CN108550801A - A kind of silicon/copper/fibrous carbon/carbide composite material and preparation, application - Google Patents
A kind of silicon/copper/fibrous carbon/carbide composite material and preparation, application Download PDFInfo
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- CN108550801A CN108550801A CN201810140175.0A CN201810140175A CN108550801A CN 108550801 A CN108550801 A CN 108550801A CN 201810140175 A CN201810140175 A CN 201810140175A CN 108550801 A CN108550801 A CN 108550801A
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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
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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 present invention discloses a kind of silicon/copper/fibrous carbon/carbide composite material, and raw material includes：Silicon particle, fibrous carbon, copper powder and carbon compound.Invention additionally discloses the preparation methods of above-mentioned silicon/copper/fibrous carbon/carbide composite material.Invention additionally discloses a kind of negative electrode of lithium ion battery, including：Metal collector is coated on above-mentioned silicon/copper/fibrous carbon/carbide composite material in metal collector and the bonding conductive agent for being coated with the silicon/copper/fibrous carbon/carbide composite material.Invention additionally discloses a kind of lithium ion batteries, including above-mentioned negative electrode of lithium ion battery.In the present invention, silicon particle volume expansion in charge and discharge process is smaller, and copper particle and fibrous carbon, carbide construct good three dimensions conductive network, it improves the electronic conduction of silicium cathode and ionic conduction and alleviates volume expansion, make the present invention that there is preferable cycle performance, high rate performance and higher specific capacity.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of silicon/copper/fibrous carbon/carbide composite woods
Material and preparation method, the application in lithium ion battery.
Background technology
Lithium ion battery is academic due to having the advantages that energy ratio height, light weight, rated voltage are high, self-discharge rate is low etc.
Boundary and industrial circle research and application extensively.As other battery systems, lithium ion battery is mainly by positive electrode, cathode material
Material, diaphragm and four big critical material of electrolyte are constituted, and the performance of material directly affects the performance of lithium ion battery.
Negative material includes mainly lithium Intercalation material, Zinc-lithium alloy material and lithium metal etc. at present.But with society into
One step develops, and such as requirement of the electric vehicle in terms of power source, existing lithium-ion battery system is in price, safety, specific volume
Amount and power-performance, the plentiful etc. of raw material all need to be improved.Develop the material of higher performance and corresponding lithium
Ion battery is particularly important.
Silicium cathode has high energy density, abundant natural resources, is that very ideal next-generation lithium ion battery is negative
Pole material becomes the area research hot spot.Compared with ordinary graphite negative material, the specific discharge capacity of silicium cathode is about
4200mAh/g is ten times or so of lamellar graphite (372mAh/g).Therefore silicon is expected to become next-generation high-energy density energy storage material
With the cathode of the lithium ion battery of automotive powerplant.However the conductivity of silicium cathode material itself is low and volume expansion problem shadow
Ring its large-scale application.
Invention content
Technical problems based on background technology, it is compound that the present invention proposes a kind of silicon/copper/fibrous carbon/carbide
Material and preparation, application improve the electronic conduction of silicium cathode and ionic conduction and alleviate volume expansion, make silicon/copper/fiber
Shape carbon/carbide composite material has preferable cycle performance, high rate performance and higher specific capacity；Method is simply easily grasped simultaneously
Make, is suitable for industrialized production.
A kind of silicon/copper/fibrous carbon/carbide composite material proposed by the present invention, raw material include：Silicon particle, fiber
Shape carbon, copper powder and carbon compound.
Preferably, the grain size of silicon particle is 0.001~100 μm, preferably 30nm.
Preferably, fibrous carbon is that multi-walled carbon nanotube, single-walled carbon nanotube, vapor-grown carbon fibers are at least one, excellent
It is selected as multi-walled carbon nanotube.
Preferably, carbon compound is at least one in sucrose, glucose, phenolic resin, polyvinyl alcohol, polyethylene glycol
Kind, preferably glucose.
