CN105070917A - Preparation method for asphalt-based nanocomposite fiber with skin-core structure and application of asphalt-based nanocomposite fiber to lithium ion battery - Google Patents
Preparation method for asphalt-based nanocomposite fiber with skin-core structure and application of asphalt-based nanocomposite fiber to lithium ion battery Download PDFInfo
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- CN105070917A CN105070917A CN201510581382.6A CN201510581382A CN105070917A CN 105070917 A CN105070917 A CN 105070917A CN 201510581382 A CN201510581382 A CN 201510581382A CN 105070917 A CN105070917 A CN 105070917A
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- asphalt
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/13—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
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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
- H01M4/13—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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
Abstract
The invention relates to a preparation method for an asphalt-based nanocomposite fiber with a skin-core structure, as well as application of the asphalt-based nanocomposite fiber to a lithium ion battery as a cathode material. The nanocomposite fiber is prepared by an electrostatic spinning method, and is easy to produce on a large scale, and a process is simple; the diameter of the fiber is 20 to 300 nanometers, a skin layer is asphalt, and a core layer is a macromolecular compound such as polyacrylonitrile; the fiber has high electrical conductivity after being carbonized, and has high electrochemical performance as the cathode material of the lithium ion battery, the first reversible specific capacity reaches 617mAhg-1, and the capacity after 200 cycles is kept over 90 percent.
Description
Technical field
Asphalt-based nano composite fibre that the present invention relates to a kind of skin-core structure and preparation method thereof, and use this material as the preparations and applicatio of the negative material of lithium ion battery.
Background technology
Lithium ion battery compared to other secondary cells, have energy density high, have extended cycle life, the advantage such as memory-less effect, be widely used in the accumulation power supply of the portable equipment such as mobile phone, notebook at present.Along with the continuous popularization of electric automobile, electric vehicle power lithium-ion battery becomes the focus of people's research.As electrokinetic cell, have large current density power and higher reversible capacity, this just has higher requirement to the high rate performance of electrode material and energy density.
Current commercial lithium ion battery negative material mainly graphite material.Graphite material can be stable realize removal lithium embedded, there is good cycle performance and useful life.But graphite electrode is 372mAh/g as the theoretical capacity of lithium ion battery negative material, and when high power charging-discharging, lithium ion can not carry out embedding and deviating from timely, and this will reduce capacity and the cycle life of battery greatly.
Hard carbon material degree of graphitization is low, and the institutional framework of graphite flake layer is in order regular unlike graphite, and comprises a large amount of amorphous region, and interlamellar spacing is larger between 0.34 ~ 0.40nm.Containing a large amount of nanometer micropore in hard carbon material, this is that the storage of lithium ion provides desirable avtive spot, has the specific capacity higher than graphite cathode.Meanwhile, the interlamellar spacing that hard carbon material is larger is conducive to lithium ion and embeds fast and deviate from, and therefore also has better high rate performance.But the avtive spot that hard carbon material surface is enriched also result in larger irreversible capacity, makes coulombic efficiency first lower.
Soft charcoal material specific surface area is lower, effectively can reduce irreversible capacity, also has good high rate performance simultaneously.Coulombic efficiency first can be improved at hard carbon material Surface coating one deck soft charcoal material, obtain the advantage having energy density height and good rate capability concurrently.
Adopt the nanometer fiber net that electro-spinning is standby, fiber overlaps mutually, for the transmission of ion and electronics provides fast and convenient path, greatly facilitates electrochemical kinetics, effectively can improve circulation and the high rate performance of battery.
Summary of the invention
In view of this, be necessary to provide a kind of simple method to prepare the combination electrode material of hard charcoal and soft charcoal.The present invention take pitch as soft charcoal presoma, and high molecular polymer is hard carbon precursor, adopts the method for electrostatic spinning to prepare a kind of skin-core structure soft charcoal/hard charcoal nano-composite fiber.Using this nano-composite fiber as the lithium ion battery of negative material, possesses the advantage of energy density height and good rate capability simultaneously.Its preparation method is simple, is beneficial to large-scale production.
