CN106784698A - Si/SiC/C composites and preparation method and lithium ion battery negative and battery - Google Patents
Si/SiC/C composites and preparation method and lithium ion battery negative and battery Download PDFInfo
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Abstract
Si/SiC/C composites of the present invention and preparation method and lithium ion battery negative and battery are related to a kind of composite for lithium ion battery, its preparation method and lithium ion battery negative and lithium ion battery comprising the composite.Its purpose is to provide a kind of Si/SiC/C composites and preparation method and lithium ion battery negative and battery, nano Si and SiC in composite are dispersed on graphite and particle between, preparation method is a kind of electrochemical method, there is good cycle performance using the lithium ion battery negative of composite, the energy density of battery is improved.Si/SiC/C composites in the present invention include graphite and the nano Si and nano SiC that are dispersed between its surface and particle, and the weight/mass percentage composition of nano SiC is 1~50%.Electrochemical preparation method present invention additionally comprises above-mentioned composite and the lithium ion battery negative and lithium ion battery using the composite.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of composite for lithium ion battery,
The preparation method of the composite and lithium ion battery negative and lithium ion battery comprising the composite.
Background technology
Development high-energy-density electrokinetic cell, improves pure electric automobile continual mileage, expands electric automobile range of application, is
Break through the key point of ev industry development bottleneck.It is to lift battery energy density most using the electrode material of height ratio capacity
Simple effective method.The theoretical specific volume of the negative material mainly carbons material that commercially uses, but carbons negative material at present
Amount closely its theoretical capacity (372mAh/g), battery performance is improved by improving battery preparation technique and has been difficult to take
Breakthrough is obtained, therefore the negative material of research and development height ratio capacity of new generation is just particularly urgent.The gold such as Si, Sn, Al and Sb
Category is that people study more high-capacity cathode materials, and wherein silicon has higher than now widely used carbon material more than 10 times
Theoretical electrochemistry capacity (theoretical capacity 4200mAh/g), it is considered to be very promising energy-density lithium ion battery negative pole material
Material.The subject matter that it is present is that volume occurs significant change (volume change in de-, process of intercalation：280%-360%),
The destruction and mechanical efflorescence of material structure are caused, between causing electrode material and electrode material is separated with collector, and then is lost
Electrical contact, causes capacity to be decayed rapidly.Therefore, how to improve the cyclical stability of silicium cathode, be allowed to tend to practical as this
The research emphasis of class material.
In order to improve the cycle performance of silicium cathode material, researcher takes many kinds of measures.It is to improve by silicon nanosizing
One of approach of silicium cathode stability.Nano material has that specific surface area is big, ion diffusion path is short, wriggling strong and plasticity
High the features such as, can to a certain extent alleviate the bulk effect of silicium cathode material, and improve its chemical property, but nanometer
Material is easily reunited in cyclic process, is insufficient to allow the performance improvement of battery to practical.Another effective method is exactly
Siliceous composite is prepared into, using the cooperative effect between composite each component, the purpose of mutual supplement with each other's advantages is reached.Research table
It is bright, nano SiC material is added in Si negative poles, nano SiC material has mechanical strength higher, can alleviate Si negative poles and exist
Destruction of the internal stress that volumetric expansion during embedding de- lithium is produced to electrode structure, improves the mechanical property of Si negative poles, thus
Improve the cycle performance of silicon electrode.Nano-silicone wire/carbon composite material is prepared for using electrochemical process in patent CN103107315A, should
Composite also comprising being dispersed in the nanometer silicon carbide of matrix carbon and nano-silicon interface, the content of nanometer silicon carbide for 0.1~
The cycle performance of silicon electrode improves limited in 3%, but the patent.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of Si/SiC/C composites and preparation method and lithium ion
GND and battery, nano Si and SiC in the composite are interdependent and give birth to, contact fully, nano Si and SiC material are equal
Even to be dispersed on graphite and graphite particle between, described preparation method is that a kind of pollution-free, raw material is easy to get, equipment is cheap, easy
In the electrochemical method of continuous production Si/SiC/C composites, had using the lithium ion battery negative of the composite fine
Cycle performance, so as to improve the energy density of lithium ion battery.
Si/SiC/C composites in the present invention, including graphite and be dispersed in interdependent between graphite surface and graphite particle
And raw nano Si and the weight/mass percentage composition of nano SiC described in nano SiC is 1~50%.
