CN107994218A - A kind of Si-C composite material, its preparation method and its application as lithium ion battery negative material - Google Patents
A kind of Si-C composite material, its preparation method and its application as lithium ion battery negative material Download PDFInfo
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Abstract
The present invention relates to a kind of Si-C composite material, its preparation method and its application as lithium ion battery negative material.The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, its specific preparation method is using the carbon for first generating one layer of transition zone in substrate using vapour deposition, then is deposited to obtain again on transition carbon-coating, the beneficial effects of the present invention are：Si-C composite material of the present invention is composed of multiple nano-scale particles, and the mechanical strength and toughness having had, can effectively mitigate coming off due to active material caused by the volumetric expansion of silicon.Without using binding agent, avoiding the electrode performance that binding agent denaturation and binding agent are brought in itself reduces electrode material prepared by the method provided at the same time in the present invention.Using organosilicon as silicon source, can to avoid using SiH4 and caused by security risk；Also without using hydrofluoric acid treatment, whole process does not have poisonous waste generation, realizes green production.
Description
Technical field
The invention belongs to the preparing technical field of nano material, more particularly to a kind of Si-C composite material, its preparation
Method and its application as lithium ion battery negative material.
Background technology
With global warming caused by greenhouse effects, the whole society is higher and higher to the attention rate of environment.At the same time, it is economical
Development it is increasing to the demand of the energy, and on the one hand belong to can not be again for the fossil energy such as traditional oil, coal, natural gas
Serious environmental problem is brought in production-goods source, on the other hand, their use, promotes people's urgent need exploitation renewable energy
Source, to meet economic, society and the sustainable development of environment.
Lithium ion battery is due to the advantages that with bigger than energy, operating voltage is high, and security is good, and environmental pollution is small, each
Kind portable electric appts, the field such as electric automobile and new energy storage have broad application prospects.It is, in general, that negative material
As the main body of lithium ion battery storage lithium, the insertion and abjection of lithium ion are realized in charge and discharge process, is to improve lithium-ion electric
The key of the correlated performances such as pond specific capacity, cyclicity, discharge and recharge.Current commercialized negative material is mainly based on graphite
Traditional carbon material, and the specific capacity of graphite theory only has 372mAh/g, this largely limits the total specific volume of lithium ion battery
Amount further improves.Therefore, the negative material with height ratio capacity of Development of Novel is very urgent.
Silicon is considered as most potential cathode material for high capacity lithium ion battery of new generation, with traditional graphite cathode material
Material is compared, and silicon has more than ten times that high specific discharge capacity (4200mAh/g) is native graphite.Heap of the silicon in alloy material
Product density is close with lithium, therefore silicon also has very high volume and capacity ratio；Different from graphite type material, the height ratio capacity of silicon comes from
The alloying process of silicon lithium, thus silicium cathode material will not occur solvent with electrolyte and be embedded in altogether, and then electrolyte is applicable in
Scope is wider；Compared to Carbon Materials, silicon has the removal lithium embedded current potential of higher, can effectively avoid the analysis of lithium during high rate charge-discharge
Go out, it is possible to increase the security of battery.But due to the volumetric expansion of silicon, in charge and discharge process its can be made destructurized, made
Active material comes off from collector, and constantly forms irreversible dielectric film, ultimately results in the low reversible appearance of silicium cathode material
The cyclical stability and high rate performance of amount, difference.Silicon-carbon composite nanostructure is to suppress a kind of very effective approach of volumetric expansion.
This is primarily due to that carbon material electric conductivity is good, volume change is small.After silicon materials are wrapped by, can reinforcing material electric conductivity
Can, the reunion between nano silicon particles and the expansion of material are avoided, so as to increase cycle life, improves high rate performance.Therefore,
Prepare that silicon-carbon composite nanostructure lithium ion battery negative material is with good economic efficiency and vast market prospect.
The content of the invention
Good the object of the present invention is to provide a kind of chemical property for above-mentioned technical problem, environmentally protective both hands close
Embrace type three-dimensional network-like structure Si-C composite material.
Another object of the present invention is to provide a kind of preparation method of Si-C composite material.
3rd purpose of the invention is to provide a kind of application of Si-C composite material as lithium ion battery negative material.
