Structure and the work of composition.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the lithium ion battery self-supporting silicon of a kind of plural layers
Base negative material and preparation method thereof.
The lithium ion battery self-supporting silicon based anode material of plural layers is to be combined by nano silicon particles and carbon nano-fiber
Forming plural layers, wherein the mass ratio of silicon and carbon is 1:0.5 ~ 1:6, and carbon fiber layer and silicon-carbon complex in plural layers are fine
Dimension layer thickness ratio is for 1:1 ~ 1:5;
The preparation method of the lithium ion battery self-supporting silicon based anode material of plural layers comprises the following steps:
1) being disperseed in organic solvent by high molecular polymer, magnetic agitation is supersound process 30 ~ 60 minutes after 18 ~ 48 hours,
To 5 ~ 15wt% macromolecule polymer solution；
2) high molecular polymer and nano silica fume that mass ratio is 1:1 ~ 12:1 being dispersed in organic solvent of the same race, magnetic force stirs
Mix 18 ~ 48 hours, supersound process 30 ~ 60 minutes, obtain high molecular polymer and nano silica fume dispersion liquid；
3) utilizing coaxial device for spinning to carry out Static Spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, and outer tube is
Macromolecule polymer solution, first injects macromolecule polymer solution, stops injecting, start to inject after 40 minutes persistent period
High molecular polymer and nano silica fume dispersion liquid, stop after 2 hours persistent period injecting, start again at and inject high molecular polymer
Solution, 40 minutes persistent period, according to the number of plies of plural layers, can be repeated several times said process, obtain plural layers；
4) prepared plural layers are put in tube furnace, at 95%Ar+5%H2Under hydrogen-argon-mixed atmosphere, it is heated to 650 oC
~1000 oC carbonization 10 ~ 0.5 hours, i.e. obtains the lithium ion battery self-supporting silicon based anode material of plural layers.
Described high molecular polymer is polyacrylonitrile, POLYPROPYLENE GLYCOL or polyvinylpyrrolidone.Described organic solvent
It is dimethylformamide or oxolane.Described electrostatic spinning environment temperature and humidity is 30 ~ 40 DEG C and 40% respectively.Described electrostatic
The positive high voltage of spinning is 12 ~ 18kV, and negative high voltage is-2kV.The shower nozzle of described coaxial device for spinning to receive device distance be 10 ~
15cm.Described high molecular polymer and nano silica fume dispersion liquid and macromolecule polymer solution inject speed be 0.005 ~
0.02mL/min.Described carburizing temperature is 650 oC ~1000 oC。
The new type lithium ion battery self-supporting silicon based anode material excellent performance of the present invention, can be used for substituting existing lithium from
Sub-battery carbon negative pole material, has a good application prospect.This negative material has good pliability, can alleviate electrode layer
Facial disfigurement, reduces capacity attenuation；The negative film material prepared with method of electrostatic spinning has self-supporting characteristic, it is not necessary to collector
And binding agent, specific discharge capacity is greatly improved；The interlayer number of plies and thickness can be controlled by controlling spinning time and flow, permissible
Prepare the negative film material of multilamellar, big thickness, obtain the highest area ratio capacity；Carbon fiber arrangement prepared by orientation spinning
Densification, space is little, can effectively suppress nano silicon particles to depart from electrode contact, alleviate capacity attenuation；The preparation technology of the present invention
Simple possible, with low cost, tin ash, ferrum oxide etc. can be promoted the use of in charge and discharge process, produce enormousness change
In the preparation of the negative material changed, there is certain universality.
Accompanying drawing explanation
Fig. 1 is three-ply sandwich structure cross section Electronic Speculum figure；
Fig. 2 is sandwich front scan electron microscopic picture.
