CN108365191A - A kind of preparation method of silicon-carbon composite cathode material - Google Patents
A kind of preparation method of silicon-carbon composite cathode material Download PDFInfo
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- CN108365191A CN108365191A CN201810082104.XA CN201810082104A CN108365191A CN 108365191 A CN108365191 A CN 108365191A CN 201810082104 A CN201810082104 A CN 201810082104A CN 108365191 A CN108365191 A CN 108365191A
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- silicon
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- carbon composite
- cathode material
- composite cathode
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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
- 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
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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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 present invention relates to a kind of preparation methods of silicon-carbon composite cathode material, include the following steps：The water soluble polymer binder that 1 20wt% is added in S1 in deionized water is stirred and is dispersed into glue, and jitter time is 1 5h；The water-soluble polymer dispersant for the silica flour and 0.1 10wt% that 5 50wt% are added in S2 in glue is stirred dispersion, and jitter time is 5 for 24 hours；Solution after disperseing in step S2 is spray-dried by S3, the solid after drying is warming up to 100 300 DEG C, 0.5 5h of constant temperature, then be warming up to 500 1500 DEG C, Si-C composite material is obtained after 2 10h of high temperature cabonization.Negative material made from the preparation method can effectively inhibit the volume change in silicon charge and discharge process, improve cycle performance of battery.
Description
Technical field
The present invention relates to lithium ion battery negative material field, it particularly relates to a kind of silicon-carbon composite cathode material
Preparation method.
Background technology
In order to further develop and popularize electric vehicle, it is desirable that electric vehicle has course continuation mileage long, the spies such as safety height
Point, and commercialized carbon negative pole material theoretical specific capacity only has 375mAh/g at present, energy density is low；Intercalation potential is close
Lithium current potential, poor safety performance far can not meet requirement of the people to electric vehicle performance.
Silicon is one of the novel anode material of popular research instantly, is considered most potential replacement carbon material, because silicon
Energy density is high, and theoretical specific capacity is up to 4200mAh/g, is carbon material more than 10 times；The intercalation potential of silicon is higher than analysis lithium current potential,
It is safe.However silicon volume change during removal lithium embedded is huge, reaches as high as 300%, volume is not in charge and discharge process for silicon
Disconnected expansion and contraction, causes SEI films persistently to rupture, and electrolyte largely consumes, active material powder of detached etc., so as to cause following
Ring degradation, capacity are decayed rapidly, battery failure, these all significantly limit the large-scale commercial application of silicium cathode.
For the problems in the relevant technologies, currently no effective solution has been proposed.
Invention content
For above-mentioned technical problem in the related technology, the present invention proposes a kind of preparation side of silicon-carbon composite cathode material
Method can reduce silicium cathode volume change, improve silicium cathode cycle performance.
To realize the above-mentioned technical purpose, the technical proposal of the invention is realized in this way：
A kind of preparation method of silicon-carbon composite cathode material, includes the following steps：
The water soluble polymer binder that 1-20wt% is added in S1 in deionized water is stirred and is dispersed into glue, jitter time
For 1-5h；
The water-soluble polymer dispersant for the silica flour and 0.1-10wt% that 5-50wt% is added in glue in S2 is stirred dispersion,
Jitter time is 5-24h；
Solution after disperseing in step S2 is spray-dried by S3, the solid after drying is warming up to 100-300 DEG C, constant temperature
0.5-5h, then it is warming up to 500-1500 DEG C, obtain Si-C composite material after high temperature cabonization 2-10h.
Further, in step S1, the water soluble polymer binder is polyvinyl alcohol, vinyl acetate esters, gathers
It is one or more in urethane class, epoxies, phenolic, organic silicon, rubber, carboxymethyl cellulose.
Further, in step S2, the water-soluble polymer dispersant is one kind in acrylic compounds, maleic acid anhydride
Or it is a variety of.
Further, in step S2, the grain size of the silica flour is 0.1-50 μm.