4th purpose of the invention is to provide a kind of lithium ion battery using Si-C composite material as negative material.
The purpose of the present invention is achieved by the following technical programs：
The present invention provides a kind of Si-C composite material, and the Si-C composite material is filled the span of a man's arms type three-dimensional network shape knot for both hands
Structure, the Si-C composite material include more using carbon network transition layer as substrate in each hand-type structure of carbon network transition layer
The component units of a " double palms and double wrists with finger " shape and " the double palm balls filled the span of a man's arms " shape, phosphorus content is 30 in the component units
~80% (wt), surplus are silicon.
Wherein, preferred embodiment according to the present invention, the thickness of carbon network transition layer is 50~200nm in the present invention, " hand
Finger " shape is that length is 0.05~1 μm of particle, and " double wrists " shape is that length is 0.2~3 μm of particle, and " the double palm balls filled the span of a man's arms " shape is long
Spend for 0.5~2 μm of particle.
The preparation method of Si-C composite material, specifically includes following steps in the present invention：
S1. aqueous solution is obtained in deionized water using dissolved organic matter as carbon source dissolving, aqueous solution is atomized,
Obtain organic matter mist pearl；
S2. organic matter mist pearl has been pre-placed the reactor of substrate by being loaded into, make organic matter mist pearl 200~
First time vapour deposition is carried out at 400 DEG C, forms carbon network transition layer；
S3. using dissolved organic matter as carbon source, being blended in dissolving in deionized water with soluble silicon source, to form water water-soluble
Liquid, aqueous solution is atomized to obtain mixing fog pearl, mixing fog pearl is loaded into reactor, in step S2 shapes at 600~1200 DEG C
Second is carried out on into the substrate of carbon network transition layer to be vapor-deposited, deposits complete postcooling to room temperature, is obtained both hands and is filled the span of a man's arms type
The Si-C composite material of three-dimensional network-like structure；
Wherein：The substrate is more than the metal or alloy for the temperature that is vapor-deposited twice for fusing point；Step S1 to S3 is whole
Keep atmosphere of inert gases.
The present invention carries out vapour deposition in substrate surface first and forms carbon network transition layer, the carbon network transition layer surface point
Nano dot or nano wire are furnished with, growth guiding function can be played in second of vapor deposition processes, generation is above-mentioned " to carry hand
The component units of the double palms and double wrists referred to " shape and " the double palm balls filled the span of a man's arms " shape.The both hands being prepared using this method are filled the span of a man's arms type
The Si-C composite material of three-dimensional network-like structure is composed of multiple nano-scale particles, the mechanical strength and toughness having had, can
Mitigate coming off due to active material caused by the volumetric expansion of silicon with effective.
Meanwhile on the basis of the metal or alloy of temperature that is vapor-deposited twice is more than in the substrate for fusing point, can
The material that copper foil, titanium foil or platinum foil etc. can be used for preparing anode plate for lithium ionic cell is selected to be generated as substrate in substrate multiple
It can be kept away after condensation material using direct slicing as lithium ion battery negative material using the negative plate without using binding agent
Having exempted from the electrode performance that binding agent denaturation and binding agent are brought in itself reduces., can be with meanwhile the present invention is using organosilicon as silicon source
Avoid using SiH4 and caused by security risk；Also without using hydrofluoric acid treatment, whole process does not have poisonous and harmful discarded
Thing produces, and realizes green production.
Preferably, carbon source described in step S1 of the present invention is glacial acetic acid, benzoic acid, squaric acid, ethanedioic acid, ethylene glycol, third
One or more mixing in triol, methanol and formaldehyde.
Preferably, the mass percentage concentration of aqueous solution described in step S1 of the present invention is 0.5~50%, preferably 5~
10%.
Preferably, step S1 and S3 atomizing types of the present invention are ultrasonic atomizatio, and step S1 and S3 are atomized using utilization
One kind for the atomising device that ultrasonic atomizatio, centrifugal atomizing, high-pressure atomization principle work, more preferably using ultrasonic atomizatio
Device, the ultrasonic atomizatio frequency range are 10000~50000Hz.
Preferably, first time vapor deposition times are 0.1~10h in step S2 of the present invention.
Preferably, second of vapor deposition times is 0.5~24h in step S3 of the present invention.