Si/SiC/C composites in the present invention, wherein the weight/mass percentage composition of the nano Si is 1~50%.
Si/SiC/C composites in the present invention, wherein the weight/mass percentage composition of the graphite is 5~80%.
Si/SiC/C composites in the present invention, wherein the composite is also coated on nano Si and nanometer
Si oxide SiO in surface of SiCX, wherein 0 ＜ X≤2, the SiOXWeight/mass percentage composition be less than 10%.
Si/SiC/C composites in the present invention, wherein the SiOXWeight/mass percentage composition be less than 5%.
Si/SiC/C composites in the present invention, wherein the existence form of the nano Si is nano wire, nanometer rods, receives
At least one in mitron and nano particle.
Si/SiC/C composites in the present invention, wherein the existence form of the nano SiC is nano wire, nanometer
At least one in grain, nanometer rods, nanotube and nanometer sheet.
Si/SiC/C composites in the present invention, wherein the graphite is native graphite, Delanium and electrically conductive graphite
In at least one.
Si/SiC/C composites in the present invention, wherein the graphite be shaped as sheet, it is spherical, spherical it is block,
At least one in wire and tubulose.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, comprises the following steps：
Using Si oxide/amorphous compound porous block materials of carbon graphite and conductive cathode collector bluk recombination as the moon
Pole,
Anode is set,
The negative electrode and anode are placed in the electrolyte comprising metallic compound fused salt,
Applied voltage, is electrolysed under inert atmosphere between a cathode and an anode, and Si/SiC/C composites are obtained in negative electrode.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, wherein the Si oxide is SiOx, its
In 0 ＜ X≤2.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, wherein the Si oxide/amorphous carbon/
Silicon atom and the mol ratio of cracking carbon atom are 1.0~10 in the compound porous block materials of graphite,
The electrochemical preparation method of the Si/SiC/C composites in the present invention, wherein described comprising metallic compound fused salt
Electrolyte in the molecular formula of metallic compound be MY, wherein M refers to Ca, Ba, Li, Al, Cs, Na, K or Sr, and Y is Cl or F,
The electrochemical preparation method of the Si/SiC/C composites in the present invention, wherein described comprising metallic compound fused salt
Electrolyte refer to one or more electrolytic salt,
The electrochemical preparation method of the Si/SiC/C composites in the present invention, wherein being electrolysed the temperature at 500-1000 DEG C
Under carry out.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, the voltage for applying between a cathode and an anode
Less than 3.2V.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, the voltage for applying between a cathode and an anode
Less than the decomposition voltage of electrolyte.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, the voltage for applying between a cathode and an anode
Higher than the decomposition voltage of Si oxide.
Lithium ion battery negative in the present invention, above-mentioned Si/SiC/C composites are carried out with conductive carbon and binding agent
Mixing, and the mixture that will be obtained is coated on support conducting base the lithium ion battery negative described in being formed.
Lithium ion battery in the present invention, by above-mentioned lithium ion battery negative negative electrode, barrier film, the electrolyte compatible with electricity
It is placed in container and forms described lithium ion battery.
The advantage of the invention is that：It is in situ with graphite using the generated in-situ nano Si of electrochemical process and nano SiC material
Compound, wherein nano SiC is interdependent with nano Si material and give birth to, and is fully contacted, and be dispersed in graphite surface and graphite particle
Between.SiC nanowire is produced due to that with mechanical strength higher, can alleviate volumetric expansion of the Si negative poles during embedding de- lithium
Destruction of the raw internal stress to electrode structure, improves the mechanical property of Si negative poles；Graphite can improve the electric conductivity of Si negative poles,
The internal stress that volumetric expansion is produced during the embedding de- lithium of simultaneous buffering Si negative poles, thus improve the cycle performance of Si electrodes, so that
Improve the energy density of lithium ion battery.The preparation method of the Si/SiC/C composites is environment-friendly, raw material is easy to get, equipment
Cheaply, it is easy to continuous production.
The invention will be further described below in conjunction with the accompanying drawings.
Brief description of the drawings
Fig. 1 amplifies 10000 times of SEM figures for the nano Si/SiC/C composites of the embodiment of the present invention 4；
Fig. 2 amplifies 50000 times of SEM figures for the nano Si/SiC/C composites of the embodiment of the present invention 4；
Fig. 3 is the XRD of the nano Si/SiC/C composites of the embodiment of the present invention 4.