Further, in step S3, heating rate when heating is 1-30 DEG C/min.
Further, in step S3, the high temperature cabonization atmosphere is nitrogen, argon gas, nitrogen hydrogen mixed gas, argon gas hydrogen
One kind in gas gaseous mixture.
Beneficial effects of the present invention：Preparation process of the present invention is simple, and solvent for use is deionized water, cheap, green
It is pollution-free, it is cost-effective without recycling, it is easy to industrialization；The Si-C composite material particles coat that the present invention prepares is uniform,
Sphericity is high, and cycle performance is excellent.
Description of the drawings
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the present invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the SEM figures of the Si-C composite material of embodiment 1；
Fig. 2 is the charging and discharging curve figure of the battery of the preparation of silicon carbon composite materials of embodiment 1；
Fig. 3 is the cyclic curve figure of the battery of the preparation of silicon carbon composite materials of embodiment 1.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained belong to what the present invention protected
Range.
A kind of preparation method of silicon-carbon composite cathode material, includes the following steps：
The water soluble polymer binder that 1-20wt% is added in S1 in deionized water is stirred and is dispersed into glue, jitter time
For 1-5h；
The water-soluble polymer dispersant for the silica flour and 0.1-10wt% that 5-50wt% is added in glue in S2 is stirred dispersion,
Jitter time is 5-24h；
Solution after disperseing in step S2 is spray-dried by S3, the solid after drying is warming up to 100-300 DEG C, constant temperature
0.5-5h, then it is warming up to 500-1500 DEG C, obtain Si-C composite material after high temperature cabonization 2-10h.
In one particular embodiment of the present invention, in step S1, the water soluble polymer binder is polyvinyl alcohol
Class, vinyl acetate esters, polyurethanes, epoxies, phenolic, organic silicon, rubber, one kind in carboxymethyl cellulose or
It is a variety of.
In one particular embodiment of the present invention, in step S2, the water-soluble polymer dispersant be acrylic compounds,
It is one or more in maleic acid anhydride.
In one particular embodiment of the present invention, in step S2, the grain size of the silica flour is 0.1-50 μm.
In one particular embodiment of the present invention, in step S3, heating rate when heating is 1-30 DEG C/min.
In one particular embodiment of the present invention, in step S3, the high temperature cabonization atmosphere is nitrogen, argon gas, nitrogen
One kind in gas hydrogen mixed gas, argon gas hydrogen mixed gas.
Embodiment 1
A kind of preparation method of silicon-carbon composite cathode material, step include：
The carboxymethyl cellulose of 5wt% is added in S1 in deionized water（CMC）It is stirred and is dispersed into glue, jitter time is
1h。
The silica flour of 0.5 μm of grain size of 10wt% is added in S2 in glue and the polyacrylic acid of 0.3wt% is stirred dispersion,
Jitter time is 10h.
The solution of step S2 is spray-dried by S3, under an argon atmosphere by the solid after drying with the speed of 3 DEG C/min
Rate is warming up to 100 DEG C, constant temperature 2h, then is warming up to 1000 DEG C with the rate of 5 DEG C/min, and silicon-carbon composite wood is obtained after high temperature cabonization 5h
Material.
Material obtained is transferred in glove box, is assembled at pole piece by batch mixing, coating, roll-in and dry backlash
Button half-cell carries out charge and discharge, charging/discharging voltage ranging from 0-3.0V, first charge-discharge song with the current density of 50mA/g
Line is as shown in Fig. 2, first discharge specific capacity 1012mAh/g, initial charge specific capacity 723mAh/g, coulombic efficiency 71.4% for the first time.
The results are shown in Figure 3 for its loop test, and the 110th circle capacity retention ratio 89.19% shows excellent cycle performance, this reality of Fig. 1
Apply the SEM figures of a Si-C composite material.
Embodiment 2
A kind of preparation method of silicon-carbon composite cathode material, step include：
The butadiene-styrene rubber of 5wt% is added in S1 in deionized water（SBR）It is stirred and is dispersed into glue, jitter time 1.5h.