Preferably, the carbon source described in step S3 of the present invention is hydro carbons, in alkene, alkane, ketone, alcohols, aldehydes, aromatic hydrocarbon
One or more；Silicon source for trim,ethylchlorosilane, tetramethylsilane, dimethyldichlorosilane, one kind in silicon tetrachloride or
It is a variety of；Carbon source and the silicon source mass ratio is 1:1~100.
Preferably, inert gas of the present invention is one or more in nitrogen, argon gas, helium.
The Si-C composite material being prepared the present invention also provides the preparation method of the Si-C composite material is as battery
The application of negative material, the battery electrode material are lithium ion battery negative material.The substrate need to be copper foil, titanium foil or platinum
Paper tinsel etc. can be used for preparing the material of anode plate for lithium ionic cell, the surface deposition have the copper foil of Si-C composite material, titanium foil or
Platinum foil can direct slicing prepare anode plate for lithium ionic cell.
The present invention also provides a kind of lithium ion battery, which includes battery container, electrode group and electrolyte, electrode group and
Electrolyte is sealed in battery container, and electrode group includes cathode, membrane and anode, wherein, the anode is answered for silicon-carbon of the present invention
Negative electrode of lithium ion battery made of condensation material.
Other parts of the battery in addition to anode use this area routine techniques.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) in the present invention, the carbon of one layer of transition zone is first generated in substrate using vapour deposition, the deposition for silicon below carries
For a stabilization, firmly, there is the attachment point of certain toughness, while improve the electric conductivity of electrode.
(2) both hands of the present invention are filled the span of a man's arms obtained by the preparation method of type three-dimensional network-like structure Si-C composite material
Composite material is composed of multiple nano-scale particles, and the mechanical strength and toughness having had, can effectively mitigate due to silicon
Active material caused by volumetric expansion comes off.The electrode material prepared in this way avoids bonding without using binding agent
The electrode performance that agent denaturation and binding agent are brought in itself reduces.Meanwhile using organosilicon as silicon source, can be to avoid using SiH4And
Caused by security risk；Also without using hydrofluoric acid treatment, whole process does not have poisonous waste generation, realizes green
Production.
(3) the both hands type three-dimensional network-like structure Si-C composite material of filling the span of a man's arms for preparing gained is used as negative electrode of lithium ion battery material
Material, under 0.1C multiplying powers during discharge and recharge, first charge-discharge cycle charging capacity is filled up to 2231~2289 mAh/g under 5C multiplying powers
During electric discharge, after circulation 500 times, capacity retention ratio is up to more than 92.4~99.7%.
(4) both hands of the present invention are filled the span of a man's arms the preparation method production process of type three-dimensional network-like structure Si-C composite material
Simply, it is with short production cycle, it is of low cost, it is environmentally safe, provided effectively to obtain the electrode material of above-mentioned excellent performance
Approach.
Brief description of the drawings
Attached drawing 1 is filled the span of a man's arms the scanning of type three-dimensional network-like structure Si-C composite material for both hands obtained by the embodiment of the present invention four
Electron microscope.
Attached drawing 2 is filled the span of a man's arms the transmission of type three-dimensional network-like structure Si-C composite material for both hands obtained by the embodiment of the present invention four
Electron microscope.
Attached drawing 3 is filled the span of a man's arms the XRD of type three-dimensional network-like structure Si-C composite material for both hands obtained by the embodiment of the present invention four
Figure.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following embodiments are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
The assembling of lithium ion battery of the present invention and test mode are as follows：
The deposition that the present invention obtains has the copper foil of Si-C composite material, directly pole piece can be washed into using punch, full of argon
In the glove box of gas, using lithium piece as to electrode, membrane is microporous polypropylene membrane, and electrolyte is volume ratio 1:1 dimethyl carbonate
(DMC) and ethylene carbonate (EC) mixes 1mol L-1Hexafluoro phosphorus lithium (LiPF6), battery is assembled into, system is tested in NEWARE
Electrochemical property test is carried out on system.
Embodiment 1
S1. at room temperature using concentration be 5% squaric acid be used as transition carbon-coating carbon source, it is agitated fully dissolving completely after add
Enter three-necked flask, be placed on ultrasonic atomizer and carry out ultrasonic atomizatio, atomization frequency 17000Hz.