Detailed description of the invention
The lithium ion battery self-supporting silicon based anode material of plural layers is to be combined by nano silicon particles and carbon nano-fiber
Forming plural layers, wherein the mass ratio of silicon and carbon is 1:0.5 ~ 1:6, and carbon fiber layer and silicon-carbon complex in plural layers are fine
Dimension layer thickness ratio is for 1:1 ~ 1:5;
The preparation method of the lithium ion battery self-supporting silicon based anode material of plural layers comprises the following steps:
1) being disperseed in organic solvent by high molecular polymer, magnetic agitation is supersound process 30 ~ 60 minutes after 18 ~ 48 hours,
To 5 ~ 15wt% macromolecule polymer solution；
2) high molecular polymer and nano silica fume that mass ratio is 1:1 ~ 12:1 being dispersed in organic solvent of the same race, magnetic force stirs
Mix 18 ~ 48 hours, supersound process 30 ~ 60 minutes, obtain high molecular polymer and nano silica fume dispersion liquid；
3) utilizing coaxial device for spinning to carry out Static Spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, and outer tube is
Macromolecule polymer solution, first injects macromolecule polymer solution, stops injecting, start to inject after 40 minutes persistent period
High molecular polymer and nano silica fume dispersion liquid, stop after 2 hours persistent period injecting, start again at and inject high molecular polymer
Solution, 40 minutes persistent period, according to the number of plies of plural layers, can be repeated several times said process, obtain plural layers；
4) prepared plural layers are put in tube furnace, at 95%Ar+5%H2Under hydrogen-argon-mixed atmosphere, it is heated to 650 oC
~1000 oC carbonization 10 ~ 0.5 hours, i.e. obtains the lithium ion battery self-supporting silicon based anode material of plural layers.
Described high molecular polymer is polyacrylonitrile, POLYPROPYLENE GLYCOL or polyvinylpyrrolidone.Described organic solvent
It is dimethylformamide or oxolane.Described electrostatic spinning environment temperature and humidity is 30 ~ 40 DEG C and 40% respectively.Described electrostatic
The positive high voltage of spinning is 12 ~ 18kV, and negative high voltage is-2kV.The shower nozzle of described coaxial device for spinning to receive device distance be 10 ~
15cm.Described high molecular polymer and nano silica fume dispersion liquid and macromolecule polymer solution inject speed be 0.005 ~
0.02mL/min.Described carburizing temperature is 650 oC ~1000 oC。
Embodiment 1
1) being dissolved in dimethyl amide by 1.5g polyacrylonitrile, magnetic agitation is supersound process 30 minutes after 24 hours, obtain
The macromolecule polymer solution of 8wt%；
2) nano silica fume and polyacrylonitrile being dispersed in organic solvent of the same race, magnetic agitation is supersound process 30 points after 24 hours
Clock, obtains high molecular polymer and nano silica fume dispersion liquid；
3) plural layers are prepared with electrostatic spinning machine spinning: regulation arranges suitable positive high voltage 18Kv, negative high voltage-2kV, environment temperature
Degree 30oC, humidity 40%, select and orient at a high speed adnexa as receiving device.Utilizing coaxial device for spinning, inner tube is high molecular polymerization
Thing and nano silica fume dispersion liquid, outer tube is macromolecule polymer solution.The shower nozzle of coaxial device for spinning to receiving device distance is
15cm.First injecting macromolecule polymer solution, injecting speed is 0.02mL/min, stops, starting to inject after continuing 40 minutes
High molecular polymer and nano silica fume dispersion liquid, injecting speed is 0.02mL/min, stops, starting to push away after 2 hours persistent period
Note macromolecule polymer solution, injecting speed is 0.02mL/min, 40 minutes persistent period；
4) prepared thin film is put in tube furnace, under hydrogen-argon-mixed atmosphere, be heated to 650 DEG C of carbonization 10h, i.e. obtain multilamellar
The lithium ion battery self-supporting silicon based anode material of thin film.
Cross-sectional scans electromicroscopic photograph such as Fig. 1 of three-ply sandwich structure carbon-to-carbon silicon compound-C film prepared by this example
Shown in, through sem analysis: carbon-to-carbon silicon compound-C film is obvious multiple structure, film thickness about 100 μm, carbon thin film layer
Thickness about 20 μm, carbon-silicon compound thin film layer thickness about 60 μm.Fig. 2 show the front scan electromicroscopic photograph of thin-film material, can
To find that carbon fiber becomes significantly to align.