The silica flour of 0.5 μm of grain size of 15wt% is added in S2 in glue and the polyacrylic acid of 0.5wt% is stirred dispersion,
Jitter time is 15h.
The solution of step S2 is spray-dried by S3, under an argon atmosphere by the solid after drying with the speed of 5 DEG C/min
Rate is warming up to 130 DEG C, constant temperature 3h, then is warming up to 1300 DEG C with the rate of 8 DEG C/min, and silicon-carbon composite wood is obtained after high temperature cabonization 7h
Material.
Embodiment 3
A kind of preparation method of silicon-carbon composite cathode material, step include：
The carboxymethyl cellulose of 2wt% is added in S1 in deionized water（CMC）With the butadiene-styrene rubber of 3wt%（SBR）It is stirred point
Dissipate into glue, jitter time 2h.
The silica flour of 0.5 μm of grain size of 20wt% is added in S2 in glue and the polyacrylic acid of 0.7wt% is stirred dispersion,
Jitter time is 20h.
The solution of step S2 is spray-dried by S3, under an argon atmosphere by the solid after drying with the speed of 7 DEG C/min
Rate is warming up to 150 DEG C, constant temperature 5h, then is warming up to 1500 DEG C with the rate of 10 DEG C/min, and it is compound to obtain silicon-carbon after high temperature cabonization 10h
Material.
The battery performance that embodiment 2, embodiment 3 obtain is similar to the battery performance of embodiment 1.
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
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (6)
1. a kind of preparation method of silicon-carbon composite cathode material, which is characterized in that include the following steps：
The water soluble polymer binder that 1-20wt% is added in S1 in deionized water is stirred and is dispersed into glue, jitter time
For 1-5h；
The water-soluble polymer dispersant for the silica flour and 0.1-10wt% that 5-50wt% is added in glue in S2 is stirred dispersion,
Jitter time is 5-24h；
Solution after disperseing in step S2 is spray-dried by S3, the solid after drying is warming up to 100-300 DEG C, constant temperature
0.5-5h, then it is warming up to 500-1500 DEG C, high temperature cabonization atmosphere is generated, obtaining silicon-carbon after 2-10h in high temperature cabonization atmosphere answers
Condensation material.
2. a kind of preparation method of silicon-carbon composite cathode material according to claim 1, which is characterized in that in step S1,
The water soluble polymer binder is polyvinyl alcohol, vinyl acetate esters, polyurethanes, epoxies, phenolic, organosilicon
It is one or more in class, rubber, carboxymethyl cellulose.
3. a kind of preparation method of silicon-carbon composite cathode material according to claim 1, which is characterized in that in step S2,
The water-soluble polymer dispersant is one or more in acrylic compounds, maleic acid anhydride.
4. a kind of preparation method of silicon-carbon composite cathode material according to claim 1, which is characterized in that in step S2,
The grain size of the silica flour is 0.1-50 μm.
5. a kind of preparation method of silicon-carbon composite cathode material according to claim 1, which is characterized in that in step S3,
Heating rate when heating is 1-30 DEG C/min.
6. a kind of preparation method of silicon-carbon composite cathode material according to claim 1, which is characterized in that in step S3,
The high temperature cabonization atmosphere is one kind in nitrogen, argon gas, nitrogen hydrogen mixed gas, argon gas hydrogen mixed gas.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810082104.XA CN108365191A (en) | 2018-01-29 | 2018-01-29 | A kind of preparation method of silicon-carbon composite cathode material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110854368A (en) * | 2019-11-21 | 2020-02-28 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode precursor material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110854368A (en) * | 2019-11-21 | 2020-02-28 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode precursor material and preparation method thereof |
| CN110854368B (en) * | 2019-11-21 | 2021-09-28 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode precursor material and preparation method thereof |
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Application publication date: 20180803 |