Preferably, the mass ratio of silicon particle and fibrous carbon is 20：1~1：20, preferably 2：1.
Preferably, the mass ratio of silicon particle and copper powder is 10：0~0：10, preferably 2：1.
Preferably, the ratio of silicon particle, fibrous carbon, the quality sum of copper powder and carbon compound quality is 10：1~1：
10, preferably 1：1.
The preparation method of above-mentioned silicon/copper/fibrous carbon/carbide composite material proposed by the present invention, by silicon particle and fibre
Dimension shape carbon, which is placed in solvent, to be uniformly dispersed, and adds copper powder and carbon compound continues to be uniformly dispersed, spray drying granulation is being protected
Calcining obtains silicon/copper/fibrous carbon/carbide composite material in shield atmosphere.
Above-mentioned calcination condition should determine corresponding parameter according to different carbon compounds.
Preferably, solvent is a kind of in water, ethyl alcohol, acetone, N-Methyl pyrrolidone, preferably water.
Preferably, protective atmosphere is argon gas.
A kind of negative electrode of lithium ion battery proposed by the present invention, including：Metal collector, be coated on it is upper in metal collector
State silicon/copper/fibrous carbon/carbide composite material and for being coated with above-mentioned silicon/copper/fibrous carbon/carbide composite material
Bind conductive agent.
Preferably, bonding conductive agent includes：Conductive agent, binder.
Preferably, conductive agent is acetylene black or carbon black conductive agent Super P.
Preferably, binder is 1 in mass ratio by carboxymethyl cellulose, butadiene-styrene rubber：1 is mixed to get.
Preferably, metal collector is fine copper or copper alloy.
The preparation method of above-mentioned negative electrode of lithium ion battery is as follows：By weight by 60-80 parts of above-mentioned silicon/copper/fibrous carbons/
Carbide composite material and 10-30 parts of conductive agent mixing, grinding obtain negative electrode active material powder；By negative electrode active material powder
Slurry is uniformly mixing to obtain with 10 parts of binders, be then coated in metal collector, 80 DEG C of vacuum drying 12-24h to obtain the final product.
Preferably, the thickness that slurry is applied to metal collector is 10-500 μm.
A kind of lithium ion battery proposed by the present invention, including to electrode lithium metal or common lithium ion cell positive, porous
Diaphragm, electrolyte further include above-mentioned negative electrode of lithium ion battery.
In the present invention, formed by spray drying by the strong nano copper particle of silicon nanoparticle, electric conductivity and fibrous carbon
Composite material, silicon particle volume expansion in charge and discharge process is smaller, and copper particle and fibrous carbon, carbide construct
Good three dimensions conductive network improves the electronic conduction of silicium cathode and ionic conduction and alleviates volume expansion, make silicon/
Copper/fibrous carbon/carbide composite material has preferable cycle performance, high rate performance and higher specific capacity；Method simultaneously
It is simple to operation, it is suitable for industrialized production.
Description of the drawings
Fig. 1 is that the SEM of 3 gained silicon of the embodiment of the present invention/copper/fibrous carbon/carbide composite material schemes.
Fig. 2 is the cycle performance comparison diagram of 1 gained lithium ion electronics of the embodiment of the present invention 3 and comparative example.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of silicon/copper/fibrous carbon/carbide composite material, by weight by 10 parts of 3 μm of silicon particles with
1 part of vapor-grown carbon fibers is placed in ethyl alcohol and is uniformly dispersed, and adds 1 part of copper powder and 120 parts of phenolic resin continue to be uniformly dispersed,
Spray drying granulation is calcined in protective atmosphere and obtains silicon/copper/fibrous carbon/carbide composite material.
Embodiment 2
A kind of preparation method of silicon/copper/fibrous carbon/carbide composite material, by weight by 1 part of 3nm silicon particle with
10 parts of single-walled carbon nanotubes are placed in N-Methyl pyrrolidone and are uniformly dispersed, add 10 parts of copper powders and 2.1 parts of polyvinyl alcohol after
Continuous to be uniformly dispersed, spray drying granulation is calcined in argon gas atmosphere and obtains silicon/copper/fibrous carbon/carbide composite material.