By charge-discharge test it appeared that the lithium ion battery self-supporting silicon based anode material of plural layers discharges first
Capacity is 1134mAh/g, and coulombic efficiency is 77% first, and after 50 circulations, capability retention is 86.2%.
Embodiment 2
1) being dissolved in dimethyl amide by 1.5g polyvinylpyrrolidone, magnetic agitation is supersound process 30 points after 24 hours
Clock, obtains the macromolecule polymer solution of 5wt%；
2) nano silica fume and polyvinylpyrrolidone being dispersed in organic solvent of the same race, magnetic agitation is supersound process after 24 hours
30 minutes, obtain high molecular polymer and nano silica fume dispersion liquid；
3) plural layers are prepared with electrostatic spinning machine spinning: regulation arranges suitable positive high voltage 15Kv, negative high voltage-2kV, environment temperature
Degree 40oC, humidity 40%, select and orient at a high speed adnexa as receiving device.Utilizing coaxial device for spinning, inner tube is high molecular polymerization
Thing and nano silica fume dispersion liquid, outer tube is macromolecule polymer solution.The shower nozzle of coaxial device for spinning to receiving device distance is
10cm.First injecting macromolecule polymer solution, injecting speed is 0.017mL/min, stops, starting to inject after continuing 40 minutes
High molecular polymer and nano silica fume dispersion liquid, injecting speed is 0.017mL/min, stops, starting to push away after 2 hours persistent period
Note macromolecule polymer solution, injecting speed is 0.017mL/min, 40 minutes persistent period；
4) prepared thin film is put in tube furnace, under hydrogen-argon-mixed atmosphere, be heated to 750 DEG C of carbonization 5h, i.e. obtain multilamellar
The lithium ion battery self-supporting silicon based anode material of thin film.
Embodiment 3
1) being dissolved in oxolane by 1.5g POLYPROPYLENE GLYCOL, magnetic agitation is supersound process 30 minutes after 24 hours, obtain 15wt%
Macromolecule polymer solution；
2) nano silica fume and POLYPROPYLENE GLYCOL being dispersed in organic solvent of the same race, magnetic agitation is supersound process 30 points after 24 hours
Clock, obtains high molecular polymer and nano silica fume dispersion liquid；
3) plural layers are prepared with electrostatic spinning machine spinning: regulation arranges suitable positive high voltage 15Kv, negative high voltage-2kV, environment temperature
Degree 30oC, humidity 40%.Utilizing coaxial device for spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, and outer tube is high score
Sub-polymer solution.The shower nozzle of coaxial device for spinning is 10cm to receiving device distance.First macromolecule polymer solution is injected,
Injecting speed is 0.02mL/min, stops, starting to inject high molecular polymer and nano silica fume dispersion liquid, push away after continuing 40 minutes
Note speed is 0.02mL/min, stops, starting to inject macromolecule polymer solution after 2 hours persistent period, and injecting speed is
0.02mL/min, 40 minutes persistent period；
4) prepared thin film is put in tube furnace, under hydrogen-argon-mixed atmosphere, be heated to 900 DEG C of carbonizations 1 hour, i.e. obtain many
The lithium ion battery self-supporting silicon based anode material of layer film.
Embodiment 4
1) being dissolved in dimethyl amide by 1.5g polyacrylonitrile, magnetic agitation is supersound process 30 minutes after 24 hours, obtain
The macromolecule polymer solution of 15wt%；
2) nano silica fume and polyacrylonitrile being dispersed in organic solvent of the same race, magnetic agitation is supersound process 30 points after 24 hours
Clock, obtains high molecular polymer and nano silica fume dispersion liquid；
3) plural layers are prepared with electrostatic spinning machine spinning: regulation arranges suitable positive high voltage 18Kv, negative high voltage-2kV, environment temperature
Degree 40oC, humidity 40%.Utilizing coaxial device for spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, and outer tube is high score
Sub-polymer solution.The shower nozzle of coaxial device for spinning is 15cm to receiving device distance.First macromolecule polymer solution is injected,
Injecting speed is 0.005mL/min, stops, starting to inject high molecular polymer and nano silica fume dispersion liquid after continuing 40 minutes,
Injecting speed is 0.005mL/min, stops, starting to inject macromolecule polymer solution after 2 hours persistent period, and injecting speed is
0.005mL/min, 40 minutes persistent period；
4) prepared thin film is put in tube furnace, under hydrogen-argon-mixed atmosphere, be heated to 1000 DEG C of carbonizations 0.5 hour, to obtain final product
Lithium ion battery self-supporting silicon based anode material to plural layers.