Specific embodiment
Si/SiC/C composites in the present invention, including graphite and be dispersed in interdependent between graphite surface and graphite particle
And raw nano Si and nano SiC, the weight/mass percentage composition of the graphite is 5~80%, and the quality percentage of the nano Si contains
It is 1~50% to measure, and the weight/mass percentage composition of the nano SiC is 1~50%.
Si/SiC/C composites in the present invention, wherein the composite is also coated on nano Si and nanometer
Si oxide SiO in surface of SiCX, wherein 0 ＜ X≤2, the SiOXWeight/mass percentage composition be less than 5%.Due to composite
Meeting and air contact, therefore nano Si and nano SiC surface can be oxidized, and produce one layer of Si oxide.
The existence form of the nano Si is at least one in nano wire, nanometer rods, nanotube and nano particle, described
The existence form of nano SiC is at least one in nano wire, nano particle, nanometer rods, nanotube and nanometer sheet, the graphite
Be at least one in native graphite, Delanium and electrically conductive graphite, the graphite be shaped as sheet, spherical, spherical piece
At least one in shape, wire and tubulose.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, comprises the following steps：
Using Si oxide/amorphous compound porous block materials of carbon graphite and conductive cathode collector bluk recombination as the moon
Pole,
Anode is set,
The negative electrode and anode are placed in the electrolyte comprising metallic compound fused salt,
Applied voltage, is electrolysed under inert atmosphere between a cathode and an anode, and Si/SiC/C composites are obtained in negative electrode.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, the Si oxide is SiOx, wherein 0 ＜
X≤2, silicon atom is with the mol ratio of cracking carbon atom in the Si oxide/amorphous compound porous block materials of carbon graphite
1.0~10, the molecular formula of the metallic compound in the electrolyte comprising metallic compound fused salt is MY, wherein M refer to Ca,
Ba, Li, Al, Cs, Na, K or Sr, Y are Cl or F, and the electrolyte comprising metallic compound fused salt refers to one or more electricity
Solution matter salt, electrolysis is carried out at a temperature of 500-1000 DEG C.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, the voltage for applying between a cathode and an anode
Less than 3.2V.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, the voltage for applying between a cathode and an anode
Less than the decomposition voltage of electrolyte.
The electrochemical preparation method of the Si/SiC/C composites in the present invention, the voltage for applying between a cathode and an anode
Higher than the decomposition voltage of Si oxide.
Lithium ion battery negative in the present invention, above-mentioned Si/SiC/C composites are carried out with conductive carbon and binding agent
Mixing, and the mixture that will be obtained is coated on support conducting base the lithium ion battery negative described in being formed.
Lithium ion battery in the present invention, by above-mentioned lithium ion battery negative negative electrode, barrier film, the electrolyte compatible with electricity
It is placed in container and forms described lithium ion battery.
The advantage of the invention is that：It is in situ with graphite using the generated in-situ nano Si of electrochemical process and nano SiC material
Compound, wherein nano SiC is interdependent with nano Si material and give birth to, and is fully contacted, and be dispersed in graphite surface and graphite particle
Between.SiC nanowire is produced due to that with mechanical strength higher, can alleviate volumetric expansion of the Si negative poles during embedding de- lithium
Destruction of the raw internal stress to electrode structure, improves the mechanical property of Si negative poles；Graphite can improve the electric conductivity of Si negative poles,
The internal stress that volumetric expansion is produced during the embedding de- lithium of simultaneous buffering Si negative poles, thus improve the cycle performance of Si electrodes, so that
Improve the energy density of lithium ion battery.The preparation method of the Si/SiC/C composites is environment-friendly, raw material is easy to get, equipment
Cheaply, it is easy to continuous production.
The present invention is described in further detail with embodiment below.
Embodiment 1
It is 2 by silicon, amorphous carbon mol ratio:1 weighs the silica and amorphous carbon of certain mass, then weighs a certain amount of
Graphite (quality of graphite accounts for 50%, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, is obtained
SiO2/ amorphous carbon/C porous electrodes, by SiO2/ amorphous carbon/C porous electrodes and conductive cathode afflux bluk recombination as negative electrode,
With graphite rod as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 900 DEG C, and electricity is controlled with voltage-stablizer
Pressure carries out constant-potential electrolysis, and tank voltage is 2.5V, electrolysis time 16h, soak electrolysate with watery hydrochloric acid successively after the completion of electrolysis,
The cleaning of deionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC/C composites, and composite is by straight
Footpath is 3~20 μm of graphite flake and the silicon nanometer of a diameter of 30~100nm being dispersed between graphite flake surface and graphite flake
The silicon carbide nanometer line of grain and a diameter of 10~50nm, rod composition.