Technical scheme of the present invention:
An asphalt-based nano composite fibre for skin-core structure, is characterized in that, fibre diameter is in 20-300 nanometer.Cortical material is pitch, and thickness is in 10-300 nanometer; Core material is the macromolecular compound such as polyacrylonitrile, Kynoar, and thickness is in 10-300 nanometer.
A preparation method for the asphalt-based nano composite material of skin-core structure, comprises following steps:
Step one: massive asphalt is smashed, spheroidal graphite 4 hours, obtains micron-sized asphalt powder;
Step 2: added to by asphalt powder in the organic solvents such as oxolane, stirs 6 ~ 24 hours, obtains homogeneous cold primer-oil;
Step 3: be dissolved in by polyacrylonitrile in intensive polar solvent, obtains the polyacrylonitrile solution that mass concentration is 8%-20%;
Step 4: polyacrylonitrile solution added in cold primer-oil, stir, obtains the mixed solution that solid content is 5%-30%;
Step 5: with gained mixed solution for spinning solution, adopts the method for Static Spinning to prepare asphalt-based nano composite fibre.
Below above steps is described in detail.
In described step 2, organic solvent used is oxolane, carbon tetrachloride and mixed solvent thereof.
In described step 3, described intensive polar solvent is one or more in following solvents: DMF, DMA, dimethyl sulfoxide (DMSO), ethylene carbonate.
Described step 5, the preparation method of asphalt-based nano composite fibre, it is characterized in that, electrostatic spinning syringe needle used is single hole syringe needle, internal diameter is 0.5-1.2mm, fiber collecting device is metallic cylinder, wire netting, metal plate etc., and the distance between syringe needle and receiving system is 5-30cm, between institute's making alive be 10-35kv.
The invention still further relates to a kind of preparation method of lithium ion battery negative; it is characterized in that, electrostatic spinning gained fleece is carried out successively pre-oxidation and charing process, pre-oxidation is carried out in the air stream; carbonization process carries out under inert gas shielding, obtains asphalt-based nano Carbon fibe net.
The preparation method of pole piece is following two kinds:
One, gained Carbon fibe net is ground, adds conductive agent and binding agent, be coated on Copper Foil, dry backlash pole piece;
Two, gained fleece directly rushes pole piece, does not add any conductive agent and binding agent.
The invention has the advantages that: the present invention adopts the method for single needle electrostatic spinning to prepare the nanofiber of skin-core structure, process is simple, is easy to operation, can large-scale production.And the In-situ reaction of soft charcoal and hard carbon material can be realized, the shape of fiber after sintering, can be kept, and there is good toughness, can directly as electrode material.This method preparing electrode, is expected to be applied to flexible battery.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of carbon fiber net.
Fig. 2 is the transmission electron microscope photo of carbon fiber.
Fig. 3 is the X-ray diffractogram of carbon fiber.
Fig. 4 is lithium ion battery first charge-discharge curve.
Fig. 5 is the cycle performance curve of lithium ion battery.
Fig. 6 is the high rate performance curve of lithium ion battery discharge and recharge under different current density.
Embodiment
Embodiment:
A kind of preparation method of asphalt-based nano composite fibre of skin-core structure and the application in lithium ion battery thereof.
The preparation method of asphalt-based nano composite material, comprises following steps:
Step one: a kind of high softening point bitumen is provided, is broken into powdered.By asphalt powder ball mill spheroidal graphite 4 hours, obtain the asphalt powder of micron-scale.
Step 2: get 3g asphalt powder art, add 7g tetrahydrofuran solvent, magnetic agitation more than 6 hours, obtains the cold primer-oil of mass concentration 30%.
Step 3: be dissolved in by polyacrylonitrile in DMF, obtains the polyacrylonitrile solution of mass concentration 15%.