Claims (9)
1. a lithium ion battery self-supporting silicon based anode material for plural layers, is characterized in that by nano silicon particles and carbon nanometer
Fiber composite forms plural layers, and wherein the mass ratio of silicon and carbon is 1:0.5 ~ 1:6, the carbon fiber layer in plural layers and silicon-carbon
Compounding fiber layer thickness is than for 1:1 ~ 1:5.
2. a preparation method for the lithium ion battery self-supporting silicon based anode material of plural layers, is characterized in that including following step
Rapid:
1) being disperseed in organic solvent by high molecular polymer, magnetic agitation is supersound process 30 ~ 60 minutes after 18 ~ 48 hours,
To 5 ~ 15wt% macromolecule polymer solution；
2) high molecular polymer and nano silica fume that mass ratio is 1:1 ~ 12:1 being dispersed in organic solvent of the same race, magnetic force stirs
Mix 18 ~ 48 hours, supersound process 30 ~ 60 minutes, obtain high molecular polymer and nano silica fume dispersion liquid；
3) utilizing coaxial device for spinning to carry out electrostatic spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, and outer tube is
Macromolecule polymer solution, first injects macromolecule polymer solution, stops injecting, start to inject high score after continuing 40 minutes
Sub-polymer and nano silica fume dispersion liquid, stop injecting after continuing 2 hours, start again at and inject macromolecule polymer solution, hold
Continuous 40 minutes, according to the number of plies of plural layers, said process can be repeated several times, obtain plural layers；
4) prepared plural layers are put in tube furnace, at 95%Ar+5%H2Under hydrogen-argon-mixed atmosphere, it is heated to 650 oC ~
1000 oC carbonization 10 ~ 0.5 hours, i.e. obtains the lithium ion battery self-supporting silicon based anode material of plural layers.
The preparation side of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers the most according to claim 2
Method, it is characterised in that described high molecular polymer is polyacrylonitrile, POLYPROPYLENE GLYCOL or polyvinylpyrrolidone.
The preparation side of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers the most according to claim 2
Method, it is characterised in that described organic solvent is dimethylformamide or oxolane.
The preparation side of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers the most according to claim 2
Method, it is characterised in that described electrostatic spinning environment temperature and humidity is 30 ~ 40 DEG C and 40% respectively.
The preparation side of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers the most according to claim 2
Method, it is characterised in that the positive high voltage of described electrostatic spinning is 12 ~ 18kV, negative high voltage is-2kV.
The preparation side of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers the most according to claim 2
Method, it is characterised in that the shower nozzle of described coaxial device for spinning is 10 ~ 15cm to receiving device distance.