S2. a mouth rubber stopper seal of three-necked flask, a mouth access argon gas, another mouth connection tube furnace, warp
The mist pearl after ultrasonic atomizatio is crossed, by argon gas as in protective gas and transmission gas inlet pipe formula stove.With 350 DEG C in tube furnace
Temperature by square acid mist pearl be vapor-deposited it is horizontal positioned in advance with tube furnace in copper foil on, sedimentation time 2h.The side for the treatment of
Shape acid is completely nebulised, and closes ultrasonic atomizer.
S3. tubular type furnace temperature is warming up to 1000 DEG C with 5 DEG C/min, then opens three-necked flask rubber stopper, it is dense to add quality
Degree is respectively 34%, 66% benzene and trim,ethylchlorosilane mixed solution, stoppers rubber stopper, open ultrasonic atomizer continue with
The frequency of 17000Hz carries out ultrasonic atomizatio.After mixing fog integument is passed through tube furnace completely, ultrasonic atomizer is closed, mist pearl exists
Be vapor-deposited 12h in tube furnace, and taking-up is cooled to room temperature, and Si-C composite material is obtained in copper foil surface.
In this experimentation, whole process keeps argon stream 500mL/min.
The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, and Si-C composite material is with the carbon network of 100nm
Transition zone is substrate, each hand-type structure of carbon network transition layer include multiple " double palms and double wrists with finger " shapes with
The component units of " the double palm balls filled the span of a man's arms " shape, " finger " shape are that length is 0.05~1 μm of particle, and " double wrists " shape is that length is 0.2
~3 μm of particles, " the double palm balls filled the span of a man's arms " shape are that length is 0.5~2 μm of particle.
Obtained Si-C composite material is assembled into lithium ion battery and discharge and recharge is carried out under 0.1C multiplying powers and in 5C multiplying powers
Lower carry out charge-discharge test, specific data are referring to table 1.
Embodiment 2
S1. at room temperature using concentration be 5% squaric acid be used as transition carbon-coating carbon source, it is agitated fully dissolving completely after add
Enter three-necked flask, be placed on ultrasonic atomizer and carry out ultrasonic atomizatio, atomization frequency 17000Hz.
S2. a mouth rubber stopper seal of three-necked flask, a mouth access argon gas, another mouth connection tube furnace, warp
The mist pearl after ultrasonic atomizatio is crossed, by argon gas as in protective gas and transmission gas inlet pipe formula stove.With 350 DEG C in tube furnace
Temperature by square acid mist pearl be vapor-deposited it is horizontal positioned in advance with tube furnace in copper foil on, sedimentation time 2h.The side for the treatment of
Shape acid is completely nebulised, and closes ultrasonic atomizer.
S3. tubular type furnace temperature is warming up to 900 DEG C with 5 DEG C/min, then opens three-necked flask rubber stopper, add mass concentration
Respectively 50%, 50% benzene and trim,ethylchlorosilane mixed solution stopper rubber stopper, open ultrasonic atomizer continue with
The frequency of 17000Hz carries out ultrasonic atomizatio.After mixing fog integument is passed through tube furnace completely, ultrasonic atomizer is closed, mist pearl exists
Be vapor-deposited 12h in tube furnace, and taking-up is cooled to room temperature, and Si-C composite material is obtained in copper foil surface.
In this experimentation, whole process keeps argon stream 500mL/min.
The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, and Si-C composite material is with the carbon network of 100nm
Transition zone is substrate, each hand-type structure of carbon network transition layer include multiple " double palms and double wrists with finger " shapes with
The component units of " the double palm balls filled the span of a man's arms " shape, " finger " shape are that length is 0.05~1 μm of particle, and " double wrists " shape is that length is
0.1-0.3 μm of particle, " the double palm balls filled the span of a man's arms " shape are that length is 0.2-2 μm of particle.
Obtained Si-C composite material is assembled into lithium ion battery and discharge and recharge is carried out under 0.1C multiplying powers and in 5C multiplying powers
Lower carry out charge-discharge test, specific data are referring to table 1.
Embodiment 3
S1. at room temperature using concentration be 5% squaric acid be used as transition carbon-coating carbon source, it is agitated fully dissolving completely after add
Enter three-necked flask, be placed on ultrasonic atomizer and carry out ultrasonic atomizatio, atomization frequency 17000Hz.