Embodiment 3
A kind of preparation method of silicon/copper/fibrous carbon/carbide composite material, by 2g 30nm silicon particles and 1g multi wall carbon
Nanotube is placed in mechanical agitation in 150mL water, and ultrasonic disperse is uniform, adds 1g copper nanoparticles and 4g glucose continues dispersion
Even, 180 DEG C of spray drying granulations are warming up to 120 DEG C, constant temperature 2h, then in argon gas atmosphere with the heating rate of 5 DEG C/min
With the heating rate of 5 DEG C/min, 580 DEG C, constant temperature 4h are warming up to, then with the heating rate of 5 DEG C/min, is warming up to 800 DEG C, perseverance
Warm 1h is down to room temperature and obtains silicon/copper/fibrous carbon/carbide composite material naturally.
A kind of preparation method of negative electrode of lithium ion battery, by the above-mentioned silicon/copper/fibrous carbon/carbide composite materials of 60g and
30g acetylene blacks ground and mixed uniformly obtains negative electrode active material powder；It is subsequently added into the mixing of 5g carboxymethyl cellulose binders, so
Deionized water is added dropwise afterwards and 5g butadiene-styrene rubber binders are uniformly mixing to obtain slurry, is then coated on slurry with automatic coating machine
In copper foil current collector, 80 DEG C of vacuum drying 12-24h obtain negative electrode of lithium ion battery.
Using above-mentioned negative electrode of lithium ion battery, lithium metal to electrode, electrolyte LiPF6- DMC/EMC/EC/FEC, and
Cegard2400 diaphragms, assemble lithium-ion button battery in the glove box full of argon gas.
Comparative example 1
Using the silicon materials of 30nm negative electrode of lithium ion battery and lithium ion battery are prepared by step same as Example 3.
Silicon/copper/fibrous carbon/carbide composite material, such as Fig. 1 as obtained by scanning electron microscope analysis embodiment 3
It is shown.As can be known from Fig. 1：The composite material is spheroidal material, and each substance of the composite material surface is evenly distributed.
At room temperature, difference testing example 3 and 1 gained button cell charge-discharge performance of comparative example, as shown in Figure 2.Its
Middle charging and discharging currents density is disposed as 200mA/g (by the Mass Calculation of gained composite material), and charge and discharge cycles 20 are enclosed, electric discharge
Blanking voltage is limited to 0.02-1.5V.
As shown in Figure 2：The performance of Si@Cu@fibrous carbon@C in silicon/copper/fibrous carbon/carbide composite material, that is, Fig. 2
It is substantially better than simple nano silicon material；The initial discharge capacity of silicon/copper/fibrous carbon/carbide composite material is
The capacity retention ratio of 1500mAh/g, 20 circles are 94.8%；Composite material has good skeleton and three-dimensional conductive network, to promote
Keep its cycle performance good.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of silicon/copper/fibrous carbon/carbide composite material, which is characterized in that its raw material includes：Silicon particle, threadiness
Carbon, copper powder and carbon compound.
2. silicon/copper/fibrous carbon/carbide composite material according to claim 1, which is characterized in that the grain size of silicon particle
It is 0.001~100 μm.
3. silicon/copper/fibrous carbon/carbide composite material according to claim 1 or claim 2, which is characterized in that fibrous carbon is
Multi-walled carbon nanotube, single-walled carbon nanotube, vapor-grown carbon fibers are at least one.
4. according to any one of the claim 1-3 silicon/copper/fibrous carbon/carbide composite materials, which is characterized in that carbon containing
Compound is at least one of sucrose, glucose, phenolic resin, polyvinyl alcohol, polyethylene glycol.
5. according to any one of the claim 1-4 silicon/copper/fibrous carbon/carbide composite materials, which is characterized in that silicon
The mass ratio of grain and fibrous carbon is 20：1~1：20；Preferably, the mass ratio of silicon particle and copper powder is 10：0~0：10；It is preferred that
Ground, silicon particle, fibrous carbon, the quality sum of copper powder and carbon compound quality ratio be 10：1~1：10.
6. a kind of preparation method of silicon/copper/fibrous carbon/carbide composite material as described in claim any one of 1-5, special
Sign is, silicon particle is placed in fibrous carbon in solvent and is uniformly dispersed, and adds copper powder and carbon compound continues dispersion
Even, spray drying granulation is calcined in protective atmosphere and obtains silicon/copper/fibrous carbon/carbide composite material.
7. the preparation method of silicon/copper/fibrous carbon/carbide composite material according to claim 6, which is characterized in that molten
Agent is a kind of in water, ethyl alcohol, acetone, N-Methyl pyrrolidone；Preferably, protective atmosphere is argon gas.
8. a kind of negative electrode of lithium ion battery, which is characterized in that including：Metal collector, be coated in metal collector as power
Profit require any one of 1-5 silicon/copper/fibrous carbon/carbide composite materials and for be coated with the silicon/copper/fibrous carbon/
The bonding conductive agent of carbide composite material.
9. negative electrode of lithium ion battery according to claim 8, which is characterized in that metal collector is fine copper or copper alloy.
10. a kind of lithium ion battery, including to electrode lithium metal or common lithium ion cell positive, porous septum, electrolyte,
It is characterized in that, further includes the negative electrode of lithium ion battery of claim 8 or 9.
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Citations (6)
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| CN105161695A (en) * | 2015-06-12 | 2015-12-16 | 南通彩都新能源科技有限公司 | Spherical active material particles for lithium ion battery negative electrode, preparation method and application of spherical active material particles |
| CN105406050A (en) * | 2015-12-31 | 2016-03-16 | 深圳市贝特瑞新能源材料股份有限公司 | Composite silicon negative electrode material, and preparation method and application thereof |
| CN105489839A (en) * | 2014-09-18 | 2016-04-13 | 微宏动力系统（湖州）有限公司 | Copper-silicon negative electrode and preparation method therefor |
| CN105810921A (en) * | 2016-06-06 | 2016-07-27 | 田东 | Preparation method of tin-based cathode material of high-capacity lithium-ion battery |
| WO2017024720A1 (en) * | 2015-08-07 | 2017-02-16 | 田东 | Preparation method for high capacity lithium-ion battery negative electrode material |
| CN107170962A (en) * | 2017-04-17 | 2017-09-15 | 厦门高容新能源科技有限公司 | A kind of lithium ion battery silicium cathode electrode slice and preparation method thereof |
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2018
- 2018-02-11 CN CN201810140175.0A patent/CN108550801A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489839A (en) * | 2014-09-18 | 2016-04-13 | 微宏动力系统（湖州）有限公司 | Copper-silicon negative electrode and preparation method therefor |
| CN105161695A (en) * | 2015-06-12 | 2015-12-16 | 南通彩都新能源科技有限公司 | Spherical active material particles for lithium ion battery negative electrode, preparation method and application of spherical active material particles |
| WO2017024720A1 (en) * | 2015-08-07 | 2017-02-16 | 田东 | Preparation method for high capacity lithium-ion battery negative electrode material |
| CN105406050A (en) * | 2015-12-31 | 2016-03-16 | 深圳市贝特瑞新能源材料股份有限公司 | Composite silicon negative electrode material, and preparation method and application thereof |
| CN105810921A (en) * | 2016-06-06 | 2016-07-27 | 田东 | Preparation method of tin-based cathode material of high-capacity lithium-ion battery |
| CN107170962A (en) * | 2017-04-17 | 2017-09-15 | 厦门高容新能源科技有限公司 | A kind of lithium ion battery silicium cathode electrode slice and preparation method thereof |
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Application publication date: 20180918 |