The preparation side of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers the most according to claim 2
Method, it is characterised in that the speed of injecting of described high molecular polymer and nano silica fume dispersion liquid and macromolecule polymer solution is
0.005~0.02mL/min。
The preparation side of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers the most according to claim 2
Method, it is characterised in that described carburizing temperature is 650 oC~1000 oC。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610628026.XA CN106058209B (en) | 2015-02-11 | 2015-02-11 | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510072080.6A CN104681787B (en) | 2015-02-11 | 2015-02-11 | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof |
| CN201610628026.XA CN106058209B (en) | 2015-02-11 | 2015-02-11 | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510072080.6A Division CN104681787B (en) | 2015-02-11 | 2015-02-11 | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106058209A true CN106058209A (en) | 2016-10-26 |
| CN106058209B CN106058209B (en) | 2018-11-09 |
Family
ID=53316568
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510072080.6A Active CN104681787B (en) | 2015-02-11 | 2015-02-11 | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof |
| CN201610628026.XA Active CN106058209B (en) | 2015-02-11 | 2015-02-11 | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510072080.6A Active CN104681787B (en) | 2015-02-11 | 2015-02-11 | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN104681787B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054368A (en) * | 2017-12-12 | 2018-05-18 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of silicon based anode material, its preparation method and the purposes in lithium ion battery |
| CN108963201A (en) * | 2018-05-28 | 2018-12-07 | 同济大学 | A kind of silicon-carbon self-supporting composite negative pole material and the preparation method and application thereof |
| CN109473633A (en) * | 2017-09-07 | 2019-03-15 | 上海杉杉科技有限公司 | A kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof |
| CN110112405A (en) * | 2019-05-29 | 2019-08-09 | 哈尔滨理工大学 | A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof |
| CN111525114A (en) * | 2020-05-09 | 2020-08-11 | 四川聚创石墨烯科技有限公司 | Method for continuously preparing current collector-free silicon-carbon negative electrode paper |
| CN113422009A (en) * | 2021-06-01 | 2021-09-21 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450165A (en) * | 2016-09-30 | 2017-02-22 | 天津工业大学 | Method for preparing unsupported ion battery electrode material |
| CN106571451A (en) * | 2016-10-26 | 2017-04-19 | 浙江天能能源科技股份有限公司 | Lithium ion battery anode material, and preparation method thereof |
| CN106549139A (en) * | 2016-11-01 | 2017-03-29 | 南京航空航天大学 | A kind of flexible self-supporting nanofiber electrode and preparation method thereof and lithium sodium-ion battery |
| CN106571450A (en) * | 2016-12-23 | 2017-04-19 | 中国石油大学(华东) | Method used for preparing multilayer flexible polyacrylonitrile/bitumen carbon fiber composite material used for lithium ion battery negative electrodes via electrostatic spinning |
| CN107863519B (en) * | 2017-11-09 | 2019-12-17 | 陕西科技大学 | Lithium ion battery negative pole piece and preparation method thereof |
| CN108417808A (en) * | 2018-03-21 | 2018-08-17 | 南京工业大学 | A kind of carbon fiber-silicon-graphene oxide composite material and preparation method thereof |
| CN108682802A (en) * | 2018-04-25 | 2018-10-19 | 福建翔丰华新能源材料有限公司 | A method of preparing lithium cell negative pole shell-core structure nanofiber |
| CN112242513A (en) * | 2020-10-19 | 2021-01-19 | 天津工业大学 | Tube-wire structure silicon-carbon negative electrode material and preparation method thereof |
| CN117954576A (en) * | 2024-03-26 | 2024-04-30 | 宁波大学 | Alloy negative electrode with high capacity and low strain |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378296A (en) * | 2001-03-27 | 2002-11-06 | 日本电气株式会社 | Anode for secondary battery and secondary battery with such anode |
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN104103809A (en) * | 2014-07-31 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Three-layer electrode structure for alloy anode of lithium ion battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094619B (en) * | 2013-01-17 | 2015-02-04 | 北京好风光储能技术有限公司 | High-energy density lithium ion battery cell and preparation method thereof |
| CN103305965B (en) * | 2013-06-04 | 2016-08-10 | 清华大学深圳研究生院 | Si-C composite material with nanometer micropore gap and preparation method thereof and purposes |
| CN104091921A (en) * | 2014-07-22 | 2014-10-08 | 厦门首能科技有限公司 | Porous silicon and carbon mixed anode plate and lithium ion secondary battery comprising same |
-
2015
- 2015-02-11 CN CN201510072080.6A patent/CN104681787B/en active Active
- 2015-02-11 CN CN201610628026.XA patent/CN106058209B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378296A (en) * | 2001-03-27 | 2002-11-06 | 日本电气株式会社 | Anode for secondary battery and secondary battery with such anode |