S2. a mouth rubber stopper seal of three-necked flask, a mouth access argon gas, another mouth connection tube furnace, warp
The mist pearl after ultrasonic atomizatio is crossed, by argon gas as in protective gas and transmission gas inlet pipe formula stove.With 350 DEG C in tube furnace
Temperature by square acid mist pearl be vapor-deposited it is horizontal positioned in advance with tube furnace in copper foil on, sedimentation time 2h.The side for the treatment of
Shape acid is completely nebulised, and closes ultrasonic atomizer.
S3. tubular type furnace temperature is warming up to 700 DEG C with 5 DEG C/min, then opens three-necked flask rubber stopper, add mass concentration
Respectively 34%, 66% benzene and trim,ethylchlorosilane mixed solution stopper rubber stopper, open ultrasonic atomizer continue with
The frequency of 17000Hz carries out ultrasonic atomizatio.After mixing fog integument is passed through tube furnace completely, ultrasonic atomizer is closed, mist pearl exists
Be vapor-deposited 5h in tube furnace, and taking-up is cooled to room temperature, and Si-C composite material is obtained in copper foil surface.
In this experimentation, whole process keeps argon stream 500mL/min.
The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, and Si-C composite material is with the carbon network of 100nm
Transition zone is substrate, each hand-type structure of carbon network transition layer include multiple " double palms and double wrists with finger " shapes with
The component units of " the double palm balls filled the span of a man's arms " shape, " finger " shape are that length is 0.05~1 μm of particle, and " double wrists " shape is that length is
0.2-0.3 μm of particle, " the double palm balls filled the span of a man's arms " shape are that length is 0.5-1.5 μm of particle.
Obtained Si-C composite material is assembled into lithium ion battery and discharge and recharge is carried out under 0.1C multiplying powers and in 5C multiplying powers
Lower carry out charge-discharge test, specific data are referring to table 1.
Embodiment 4
S1. at room temperature using concentration be 5% squaric acid be used as transition carbon-coating carbon source, it is agitated fully dissolving completely after add
Enter three-necked flask, be placed on ultrasonic atomizer and carry out ultrasonic atomizatio, atomization frequency 17000Hz.
S2. a mouth rubber stopper seal of three-necked flask, a mouth access argon gas, another mouth connection tube furnace, warp
The mist pearl after ultrasonic atomizatio is crossed, by argon gas as in protective gas and transmission gas inlet pipe formula stove.With 350 DEG C in tube furnace
Temperature by square acid mist pearl be vapor-deposited it is horizontal positioned in advance with tube furnace in copper foil on, sedimentation time 2h.The side for the treatment of
Shape acid is completely nebulised, and closes ultrasonic atomizer.
S3. tubular type furnace temperature is warming up to 900 DEG C with 5 DEG C/min, then opens three-necked flask rubber stopper, add mass concentration
Respectively 34%, 66% benzene and trim,ethylchlorosilane mixed solution stopper rubber stopper, open ultrasonic atomizer continue with
The frequency of 17000Hz carries out ultrasonic atomizatio.After mixing fog integument is passed through tube furnace completely, ultrasonic atomizer is closed, mist pearl exists
Be vapor-deposited 5h in tube furnace, and taking-up is cooled to room temperature, and Si-C composite material is obtained in copper foil surface.
In this experimentation, whole process keeps argon stream 500mL/min.
The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, and Si-C composite material is with the carbon network of 100nm
Transition zone is substrate, each hand-type structure of carbon network transition layer include multiple " double palms and double wrists with finger " shapes with
The component units of " the double palm balls filled the span of a man's arms " shape, " finger " shape are that length is 0.5-0.8 μm of particle, and " double wrists " shape is that length is
0.2-1 μm of particle, " the double palm balls filled the span of a man's arms " shape are that length is 0.2-0.5 μm of particle.
Attached drawing 1 is filled the span of a man's arms the scanning electron microscope of type three-dimensional network-like structure Si-C composite material for both hands obtained by the present embodiment
Figure.It can be seen from the figure that length is about the finger shape that 0.5-0.8 μm of particle constitutes composite material, length is about 0.2-
The palm structure of 0.5 μm of particle composition composite material, the wrist knot for the particle composition composite material that length is about 0.2-1 μm
Structure.