Embodiment 2
It is 3 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of graphite
(quality of graphite accounts for 50%, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, obtains SiO2/
Amorphous carbon/C porous electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 900 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 7h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC/C composites, and composite is by diameter
For 3~20 μm of graphite flakes and a diameter of 30~100nm being dispersed between graphite flake surface and graphite flake nano silicon particles,
The silicon carbide nanometer line of rod and a diameter of 10~50nm, particle, rod composition.
Embodiment 3
It is 4 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of graphite
(quality of graphite accounts for 50%, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, obtains porous
SiO2/ amorphous carbon/C electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 900 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 8h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC/C composites, and composite is by diameter
For 3~20 μm of graphite flakes and a diameter of 30~150nm being dispersed between graphite flake surface and graphite flake silicon nanorod,
The silicon carbide nanometer line of grain and a diameter of 10~50nm, rod, particle composition.
Embodiment 4
It is 5 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of graphite
(quality of graphite accounts for 50%, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, obtains SiO2/
Amorphous carbon/C porous electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 900 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 9h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain composite, and the composition to composite is carried out
Characterize, its XRD (see Fig. 3) display composite is made up of Si, SiC and C, and as shown in Figure 1, 2, composite is by a diameter of 3
Silicon nanorod, the particle of~20 μm of graphite flake and a diameter of 30~200nm being dispersed between graphite flake surface and graphite flake
And silicon carbide nanometer line, the rod composition of a diameter of 10~50nm.
Embodiment 5
It is 6 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of graphite
(quality of graphite accounts for 50%, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, obtains SiO2/
Amorphous carbon/C porous electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 900 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 10h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC/C composites, and composite is by diameter
For 3~20 μm of graphite flakes and a diameter of 30~300nm being dispersed between graphite flake surface and graphite flake silicon nanorod,
The silicon carbide nano bar of grain and a diameter of 10~50nm, particle composition.
Embodiment 6
It is 10 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of stone
(quality of graphite accounts for 50% to ink, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, obtains porous
SiO2/ amorphous carbon/C electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 900 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 12h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC/C composites, and composite is by diameter
For 3~20 μm of graphite flakes and a diameter of 30~500nm being dispersed between graphite flake surface and graphite flake silicon nanorod,
The silicon carbide nano bar of grain and a diameter of 10~50nm, particle composition.
Embodiment 7
It is 5 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of graphite
(quality of graphite accounts for 40%, and silica is accounted for the quality of amorphous carbon and 60%) is well mixed, compressing, obtains SiO2/
Amorphous carbon/C porous electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 900 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 20h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC composites, and composite is by a diameter of 3
Silicon nanorod, the particle of~20 μm of graphite flake and a diameter of 30~200nm being dispersed between graphite flake surface and graphite flake
And silicon carbide nano bar, the particle composition of a diameter of 10~50nm.
Embodiment 8
It is 5 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of graphite
(quality of graphite accounts for 50%, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, obtains SiO2/
Amorphous carbon/C porous electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 950 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 16h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC/C composites, and composite is by diameter
For 3~20 μm of graphite flakes and a diameter of 30~200nm being dispersed between graphite flake surface and graphite flake silicon nanorod,
The silicon carbide nanometer line of grain and a diameter of 10~50nm, rod composition.
Embodiment 9
It is 5 by silicon, amorphous carbon mol ratio:1 weighs the silica and carbon of certain mass, then weighs a certain amount of graphite
(quality of graphite accounts for 50%, and silica is accounted for the quality of amorphous carbon and 50%) is well mixed, compressing, obtains SiO2/
Amorphous carbon/C porous electrodes, by SiO2/ amorphous carbon/C porous electrodes and the bluk recombination of conductive cathode afflux as negative electrode, with stone
Inker as anode, to melt CaCl2It is electrolyte, in the environment of argon gas, temperature is 850 DEG C, uses voltage-stablizer control voltage
Constant-potential electrolysis is carried out, tank voltage is 2.5V, electrolysis time 16h, electrolysate is soaked with watery hydrochloric acid successively after the completion of electrolysis, is gone
The cleaning of ionized water suction filtration, the cleaning of absolute ethyl alcohol suction filtration, vacuum drying obtain Si/SiC/C composites, and composite is by diameter
For 3~20 μm of graphite flakes and a diameter of 10~200nm being dispersed between graphite flake surface and graphite flake silicon nanorod,
The silicon carbide nanometer line of grain and a diameter of 5~50nm, rod composition.
Embodiment 10
Novel nano Si/SiC/C composites and the conductive agent (S-p) that to be prepared in embodiment 4, binding agent (PVDF) with
80%:10%:10% (weight ratio) mixes, and adds NMP, is placed in and is made anode sizing agent, is then applied in copper foil current collector, made
The pole piece coating layer thickness for obtaining is 90 microns, by pole piece roll-in to 65 microns, with above-mentioned pole piece as negative electrode, and with Li as anode, barrier film
The selection films of Celgard 2400, electrolyte is LiPF6 bases electrolyte (LiPF6-EC/DMC/EMC of 1mol/L, 1:1:1
(vol%)).Battery is assembled into glove box, open-circuit voltage is measured for 2.85V.
The battery of above-mentioned preparation is carried out into charge-discharge performance test at room temperature, limitation voltage is 0.005V~2.0V, electricity
Current density is 80mA/g (0.1C), and the discharge capacity first of battery reaches 795.7mAh/g, hence it is evident that higher than putting first for comparative example
Capacitance.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to model of the invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical side of the invention
Various modifications and improvement that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (20)
1. a kind of Si/SiC/C composites, it is characterised in that：Including graphite and it is dispersed between graphite surface and graphite particle
Interdependent and raw nano Si and nano SiC, the weight/mass percentage composition of the nano SiC is 1~50%.
2. Si/SiC/C composites according to claim 1, it is characterised in that：The weight/mass percentage composition of the nano Si
It is 1~50%.
3. Si/SiC/C composites according to claim 1 and 2, it is characterised in that：The quality percentage of the graphite contains
Measure is 5~80%.
4. Si/SiC/C composites according to claim 3, it is characterised in that：The composite is also coated on
Si oxide SiO on nano Si and nano SiC surfaceX, wherein 0 ＜ X≤2, the SiOXWeight/mass percentage composition be less than
10%.
5. Si/SiC/C composites according to claim 4, it is characterised in that：The SiOXWeight/mass percentage composition it is small
In 5%.
6. Si/SiC/C composites according to claim 5, it is characterised in that：The existence form of the nano Si is to receive
At least one in rice noodles, nanometer rods, nanotube and nano particle.
7. Si/SiC/C composites according to claim 6, it is characterised in that：The existence form of the nano SiC is
At least one in nano wire, nano particle, nanometer rods, nanotube and nanometer sheet.
8. Si/SiC/C composites according to claim 7, it is characterised in that：The graphite is native graphite, artificial
At least one in graphite and electrically conductive graphite.
9. Si/SiC/C composites according to claim 8, it is characterised in that：The graphite is shaped as sheet, ball
At least one in shape, spherical block, wire and tubulose.
10. a kind of electrochemical preparation method of Si/SiC/C composites, it is characterised in that comprise the following steps：
Using Si oxide/amorphous compound porous block materials of carbon graphite with conductive cathode collector bluk recombination as negative electrode,
Anode is set,
The negative electrode and anode are placed in the electrolyte comprising metallic compound fused salt,
Applied voltage, is electrolysed under inert atmosphere between a cathode and an anode, and Si/SiC/C composites are obtained in negative electrode.
The electrochemical preparation method of 11. Si/SiC/C composites according to claim 10, it is characterised in that：The silicon
Oxide is SiOx, wherein 0 ＜ X≤2.
The electrochemical preparation method of the 12. Si/SiC/C composites according to claim 10 or 11, it is characterised in that：Institute
State the mol ratio of silicon atom and cracking carbon atom in Si oxide/amorphous compound porous block materials of carbon graphite for 1.0~
10。
The electrochemical preparation method of 13. Si/SiC/C composites according to claim 12, it is characterised in that：The bag
The molecular formula of the metallic compound in the electrolyte of metal-containing compound fused salt be MY, wherein M refer to Ca, Ba, Li, Al, Cs,
Na, K or Sr, Y are Cl or F.
The electrochemical preparation method of 14. Si/SiC/C composites according to claim 13, it is characterised in that：The bag
The electrolyte of metal-containing compound fused salt refers to one or more electrolytic salt.
The electrochemical preparation method of 15. Si/SiC/C composites according to claim 14, it is characterised in that：Electrolysis exists
Carried out at a temperature of 500-1000 DEG C.
The electrochemical preparation method of 16. Si/SiC/C composites according to claim 15, it is characterised in that：In negative electrode
The voltage applied and anode between is less than 3.2V.
The electrochemical preparation method of 17. Si/SiC/C composites according to claim 15, it is characterised in that：In negative electrode
Decomposition voltage of the voltage applied and anode between less than electrolyte.
The electrochemical preparation method of 18. Si/SiC/C composites according to claim 15, it is characterised in that：In negative electrode
Decomposition voltage of the voltage applied and anode between higher than Si oxide.
A kind of 19. lithium ion battery negatives, it is characterised in that：Si/SiC/C described in claim 1-9 any one is combined
Material is mixed with conductive carbon and binding agent, and the mixture that will be obtained is coated on support conducting base and forms described lithium
Ion battery negative pole.
A kind of 20. lithium ion batteries, it is characterised in that：By the moon compatible with electricity of the lithium ion battery negative described in claim 19
Pole, barrier film, electrolyte are placed in container and form described lithium ion battery.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108717975A (en) * | 2018-08-14 | 2018-10-30 | 银隆新能源股份有限公司 | A kind of preparation method of negative material, battery and its negative material |
| CN110571426A (en) * | 2019-09-10 | 2019-12-13 | 石家庄尚太科技有限公司 | Nitrogen-doped silicon-carbon composite negative electrode material and preparation method thereof |
| CN112687853A (en) * | 2020-12-10 | 2021-04-20 | 安普瑞斯（南京）有限公司 | Silica particle aggregate, preparation method thereof, negative electrode material and battery |
| CN114702036A (en) * | 2022-05-06 | 2022-07-05 | 台州学院 | Preparation method of Si/SiC/C in-situ nano composite micro spindle material |
| CN114843511A (en) * | 2021-02-02 | 2022-08-02 | 恒大新能源技术(深圳)有限公司 | Silicon-graphite composite negative electrode material, negative plate and secondary battery |
| CN115312780A (en) * | 2022-10-10 | 2022-11-08 | 宁德新能源科技有限公司 | Negative electrode material, secondary battery, and electronic device |
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| CN103107315A (en) * | 2011-11-10 | 2013-05-15 | 北京有色金属研究总院 | Nano silicon-carbon composite material and preparation method thereof |
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| CN103107315A (en) * | 2011-11-10 | 2013-05-15 | 北京有色金属研究总院 | Nano silicon-carbon composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108717975A (en) * | 2018-08-14 | 2018-10-30 | 银隆新能源股份有限公司 | A kind of preparation method of negative material, battery and its negative material |
| CN110571426A (en) * | 2019-09-10 | 2019-12-13 | 石家庄尚太科技有限公司 | Nitrogen-doped silicon-carbon composite negative electrode material and preparation method thereof |
| CN112687853A (en) * | 2020-12-10 | 2021-04-20 | 安普瑞斯（南京）有限公司 | Silica particle aggregate, preparation method thereof, negative electrode material and battery |
| CN114843511A (en) * | 2021-02-02 | 2022-08-02 | 恒大新能源技术(深圳)有限公司 | Silicon-graphite composite negative electrode material, negative plate and secondary battery |
| CN114702036A (en) * | 2022-05-06 | 2022-07-05 | 台州学院 | Preparation method of Si/SiC/C in-situ nano composite micro spindle material |
| CN114702036B (en) * | 2022-05-06 | 2023-03-21 | 台州学院 | Preparation method of Si/SiC/C in-situ nano composite micro spindle material |
| CN115312780A (en) * | 2022-10-10 | 2022-11-08 | 宁德新能源科技有限公司 | Negative electrode material, secondary battery, and electronic device |
| CN117174848A (en) * | 2023-05-17 | 2023-12-05 | 渤海大学 | Preparation method and application of pomegranate seed-shaped nanocomposite for potassium ion battery |
| CN117174848B (en) * | 2023-05-17 | 2024-04-02 | 渤海大学 | Preparation method and application of pomegranate seed-shaped nanocomposite for potassium ion battery |
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