CN108400317A - A kind of integration lithium ion battery silicon/carbon cathode material and preparation method thereof - Google Patents
A kind of integration lithium ion battery silicon/carbon cathode material and preparation method thereof Download PDFInfo
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- CN108400317A CN108400317A CN201810234257.1A CN201810234257A CN108400317A CN 108400317 A CN108400317 A CN 108400317A CN 201810234257 A CN201810234257 A CN 201810234257A CN 108400317 A CN108400317 A CN 108400317A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
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Abstract
The invention discloses a kind of integrated lithium ion battery silicon/carbon cathode materials and preparation method thereof, wherein integrated lithium ion battery silicon/carbon cathode material is using silica flour as silicon source, pyrolytic carbon is carbon matrix, nano-sized carbon is to enhance integrated lithium ion battery silicon/carbon cathode material of skeleton.The nano-carbon material introduced in structure of the invention design can form good conductive network, the nano-sized carbon being dispersed in simultaneously in pyrolysis carbon matrix can alleviate the local stress that silicon is brought by bulk effect in charge and discharge process, the problems such as electrode cracking caused by avoiding thus or even dusting, to stablize overall structure so that the novel higher specific capacity of cathode and excellent high rate performance and cycle performance.
Description
Technical field
The present invention relates to a kind of integrated lithium ion battery silicon/carbon cathode materials and preparation method thereof.
Background technology
Lithium ion battery has the characteristics that energy density is high, easy to use, without geographical restrictions, be widely used in mobile phone,
On the vehicles such as the consumption electronic products such as computer and electric vehicle.Various fields are close to the energy of lithium ion battery at present
Degree proposes increasingly higher demands, and there is an urgent need to seek high power capacity, longevity for the development of the lithium ion battery of high-energy density
Life and safe and reliable novel anode material.
Silicon is a kind of novel cathode material for lithium ion battery of great application potential, can be formed completely with lithium at room temperature
Li15Si4Alloy, theoretical capacity are up to 3590mA h g-1, about ten times of (372mAh g of graphite theoretical specific capacity-1).However,
The Li that the embedding lithium of silicium cathode material is formed15Si4Phase volume expands more than 300%, thus can be generated instead during embedding and removing
Multiple volume expansion and contraction so as to cause broken and electrode the differentiation cracking of particle, and causes silicon materials to add with conduction
Agent and collector is added to lose good electrical contact.This bulk effect also results in silicon and is difficult to form stable consolidate in the electrolytic solution
Body electrolyte interface (SEI) film.Along with the destruction of electrode structure, new SEI films are constantly formed in the silicon face exposed, are led
It causes constantly thickening for SEI films, ion and electronics disengaging to be obstructed, exacerbates corrosion and the capacity attenuation of silicon.In addition, silicon is a kind of half
Conductor, electric conductivity is poor, and which also limits pure phase silicon to use directly as lithium ion battery negative material.To improve silicium cathode material
The chemical property of material improves structural stability of the material in cyclic process, and researchers have found, will reduce the ruler of silicon particle
Degree and the material of compound high conductivity can efficiently solve the above problem.Thus, development high performance lithium ion battery silicon/charcoal
Cathode is one of the effective way for realizing lithium ion battery with high energy density.
Invention content
The present invention is for the shortcoming present in prior art, it is desirable to provide a kind of integration lithium ion battery silicon/charcoal
Negative material and preparation method thereof, with high rate performance and the cyclical stability etc. for promoting Silicon Based Anode Materials for Lithium-Ion Batteries.
It is carbon matrix that integration lithium ion battery silicon/carbon cathode material of the invention, which is using silica flour as silicon source, pyrolytic carbon, is received
Rice carbon is the integrated lithium ion battery silicon/carbon cathode material for enhancing skeleton.
The preparation method of integration lithium ion battery silicon/carbon cathode material of the invention, includes the following steps：
Step 1：Silica flour, binder, nano-sized carbon and solvent are mixed into the slurrying that is uniformly dispersed；
Step 2：By step 1 gained slurry coating, pole piece is made in drying on copper current collector；
Step 3：Step 2 gained pole piece is obtained into integrated lithium ion battery silicon/carbon cathode material after charing process.
In step 1, average grain diameter≤1 μm of the silica flour；The binder is Kynoar, polytetrafluoroethylene (PTFE), gathers
Vinyl alcohol, polyolefin, sodium carboxymethylcellulose, sodium alginate or rubber；The nano-sized carbon is that carbon nanotube, graphene or carbon are received
Rice fiber.
In step 1, the selection of solvent is related to binder, and binder is divided into organic binder and water-based binder, if
When organic binder such as PVDF, the solvent of selection is NMP；And water-based binder such as sodium alginate, solvent for use are water.Solvent
Additive amount rule of thumb makes manufactured slurry tool be a bit sticky, and includes the variation of binder according to the above amount of solid
And it is different, do not require specifically.
In step 1, the quality of the silica flour is the 50%~80% of silicon/carbon cathode material quality (not including collector)；
Pyrolytic carbon substrate quality after binder charing is the 10%~50% of silicon/carbon cathode material quality (not including collector)；It receives
Rice carbonaceous amount is the 1%~20% of silicon/carbon cathode material quality (not including collector).
In step 2, the coating thickness of slurry is 25~500 μm.
In step 3, the treatment temperature of the charing process is 500~900 DEG C, and processing time is 1~4h, and atmosphere is nitrogen
Or argon gas.
Integration lithium ion battery silicon/carbon cathode material of the invention is using silica flour as silicon source, and pyrolytic carbon is carbon matrix, nanometer
Carbon is the integrated lithium ion battery silicon/charcoal cathode for enhancing skeleton.
The lithium ion battery silicon reported/charcoal cathode all first synthesizes silicon/carbon composite (more needing to be heat-treated) mostly,
Then electrode slice is made jointly with binder, conductive agent again, the step complexity is cumbersome.And the preparation method of the present invention is to existing lithium
Ion battery cathode preparation process is innovated, and it is negative can simply and effectively to directly obtain integrated lithium ion battery silicon/charcoal
Pole obtains the electrode slice that nano-sized carbon is added, then directly in certain temperature with existing negative electrode of lithium ion battery preparation process
It is lower that binder is converting at pyrolytic carbon.The nano-carbon material introduced in this structure design can form good conductive mesh
Network, while the nano-sized carbon being dispersed in pyrolysis carbon matrix can alleviate in charge and discharge process silicon because the part that bulk effect is brought is answered
The problems such as power, electrode cracking caused by avoiding thus or even dusting, to stablize overall structure so that the novel cathode is higher
Specific capacity and excellent high rate performance and cycle performance.
The preparation method of the present invention is simple and effective, and the integrated lithium ion battery silicon substrate cathode of preparation has following significantly excellent
Gesture：
1, silica flour can significantly be alleviated in charge and discharge by being dispersed in the nano-sized carbon of integrated lithium ion battery silicon/charcoal cathode
Process avoids electrode cracking, dusting from destroying because of local stress caused by bulk effect, plays the role of structure enhancing；
2, good conductive network can be formed by being dispersed in the nano-sized carbon of integrated lithium ion battery silicon/charcoal cathode,
Play the role of charge transmission enhancing；
3, integrated lithium ion battery silicon/charcoal cathode can be compatible with the preparation process of existing negative electrode of lithium ion battery.It should
Novel all-in-one lithium ion battery silicon/charcoal cathode shows higher specific capacity and excellent multiplying power and cycle performance.
Description of the drawings
Fig. 1 is the SEM photograph of integrated lithium ion battery silicon/charcoal cathode prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD diagram of integrated lithium ion battery silicon/charcoal cathode prepared by the embodiment of the present invention 1；
Fig. 3 is integrated lithium ion battery silicon/charcoal cathode prepared by the embodiment of the present invention 1 and with conventional lithium ion cathode
Cycle performance figure of the silicium cathode that preparation process obtains under 0.5C multiplying powers.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1：
The present embodiment prepares lithium ion battery silicon-carbon cathode material as follows：
1,0.12g silica flours (average grain diameter 200nm), 0.09g Kynoar and 0.02g carbon nanotubes are uniformly mixed
Nmp solvent stirring 16h is added afterwards, slurry is made；
2, by slurry obtained with 50 μm it is in homogeneous thickness be coated in copper foil on, 80 DEG C baking ovens drying after roll,
It is then cut into the electrode slice of diameter 14mm；
3, under nitrogen atmosphere protection, electrode slice is placed in 600 DEG C of heat treatment 2h, integrated lithium is obtained after being cooled to room temperature
Ion battery silicon/charcoal cathode.
Fig. 1 is the SEM photograph of integrated lithium ion battery silicon/charcoal cathode prepared by the present embodiment, it can be seen that nanometer
The surface of silicon ball is pyrolyzed charcoal cladding, and it (is that integrated lithium ion battery silicon/charcoal is negative in illustration that carbon nanotube, which interweaves outside particle,
The photo of pole).
Fig. 2 is the XRD diagram of integrated lithium ion battery silicon/charcoal cathode prepared by the present embodiment.Corresponding to square icon
Be copper foil diffraction maximum (PDF#04-0836), corresponding to round icon is the diffraction maximum (PDF#27-140) of silicon, and 20 °
The broad peak of left and right is the diffraction maximum of unformed pyrolytic carbon.
Fig. 3 is integrated lithium ion battery silicon/charcoal cathode prepared by the present embodiment and is prepared with conventional lithium ion cathode
Cycle performance figure of the silicium cathode that technique obtains under 0.5C multiplying powers.Prepared integrated lithium ion battery silicon/charcoal cathode is straight
It connects and is assembled into button half-cell and is tested.In addition, being 6 according to nano-silicon, binder and conductive agent:2:2 ratio is in copper foil
Cut-parts are fabricated to negative electricity pole piece assembling button half-cell and are tested after upper coating rolling is dry, in this, as comparison.From Fig. 3
As can be seen that integrated lithium ion battery silicon/charcoal cathode prepared by the present embodiment is 0.5C (defining 1C=4200mA/g) times
Specific discharge capacity can still remain 1380mAh/g after being recycled under rate 200 times, and capacity retention ratio is up to 82%.And with tradition
Although capacity is close with integrated lithium ion battery silicon/charcoal cathode for the first time for the silicium cathode that lithium-ion negative pole preparation process obtains,
Capacity just decays to 0 after recycling several times.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. a kind of integration lithium ion battery silicon/carbon cathode material, it is characterised in that：Be using silica flour it is silicon source, pyrolytic carbon for charcoal
Matrix, nano-sized carbon are to enhance integrated lithium ion battery silicon/carbon cathode material of skeleton.
2. a kind of preparation method of integrated lithium ion battery silicon/carbon cathode material described in claim 1, it is characterised in that packet
Include following steps：
Step 1：Silica flour, binder and nano-sized carbon are mixed into the slurrying that is uniformly dispersed；
Step 2：By step 1 gained slurry coating, pole piece is made in drying on copper current collector；
Step 3：Step 2 gained pole piece is obtained into integrated lithium ion battery silicon/carbon cathode material after charing process.
3. preparation method according to claim 2, it is characterised in that：
In step 1, average grain diameter≤1 μm of the silica flour.
4. preparation method according to claim 2, it is characterised in that：
In step 1, the binder be Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyolefin, sodium carboxymethylcellulose,
Sodium alginate or rubber.
5. preparation method according to claim 2, it is characterised in that：
In step 1, the nano-sized carbon is carbon nanotube, graphene or carbon nano-fiber.
6. preparation method according to claim 2, it is characterised in that：
In step 1, the quality of the silica flour is the 50%~80% of silicon/carbon cathode material quality；Pyrolysis after binder charing
Carbon matrix quality is the 10%~50% of silicon/carbon cathode material quality；Nano-sized carbon quality is the 1% of silicon/carbon cathode material quality
~20%.
7. preparation method according to claim 2, it is characterised in that：
In step 2, the coating thickness of slurry is 25~500 μm.
8. preparation method according to claim 2, it is characterised in that：
In step 3, carbonization temperature is 500~900 DEG C, and processing time is 1~4h.
9. the preparation method according to claim 2 or 8, it is characterised in that：
In step 3, the atmosphere of charing process is nitrogen or argon gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378457A (en) * | 2018-10-16 | 2019-02-22 | 周昊宸 | A kind of high compacted density porous silicon chip/carbon compound cathode materials and preparation method |
| CN109546103A (en) * | 2018-10-25 | 2019-03-29 | 北京化工大学 | A kind of electrode material and its preparation method and application of binder as carbon precursor |
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| CN102013487A (en) * | 2010-10-29 | 2011-04-13 | 济南大学 | Carbon/silicon composite lithium ion battery negative material and preparation method thereof |
| CN103311522A (en) * | 2013-05-31 | 2013-09-18 | 中国科学院过程工程研究所 | Silicon/carbon composite microsphere negative electrode material as well as preparation method and application for same |
| US20140154578A1 (en) * | 2012-11-30 | 2014-06-05 | Lg Chem, Ltd. | Anode active material including porous silicon oxide-carbon material composite and method of preparing the same |
| CN104466096A (en) * | 2014-12-11 | 2015-03-25 | 江西先材纳米纤维科技有限公司 | Silicon negative electrode plate of lithium ion battery and preparation method of silicon negative electrode plate |
| CN104681797A (en) * | 2015-02-09 | 2015-06-03 | 江苏中兴派能电池有限公司 | Method for preparing silicon-carbon composite anode and lithium ion battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102013487A (en) * | 2010-10-29 | 2011-04-13 | 济南大学 | Carbon/silicon composite lithium ion battery negative material and preparation method thereof |
| US20140154578A1 (en) * | 2012-11-30 | 2014-06-05 | Lg Chem, Ltd. | Anode active material including porous silicon oxide-carbon material composite and method of preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109378457A (en) * | 2018-10-16 | 2019-02-22 | 周昊宸 | A kind of high compacted density porous silicon chip/carbon compound cathode materials and preparation method |
| CN109546103A (en) * | 2018-10-25 | 2019-03-29 | 北京化工大学 | A kind of electrode material and its preparation method and application of binder as carbon precursor |
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