Step 4: the polyacrylonitrile solution of getting 20g concentration 15% is added in above-mentioned cold primer-oil, stirs, obtains pitch and polyacrylonitrile mass ratio is the mixed solution of 1: 1.
Step 5: add in syringe by this mixed solution, adopts internal diameter 0.8mm syringe needle to carry out electrostatic spinning.Apply voltage 28KV, employing corrosion resistant plate is receiving system, and the distance between needle point and dash receiver is 15cm, and fltting speed is that 1.5mL is per hour.
Asphalt-based nano composite fibre is used as lithium ion battery negative material, and electrode preparation method is as follows:
Composite fibre is put in tube furnace, passes to air atmosphere, be heated to 300 DEG C, keep 2 hours, pre-oxidation is carried out to fiber.
The fiber after described pre-oxidation under the protection of argon gas, be heated to 700 DEG C and carbonize.
Fig. 1 is the SEM figure of described carbon fiber, and after can finding out charing, fiber shape remains intact, and diameter is more homogeneous, and between 200-300 nanometer, fiber is interweaved and overlaps, and forms three-dimensional electron propagation ducts.
Fig. 2 is the TEM figure of described carbon fiber, and two-phase interface clearly appears in fiber, illustrates that the fiber formed is skin-core structure.The brighter part of cortex is bitumen layer, and sandwich layer is comparatively dark, is polyacrylonitrile.
Fig. 3 is the X-ray diffractogram of described fiber.This figure is the XRD collection of illustrative plates of typical amorphous carbon.
By direct for the fiber after described charing punching, as lithium ion battery negative.
The assembling of battery and test
As previously mentioned, barrier film is polyethylene one polypropylene one polyethylene trilamellar membrane, and electrolyte is 1MLiPF in the making of negative plate
6volume ratio be the mixed liquor of EC and DMC of 1: 1.Above-mentioned negative plate and lithium sheet, barrier film and electrolyte are assembled into CR2430 button cell in the glove box being full of hydrogen.
Fig. 4 is the first charge-discharge curve of described nanofiber as lithium ion battery negative material.Charging/discharging voltage scope 0.005-2.5V, current density 20mAg
-1.As seen from the figure, its first reversible capacity be 852mAhg
-1, far above the theoretical specific capacity of graphite cathode.Discharge curve is made up of the power of the oblique line between 1V-0.2 and below 0.2V, does not have the typical discharge platform of graphite cathode material.Coulombic efficiency 69.4% first, higher than hard carbon material.
Fig. 5 is the cycle performance curve of described nanofiber as lithium ion battery negative material.Charging/discharging voltage scope 0.005-2.5V, current density 200mAg
-1.This material visible shows goodish cyclical stability, and only decay to some extent at front circulation volume several times, coulombic efficiency is close to 100% afterwards.
Fig. 6 is the high rate performance curve of described nanofiber as lithium ion battery negative material discharge and recharge under different current density, charging/discharging voltage scope 0.005-2.5V.Reversible capacity under 50mAg-1,0.1Ag-1,0.2Ag-1,0.4Ag-1 and 1Ag-1 current density is respectively 577.6,490.2,383.3,337.3 and 277.5mAhg
-1.Described nano-composite fiber is at 400mAg
-1high current density under discharge and recharge, capacity reaches 337.3mAhg
-1, close to the theoretical specific capacity of graphite material under low current density.
Claims (7)
1. an asphalt-based nano composite fibre for skin-core structure, is characterized in that, fibre diameter is in 20-300 nanometer.Cortical material is pitch, and thickness is in 10-300 nanometer; Core material is the macromolecular compound such as polyacrylonitrile, Kynoar, and thickness is in 10-300 nanometer.
2. a preparation method for the asphalt-based nano composite material of skin-core structure, is characterized in that, comprises following steps:
1) massive asphalt is smashed, spheroidal graphite 4 hours, obtain micron-sized asphalt powder;
2) asphalt powder is added in the organic solvents such as oxolane, stir 6 ~ 24 hours, obtain homogeneous cold primer-oil;
3) polyacrylonitrile is dissolved in intensive polar solvent, obtains the polyacrylonitrile solution that mass concentration is 8%-20%;
4) polyacrylonitrile solution is added in cold primer-oil, stir, obtain the mixed solution that solid content is 5%-30%;
5) with gained mixed solution for spinning solution, adopt the method for Static Spinning to prepare asphalt-based nano composite fibre.
3. the preparation method of asphalt-based nano composite fibre as claimed in claim 2, is characterized in that, step 2) in organic solvent used be oxolane, carbon tetrachloride and mixed solvent thereof.
4. the preparation method of asphalt-based nano composite fibre as claimed in claim 2, it is characterized in that, step 3) described in intensive polar solvent be one or more in following solvents: DMF, DMA, dimethyl sulfoxide (DMSO), ethylene carbonate.
5. the preparation method of asphalt-based nano composite fibre as claimed in claim 2, it is characterized in that, electrostatic spinning syringe needle used is single hole syringe needle, internal diameter is 0.5-1.2mm, fiber collecting device is metallic cylinder, wire netting, metal plate etc., distance between syringe needle and receiving system is 5-30cm, between institute's making alive be 10-35kv.
6. the invention still further relates to a kind of preparation method of lithium ion battery negative; it is characterized in that; electrostatic spinning gained fleece is carried out successively pre-oxidation and charing process; pre-oxidation is carried out in the air stream; different temperatures carbonization process carries out under inert gas shielding, obtains asphalt-based nano Carbon fibe net.
7. the preparation method of lithium ion battery negative as claimed in claim 6, is characterized in that, the production method of pole piece is two kinds: one, is ground by gained Carbon fibe net, adds conductive agent and binding agent, be coated on Copper Foil, dry backlash pole piece; Two, gained fleece directly rushes pole piece, does not add any conductive agent and binding agent.
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|---|---|---|---|
| CN201510581382.6A CN105070917A (en) | 2015-09-10 | 2015-09-10 | Preparation method for asphalt-based nanocomposite fiber with skin-core structure and application of asphalt-based nanocomposite fiber to lithium ion battery |
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| CN201510581382.6A CN105070917A (en) | 2015-09-10 | 2015-09-10 | Preparation method for asphalt-based nanocomposite fiber with skin-core structure and application of asphalt-based nanocomposite fiber to lithium ion battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637522A (en) * | 2016-10-19 | 2017-05-10 | 南通大学 | High-dispersion PAN (polyacrylonitrile) fiber for asphalt concrete and method for preparing high-dispersion PAN fiber |
| CN107881600A (en) * | 2017-09-18 | 2018-04-06 | 大连理工大学 | A kind of preparation method and applications of carbon nano-fiber for negative electrode of lithium ion battery |
| CN114122390A (en) * | 2021-11-16 | 2022-03-01 | 宁波杉杉新材料科技有限公司 | Preparation method of carbon electrode material and carbon electrode material |
| CN114808197A (en) * | 2022-04-20 | 2022-07-29 | 山东大学 | Integrated two-phase asphalt-based carbon nanofiber and preparation method and application thereof |
-
2015
- 2015-09-10 CN CN201510581382.6A patent/CN105070917A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637522A (en) * | 2016-10-19 | 2017-05-10 | 南通大学 | High-dispersion PAN (polyacrylonitrile) fiber for asphalt concrete and method for preparing high-dispersion PAN fiber |
| CN107881600A (en) * | 2017-09-18 | 2018-04-06 | 大连理工大学 | A kind of preparation method and applications of carbon nano-fiber for negative electrode of lithium ion battery |
| CN114122390A (en) * | 2021-11-16 | 2022-03-01 | 宁波杉杉新材料科技有限公司 | Preparation method of carbon electrode material and carbon electrode material |
| CN114808197A (en) * | 2022-04-20 | 2022-07-29 | 山东大学 | Integrated two-phase asphalt-based carbon nanofiber and preparation method and application thereof |
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