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN104103809A (en) * | 2014-07-31 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Three-layer electrode structure for alloy anode of lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| KUN FU等: ""Effect of CVD carbon coatings on Si@CNF composite as anode for lithium-ion batteries"", 《NANO ENERGY》 * |
| YUPING LIU等: ""Binder-free Si nanoparticles@carbon nanofiber fabric as energy storage material"", 《ELECTROCHIMICA ACTA》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473633A (en) * | 2017-09-07 | 2019-03-15 | 上海杉杉科技有限公司 | A kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof |
| CN108054368A (en) * | 2017-12-12 | 2018-05-18 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of silicon based anode material, its preparation method and the purposes in lithium ion battery |
| US11515530B2 (en) | 2017-12-12 | 2022-11-29 | Btr New Material Group Co., Ltd. | Silicon-based negative electrode material, preparation method therefor and use thereof in lithium-ion battery |
| CN108963201A (en) * | 2018-05-28 | 2018-12-07 | 同济大学 | A kind of silicon-carbon self-supporting composite negative pole material and the preparation method and application thereof |
| CN110112405A (en) * | 2019-05-29 | 2019-08-09 | 哈尔滨理工大学 | A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof |
| CN110112405B (en) * | 2019-05-29 | 2021-05-18 | 哈尔滨理工大学 | Core-shell structure silicon/carbon fiber flexible composite electrode material and preparation method and application thereof |
| CN111525114A (en) * | 2020-05-09 | 2020-08-11 | 四川聚创石墨烯科技有限公司 | Method for continuously preparing current collector-free silicon-carbon negative electrode paper |
| CN113422009A (en) * | 2021-06-01 | 2021-09-21 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
| CN113422009B (en) * | 2021-06-01 | 2022-03-18 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106058209B (en) | 2018-11-09 |
| CN104681787B (en) | 2017-03-01 |
| CN104681787A (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104681787B (en) | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof | |
| CN102769139B (en) | Preparation method of high power capacity lithium ion battery cathode material | |
| CN104085877B (en) | A kind of based on Chitosan-phospholipid complex porous carbon electrode material and its production and use | |
| CN112582615B (en) | One-dimensional porous silicon-carbon composite negative electrode material, preparation method and application thereof | |
| CN107681142B (en) | Molybdenum disulfide coated carbon nanofiber used as lithium ion battery negative electrode material and preparation method thereof | |
| KR101504709B1 (en) | Lithium secondary battery having improved electrochemical property and preparation method thereof | |
| CN104868106A (en) | Method for coating graphite anode material of lithium ion battery with graphene and application thereof | |
| CN110048101B (en) | Silicon-oxygen-carbon microsphere composite negative electrode material and preparation method and application thereof | |
| CN111816852B (en) | Preparation method of silicon-based composite negative electrode material | |
| CN110993892B (en) | Flexible lithium metal negative electrode framework material and preparation method and application thereof | |
| CN103633295A (en) | Silicon-carbon composite material, lithium ion battery, and preparation method and application of silicon-carbon composite material | |
| CN110010895B (en) | Carbon fiber loaded magnesium oxide particle cross-linked nanosheet array composite material and preparation method and application thereof | |
| CN104178929B (en) | Electrostatic spinning prepares LiNi1/3Co1/3Mn1/3O2The method of fibrous material | |
| CN102074683A (en) | Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof | |
| CN104303339B (en) | Anode material of secondary cell and preparation method thereof | |
| CN105118974A (en) | Silicon-based negative electrode material and preparation method thereof | |
| CN113972368B (en) | High-stability fibrous lithium ion battery anode lithium supplementing material, preparation and application thereof | |
| CN109286039A (en) | A kind of solid state battery dielectric film and preparation method thereof and the solid state battery with the dielectric film | |
| CN107464924A (en) | A kind of sheet oxygen defect lithium vanadate anode material and preparation method thereof | |
| CN106711412B (en) | Composite lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN108808008B (en) | Three-dimensional mixed ion electron conductor current collector and preparation method and application thereof | |
| CN104966814A (en) | High-security metallic lithium cathode and preparation method thereof | |
| CN114122352A (en) | Silicon-carbon negative electrode material for inducing silicon deposition by doping porous carbon and preparation method thereof | |
| CN113097478A (en) | Double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery cathode material and preparation method thereof | |
| CN112201771A (en) | Pole piece, preparation method thereof and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |