CN106058209B - Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof - Google Patents
Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 41
- 239000010703 silicon Substances 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 229910021487 silica fume Inorganic materials 0.000 claims description 31
- 229920002521 macromolecule Polymers 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 238000009987 spinning Methods 0.000 claims description 22
- 238000013019 agitation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004815 dispersion polymer Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004917 carbon fiber Substances 0.000 abstract description 5
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 5
- 239000002134 carbon nanofiber Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000000835 fiber Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 35
- 239000000463 material Substances 0.000 description 19
- 239000010408 film Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- -1 LiCoO2 Chemical class 0.000 description 2
- 229910013119 LiMxOy Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 206010061619 Deformity Diseases 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910005001 Li12Si7 Inorganic materials 0.000 description 1
- 229910005321 Li15Si4 Inorganic materials 0.000 description 1
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011867 silicon-carbon complex material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
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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
- H01M4/628—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
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- 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 lithium ion battery self-supporting silicon based anode materials of a kind of plural layers and preparation method thereof.The Silicon Based Anode Materials for Lithium-Ion Batteries of the plural layers is combined by nano silicon particles and carbon nano-fiber, and the mass ratio of silicon and carbon is 1:0.5~1:6, carbon fiber layer and silicon-carbon compounding fiber layer thickness ratio are 1:1~1:5.The preparation method includes the following steps：First the mixture that nano silicon particles/organic high molecular polymer is formed is disperseed in organic solvent, to be sufficiently stirred respectively with organic high molecular polymer, respectively obtains uniform suspension and solution；Then by controlling electrostatic spinning bolus amount the multilayered cylindrical shell of carbon-to-carbon silicon compound-carbon-to-carbon silicon compound ...-carbon is obtained with the time；Next carbonization treatment is carried out under protective atmosphere, that is, prepares the lithium ion battery self-supporting silicon based anode material with plural layers.The present invention have the characteristics that self-supporting, capacity height, good cycling stability, prepare it is simple.
Description
Technical field
The present invention relates to lithium ion battery self-supporting silicon based anode materials of a kind of plural layers and preparation method thereof, belong to
Field of energy source materials.
Background technology
With the extensive use of electric vehicle, hybrid vehicle and solar energy, wind power generation etc., high-performance storage device
Become to become more and more important.Lithium ion battery has the advantages that energy density is high, and good cycle is higher than energy, and environmental pollution is small,
It is thus one of currently the most important ones energy storage device.
Lithium ion battery refer to that Li+ is embedded and abjection positive and negative pole material it is a kind of can charge and discharge high-energy battery.At present its
Positive electrode is generally using slotting lithium compound, such as LiCoO2、LiNiO2、LiMnO2Deng；Its negative material uses stratiform carbon material such as
Graphite；Dielectric is to have 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+Round-trip between two electrodes to be inserted into 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 when charging+It is embedded into cathode by electrolyte, electronics is logical
External circuit compensation is crossed to cathode, it is ensured that charge balance.Then on the contrary, Li when electric discharge+It is embedded into anode by electrolyte, electronics passes through
External circuit compensation ensures charge balance to anode.
By above-mentioned lithium ion battery operation principle it is found that negative material carries the effect of embedding and removing, negative material
Performance quality there is strong influence to the performance of lithium ion battery.The lithium ion battery negative material of existing market is stone
Ink, specific capacity is relatively low (only 372mAh/g), and energy density is relatively low, it is difficult to meet the fields such as electric vehicle, mobile electronic device
Requirement to heavy-duty battery, thus how to obtain the negative material with height ratio capacity and good circulation performance be lithium from
The important research direction of sub- battery material.
Silicon can be reacted with lithium, reversibly form a variety of alloys, such as Li22Si5、Li15Si4、Li12Si7Deng as negative
Theoretical Mass specific capacity is up to (4200mAh/g, Li when the material of pole22Si5), it is highest in the negative material being currently known, and
(0.4V) relatively low to lithium current potential, therefore be one of most promising negative material.
But silicon can undergo the volume change more than 400% during charge and discharge cycles, easily lead to active material dusting
And poor electric contact is caused from collector disengaging, and lead to that SEI films are unstable and constantly consume active material, to make it
Cycle performance is very poor.How to improve the cycle performance of silicon and do not influence its capacity excessively, is grinding for 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 a large amount of work
Make, devises the structure of a variety of silicon, such as the carbon silicon microballoon of silicon nanowire array, carbon-coated nano silicone tube, nucleocapsid, three-dimensional
Porous silicon carbon complex etc..These work achieve better achievement, to the specific capacity and cyclicity of silicon based anode material
Larger improvement can all be played.But its preparation process is mostly very complicated, area specific capacity is all relatively low；And current research
All it is to optimize structure design in microstructure level, there are no people to do macroscopic aspect and microcosmic point collaboration optimization material
The work of structure and ingredient.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of lithium ion battery self-supporting silicon of plural layers
Base negative material and preparation method thereof.
The lithium ion battery self-supporting silicon based anode material of plural layers is compound by nano silicon particles and carbon nano-fiber
Into plural layers, the wherein mass ratio of silicon and carbon is 1:0.5~1:6, the carbon fiber layer and silicon-carbon compound in plural layers are fine
It is 1 to tie up layer thickness ratio:1~1:5.
The preparation method of the lithium ion battery self-supporting silicon based anode material of plural layers includes the following steps：
1) in organic solvent by high molecular polymer dispersion, magnetic agitation is ultrasonically treated 30 ~ 60 points after 18 ~ 48 hours
Clock obtains 5 ~ 15wt% macromolecule polymer solutions；
2) it is 1 by mass ratio:1~12:1 high molecular polymer and nano silica fume is dispersed in organic solvent of the same race, magnetic
Power stirs 18 ~ 48 hours, is ultrasonically treated 30 ~ 60 minutes, obtains high molecular polymer and nano silica fume dispersion liquid；
3) using coaxial device for spinning carry out Jing electricity Fang Silk, inner tube be high molecular polymer and nano silica fume dispersion liquid, outside
Pipe is macromolecule polymer solution, injects macromolecule polymer solution first, and the duration stops injecting after forty minutes, is started
High molecular polymer and nano silica fume dispersion liquid are injected, stops injecting after 2 hours duration, starts again at and inject polyphosphazene polymer
Polymer solution, 40 minutes duration can be repeated several times the above process, obtain plural layers according to the number of plies of plural layers；
4) plural layers obtained are put into tube furnace, in 95%Ar+5%H2Under hydrogen-argon-mixed atmosphere, it is heated to
650 oC ~1000 oC is carbonized 10 ~ 0.5 hours to get to the lithium ion battery self-supporting silicon based anode material of plural layers.
The high molecular polymer is polyacrylonitrile, POLYPROPYLENE GLYCOL or polyvinylpyrrolidone.The organic solvent
It is dimethylformamide or tetrahydrofuran.The electrostatic spinning environment temperature and humidity is 30 ~ 40 DEG C and 40% respectively.The electrostatic
The positive high voltage of spinning is 12 ~ 18kV, and negative high voltage is -2kV.The nozzle of the coaxial device for spinning to reception device distance for 10 ~
15cm.The high molecular polymer and nano silica fume dispersion liquid and macromolecule polymer solution inject speed be 0.005 ~
0.02mL/min.The carburizing temperature is 650 oC ~1000 oC。
The present invention new type lithium ion battery self-supporting silicon based anode material have excellent performance, can be used for substituting existing lithium from
Sub- battery carbon negative pole material, has a good application prospect.The negative material has good flexibility, can alleviate electrode layer
Facial disfigurement reduces capacity attenuation；There is self-supporting characteristic with negative film material prepared by method of electrostatic spinning, do not need collector
And binder, greatly improve specific discharge capacity；The interlayer number of plies and thickness can be controlled by controlling spinning time and flow, it can be with
Prepare multilayer, big thickness negative film material, obtain very high area specific capacity；Orient carbon fiber arrangement prepared by spinning
Densification, gap is small, can effectively inhibit nano silicon particles to be detached from electrode contact, alleviate capacity attenuation；The preparation process of the present invention
Simple possible, it is of low cost, stannic oxide, iron oxide etc. can be promoted the use of and generate enormousness change in charge and discharge process
In the preparation of the negative material of change, there is certain universality.
Description of the drawings
Fig. 1 is three-ply sandwich structure section electron microscope；
Fig. 2 is sandwich front scan electron microscopic picture.
Specific implementation mode
The lithium ion battery self-supporting silicon based anode material of plural layers is compound by nano silicon particles and carbon nano-fiber
Into plural layers, the wherein mass ratio of silicon and carbon is 1:0.5~1:6, the carbon fiber layer and silicon-carbon compound in plural layers are fine
It is 1 to tie up layer thickness ratio:1~1:5.
The preparation method of the lithium ion battery self-supporting silicon based anode material of plural layers includes the following steps：
1) in organic solvent by high molecular polymer dispersion, magnetic agitation is ultrasonically treated 30 ~ 60 points after 18 ~ 48 hours
Clock obtains 5 ~ 15wt% macromolecule polymer solutions；
2) it is 1 by mass ratio:1~12:1 high molecular polymer and nano silica fume is dispersed in organic solvent of the same race, magnetic
Power stirs 18 ~ 48 hours, is ultrasonically treated 30 ~ 60 minutes, obtains high molecular polymer and nano silica fume dispersion liquid；
3) using coaxial device for spinning carry out Jing electricity Fang Silk, inner tube be high molecular polymer and nano silica fume dispersion liquid, outside
Pipe is macromolecule polymer solution, injects macromolecule polymer solution first, and the duration stops injecting after forty minutes, is started
High molecular polymer and nano silica fume dispersion liquid are injected, stops injecting after 2 hours duration, starts again at and inject polyphosphazene polymer
Polymer solution, 40 minutes duration can be repeated several times the above process, obtain plural layers according to the number of plies of plural layers；
4) plural layers obtained are put into tube furnace, in 95%Ar+5%H2Under hydrogen-argon-mixed atmosphere, it is heated to
650 oC ~1000 oC is carbonized 10 ~ 0.5 hours to get to the lithium ion battery self-supporting silicon based anode material of plural layers.
The high molecular polymer is polyacrylonitrile, POLYPROPYLENE GLYCOL or polyvinylpyrrolidone.The organic solvent
It is dimethylformamide or tetrahydrofuran.The electrostatic spinning environment temperature and humidity is 30 ~ 40 DEG C and 40% respectively.The electrostatic
The positive high voltage of spinning is 12 ~ 18kV, and negative high voltage is -2kV.The nozzle of the coaxial device for spinning to reception device distance for 10 ~
15cm.The high molecular polymer and nano silica fume dispersion liquid and macromolecule polymer solution inject speed be 0.005 ~
0.02mL/min.The carburizing temperature is 650 oC ~1000 oC。
Embodiment 1
1）1.5g polyacrylonitrile is dissolved in dimethyl amide, magnetic agitation is ultrasonically treated 30 minutes after 24 hours,
Obtain the macromolecule polymer solution of 8wt%；
2）Nano silica fume and polyacrylonitrile are dispersed in organic solvent of the same race, magnetic agitation is ultrasonically treated 30 after 24 hours
Minute, obtain high molecular polymer and nano silica fume dispersion liquid；
3）Plural layers are prepared with electrostatic spinning machine spinning：It adjusts and suitable positive high voltage 18Kv, negative high voltage -2kV, ring is set
Border temperature 30oC, humidity 40% select high speed orientation attachment as reception device.Using coaxial device for spinning, inner tube is macromolecule
Polymer and nano silica fume dispersion liquid, outer tube are macromolecule polymer solution.The nozzle of coaxial device for spinning to reception device away from
From for 15cm.Macromolecule polymer solution is injected first, and it is 0.02mL/min to inject speed, continues to stop after forty minutes, is started
High molecular polymer and nano silica fume dispersion liquid are injected, it is 0.02mL/min to inject speed, stops after 2 hours duration, opens
Beginning injects macromolecule polymer solution, and it is 0.02mL/min, 40 minutes duration to inject speed；
4）Film obtained is put into tube furnace, under hydrogen-argon-mixed atmosphere, be heated to 650 DEG C carbonization 10h to get to
The lithium ion battery self-supporting silicon based anode material of plural layers.
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
It is shown, through sem analysis：Carbon-to-carbon silicon compound-C film is in apparent multilayered structure, about 100 μm of film thickness, carbon thin film layer
About 20 μm of thickness, about 60 μm of carbon-silicon compound thin film layer thickness.Fig. 2 show the front scan electromicroscopic photograph of thin-film material, can
To find carbon fiber at significantly aligning.
By charge-discharge test it can be found that the lithium ion battery self-supporting silicon based anode material of plural layers discharges for the first time
Capacity is 1134mAh/g, and coulombic efficiency is 77% for the first time, and capacity retention ratio is 86.2% after 50 cycles.
Embodiment 2
1）1.5g polyvinylpyrrolidones are dissolved in dimethyl amide, magnetic agitation is ultrasonically treated 30 after 24 hours
Minute, obtain the macromolecule polymer solution of 5wt%；
2）Nano silica fume and polyvinylpyrrolidone are dispersed in organic solvent of the same race, magnetic agitation is ultrasonic after 24 hours
Processing 30 minutes, obtains high molecular polymer and nano silica fume dispersion liquid；
3）Plural layers are prepared with electrostatic spinning machine spinning：It adjusts and suitable positive high voltage 15Kv, negative high voltage -2kV, ring is set
Border temperature 40oC, humidity 40% select high speed orientation attachment as reception device.Using coaxial device for spinning, inner tube is macromolecule
Polymer and nano silica fume dispersion liquid, outer tube are macromolecule polymer solution.The nozzle of coaxial device for spinning to reception device away from
From for 10cm.Macromolecule polymer solution is injected first, and it is 0.017mL/min to inject speed, continues to stop after forty minutes, is started
High molecular polymer and nano silica fume dispersion liquid are injected, it is 0.017mL/min to inject speed, stops after 2 hours duration, opens
Beginning injects macromolecule polymer solution, and it is 0.017mL/min, 40 minutes duration to inject speed；
4）Film obtained is put into tube furnace, under hydrogen-argon-mixed atmosphere, be heated to 750 DEG C carbonization 5h to get to
The lithium ion battery self-supporting silicon based anode material of plural layers.
Embodiment 3
1）1.5g POLYPROPYLENE GLYCOLs are dissolved in tetrahydrofuran, magnetic agitation is ultrasonically treated 30 minutes after 24 hours, is obtained
The macromolecule polymer solution of 15wt%；
2）Nano silica fume and POLYPROPYLENE GLYCOL are dispersed in organic solvent of the same race, magnetic agitation is ultrasonically treated 30 after 24 hours
Minute, obtain high molecular polymer and nano silica fume dispersion liquid；
3）Plural layers are prepared with electrostatic spinning machine spinning：It adjusts and suitable positive high voltage 15Kv, negative high voltage -2kV, ring is set
Border temperature 30oC, humidity 40%.Using coaxial device for spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, outer tube are
Macromolecule polymer solution.The nozzle of coaxial device for spinning to reception device distance be 10cm.High molecular polymer is injected first
Solution, it is 0.02mL/min to inject speed, continues to stop after forty minutes, starts to inject high molecular polymer and nano silica fume dispersion
Liquid, it is 0.02mL/min to inject speed, stops after 2 hours duration, starts to inject macromolecule polymer solution, inject speed
For 0.02mL/min, 40 minutes duration；
4）Film obtained is put into tube furnace, under hydrogen-argon-mixed atmosphere, be heated to 900 DEG C carbonization 1 hour to get
To the lithium ion battery self-supporting silicon based anode material of plural layers.
Embodiment 4
1）1.5g polyacrylonitrile is dissolved in dimethyl amide, magnetic agitation is ultrasonically treated 30 minutes after 24 hours,
Obtain the macromolecule polymer solution of 15wt%；
2）Nano silica fume and polyacrylonitrile are dispersed in organic solvent of the same race, magnetic agitation is ultrasonically treated 30 after 24 hours
Minute, obtain high molecular polymer and nano silica fume dispersion liquid；
3）Plural layers are prepared with electrostatic spinning machine spinning：It adjusts and suitable positive high voltage 18Kv, negative high voltage -2kV, ring is set
Border temperature 40oC, humidity 40%.Using coaxial device for spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, outer tube are
Macromolecule polymer solution.The nozzle of coaxial device for spinning to reception device distance be 15cm.High molecular polymer is injected first
Solution, it is 0.005mL/min to inject speed, continues to stop after forty minutes, starts to inject high molecular polymer and nano silica fume point
Dispersion liquid, it is 0.005mL/min to inject speed, stops after 2 hours duration, starts to inject macromolecule polymer solution, inject
Speed is 0.005mL/min, 40 minutes duration；
4）Film obtained is put into tube furnace, under hydrogen-argon-mixed atmosphere, 1000 DEG C is heated to and is carbonized 0.5 hour,
Obtain the lithium ion battery self-supporting silicon based anode material of plural layers.
Claims (7)
1. the preparation method of the lithium ion battery self-supporting silicon based anode material of a kind of plural layers, it is characterized in that including following step
Suddenly：
1) in organic solvent by high molecular polymer dispersion, magnetic agitation is ultrasonically treated 30 ~ 60 minutes after 18 ~ 48 hours, is obtained
To 5 ~ 15wt% macromolecule polymer solutions；
2) it is 1 by mass ratio:1~12:1 high molecular polymer and nano silica fume is dispersed in and step 1）Identical organic solvent
In, magnetic agitation 18 ~ 48 hours is ultrasonically treated 30 ~ 60 minutes, obtains high molecular polymer and nano silica fume dispersion liquid；
3) electrostatic spinning is carried out using coaxial device for spinning, inner tube is high molecular polymer and nano silica fume dispersion liquid, outer tube are
Macromolecule polymer solution injects macromolecule polymer solution first, continues to stop injecting after forty minutes, starts to inject macromolecule
Polymer and nano silica fume dispersion liquid stop injecting, start again at and inject macromolecule polymer solution after continuing 2 hours, continue
40 minutes, according to the number of plies of plural layers, the above process can be repeated several times, obtain plural layers；
4) plural layers obtained are put into tube furnace, in 95%Ar+5%H2Under hydrogen-argon-mixed atmosphere, be heated to 650 DEG C ~
1000 DEG C of carbonizations 10 ~ 0.5 hours are to get to the lithium ion battery self-supporting silicon based anode material of plural layers.
2. a kind of preparation side of the lithium ion battery self-supporting silicon based anode material of plural layers according to claim 1
Method, it is characterised in that the high molecular polymer is polyacrylonitrile, POLYPROPYLENE GLYCOL or polyvinylpyrrolidone.
3. a kind of preparation side of the lithium ion battery self-supporting silicon based anode material of plural layers according to claim 1
Method, it is characterised in that the organic solvent is dimethylformamide or tetrahydrofuran.
4. a kind of preparation side of the lithium ion battery self-supporting silicon based anode material of plural layers according to claim 1
Method, it is characterised in that the electrostatic spinning environment temperature, humidity are 30 ~ 40 DEG C and 40% respectively.
5. a kind of preparation side of the lithium ion battery self-supporting silicon based anode material of plural layers according to claim 1
Method, it is characterised in that the positive high voltage of the electrostatic spinning is 12 ~ 18kV, and negative high voltage is -2kV.
6. a kind of preparation side of the lithium ion battery self-supporting silicon based anode material of plural layers according to claim 1
Method, it is characterised in that the nozzle of the coaxial device for spinning to reception device distance is 10 ~ 15cm.
7. a kind of preparation side of the lithium ion battery self-supporting silicon based anode material of plural layers according to claim 1
Method, it is characterised in that the speed of injecting of the high molecular polymer and nano silica fume dispersion liquid and macromolecule polymer solution is
0.005~0.02mL/min。
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| 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 |
| CN113745490B (en) * | 2017-09-07 | 2022-11-29 | 上海杉杉科技有限公司 | Nano silicon-based composite fiber negative electrode material of lithium ion battery |
| CN107863519B (en) * | 2017-11-09 | 2019-12-17 | 陕西科技大学 | Lithium ion battery negative pole piece and preparation method thereof |
| CN108054368B (en) * | 2017-12-12 | 2020-08-11 | 贝特瑞新材料集团股份有限公司 | Silicon-based negative electrode material, preparation method thereof and application thereof in lithium ion battery |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN117954576A (en) * | 2024-03-26 | 2024-04-30 | 宁波大学 | Alloy negative electrode with high capacity and low strain |
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