Attached drawing 2 is filled the span of a man's arms the transmission electron microscope of type three-dimensional network-like structure Si-C composite material for both hands obtained by the present embodiment
Figure.Under a lens, it can be seen that material structure is filled the span of a man's arms type three-dimensional network-like structure for both hands, is met in scanning electron microscope (SEM) photograph and is observed
Structure, and can be found that a large amount of lattice fringes for being spaced about 0.33nm in (111) crystal face of silicon.
Attached drawing 3 for both hands obtained by the present embodiment fill the span of a man's arms type three-dimensional network-like structure Si-C composite material XRD figure, this
Show the reaction between Si atoms at high temperature and the Cu atoms of escape.However, not it is observed that carbon diffraction maximum, shows that there are nothing
Shape carbon.
Obtained Si-C composite material is assembled into lithium ion battery and discharge and recharge is carried out under 0.1C multiplying powers and in 5C multiplying powers
Lower carry out charge-discharge test, specific data are referring to table 1.
Embodiment 5
S1. at room temperature using concentration be 5% glacial acetic acid be used as transition carbon-coating carbon source, it is agitated fully dissolving completely after add
Enter three-necked flask, be placed on ultrasonic atomizer and carry out ultrasonic atomizatio, atomization frequency 17000Hz.
S2. a mouth rubber stopper seal of three-necked flask, a mouth access argon gas, another mouth connection tube furnace, warp
The mist pearl after ultrasonic atomizatio is crossed, by argon gas as in protective gas and transmission gas inlet pipe formula stove.With 500 DEG C in tube furnace
Temperature by square acid mist pearl be vapor-deposited it is horizontal positioned in advance with tube furnace in copper foil on, sedimentation time 2h.The side for the treatment of
Shape acid is completely nebulised, and closes ultrasonic atomizer.
S3. tubular type furnace temperature is warming up to 900 DEG C with 5 DEG C/min, then opens three-necked flask rubber stopper, add mass concentration
Respectively 34%, 66% benzene and trim,ethylchlorosilane mixed solution stopper rubber stopper, open ultrasonic atomizer continue with
The frequency of 17000Hz carries out ultrasonic atomizatio.After mixing fog integument is passed through tube furnace completely, ultrasonic atomizer is closed, mist pearl exists
Be vapor-deposited 5h in tube furnace, and taking-up is cooled to room temperature, and Si-C composite material is obtained in copper foil surface.
In this experimentation, whole process keeps argon stream 500mL/min.
The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, and Si-C composite material is with the carbon network mistake of 50nm
It is substrate to cross layer, includes multiple " double palms and double wrists with finger " shapes in each hand-type structure of carbon network transition layer and " closes
The component units of the double palm balls embraced " shape, " finger " shape are that length is 0.05-1 μm of particle, and " double wrists " shape is that length is 0.2-1 μm
Particle, " the double palm balls filled the span of a man's arms " shape are that length is 0.5-2 μm of particle.
Obtained Si-C composite material is assembled into lithium ion battery and discharge and recharge is carried out under 0.1C multiplying powers and in 5C multiplying powers
Lower carry out charge-discharge test, specific data are referring to table 1.
Embodiment 6
S1., the squaric acid that concentration is 10% is used as to the carbon source of transition carbon-coating at room temperature, after agitated fully dissolving is complete
Three-necked flask is added, is placed on ultrasonic atomizer and carries out ultrasonic atomizatio, atomization frequency 17000Hz.
S2. a mouth rubber stopper seal of three-necked flask, a mouth access argon gas, another mouth connection tube furnace, warp
The mist pearl after ultrasonic atomizatio is crossed, by argon gas as in protective gas and transmission gas inlet pipe formula stove.With 350 DEG C in tube furnace
Temperature by square acid mist pearl be vapor-deposited it is horizontal positioned in advance with tube furnace in copper foil on, sedimentation time 2h.The side for the treatment of
Shape acid is completely nebulised, and closes ultrasonic atomizer.
S3. tubular type furnace temperature is warming up to 900 DEG C with 5 DEG C/min, then opens three-necked flask rubber stopper, add mass concentration
Respectively 34%, 66% benzene and trim,ethylchlorosilane mixed solution stopper rubber stopper, open ultrasonic atomizer continue with
The frequency of 17000Hz carries out ultrasonic atomizatio.After mixing fog integument is passed through tube furnace completely, ultrasonic atomizer is closed, mist pearl exists
Be vapor-deposited 5h in tube furnace, and taking-up is cooled to room temperature, and Si-C composite material is obtained in copper foil surface.
In this experimentation, whole process keeps argon stream 500mL/min.
The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, and Si-C composite material is with the carbon network of 100nm
Transition zone is substrate, each hand-type structure of carbon network transition layer include multiple " double palms and double wrists with finger " shapes with
The component units of " the double palm balls filled the span of a man's arms " shape, " finger " shape are that length is 0.05-1 μm of particle, and " double wrists " shape is that length is 0.2-
1.5 μm of particles, " the double palm balls filled the span of a man's arms " shape are that length is 0.5-2 μm of particle.
Obtained Si-C composite material is assembled into lithium ion battery and discharge and recharge is carried out under 0.1C multiplying powers and in 5C multiplying powers
Lower carry out charge-discharge test, specific data are referring to table 1.
Embodiment 7
S1., the squaric acid that concentration is 10% is used as to the carbon source of transition carbon-coating at room temperature, after agitated fully dissolving is complete
Three-necked flask is added, is placed on ultrasonic atomizer and carries out ultrasonic atomizatio, atomization frequency 17000Hz.
S2. a mouth rubber stopper seal of three-necked flask, a mouth access argon gas, another mouth connection tube furnace, warp
The mist pearl after ultrasonic atomizatio is crossed, by argon gas as in protective gas and transmission gas inlet pipe formula stove.With 350 DEG C in tube furnace
Temperature by square acid mist pearl be vapor-deposited it is horizontal positioned in advance with tube furnace in copper foil on, sedimentation time 0.5h.Treat
Squaric acid is completely nebulised, and closes ultrasonic atomizer.
S3. tubular type furnace temperature is warming up to 900 DEG C with 5 DEG C/min, then opens three-necked flask rubber stopper, add mass concentration
Respectively 25%, 75% benzene and trim,ethylchlorosilane mixed solution stopper rubber stopper, open ultrasonic atomizer continue with
The frequency of 17000Hz carries out ultrasonic atomizatio.After mixing fog integument is passed through tube furnace completely, ultrasonic atomizer is closed, mist pearl exists
Be vapor-deposited 5h in tube furnace, and taking-up is cooled to room temperature, and Si-C composite material is obtained in copper foil surface.
In this experimentation, whole process keeps argon stream 500mL/min.
The Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, and Si-C composite material is with the carbon network of 200nm
Transition zone is substrate, each hand-type structure of carbon network transition layer include multiple " double palms and double wrists with finger " shapes with
The component units of " the double palm balls filled the span of a man's arms " shape, " finger " shape are that length is 0.05-1 μm of particle, and " double wrists " shape is that length is 0.2-
2 μm of particles, " the double palm balls filled the span of a man's arms " shape are that length is 0.5-1.5 μm of particle.
The composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, the network-like material of each hand-type structure silicon-carbon composite Nano
Material is made of the unit of many double palms with finger and double wrists, and finger length is 0.05-1 μm, and the double palm balls filled the span of a man's arms are, double
Wrist is particle；Transition carbon layers having thicknesses are 200nm.
Obtained Si-C composite material is assembled into lithium ion battery and discharge and recharge is carried out under 0.1C multiplying powers and in 5C multiplying powers
Lower carry out charge-discharge test, specific data are referring to table 1.
Table 1
From table 1 it follows that the both hands for preparing gained are filled the span of a man's arms, type three-dimensional network-like structure Si-C composite material is used as lithium
Ion battery cathode material, under 0.1C multiplying powers during discharge and recharge, first charge-discharge cycle charging capacity upto 2289mAh/g,
Under 5C multiplying powers during discharge and recharge, after circulation 500 times, capacity retention ratio reaches as high as more than 99.7%.
Inventor states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
- A kind of 1. Si-C composite material, it is characterised in that the Si-C composite material is filled the span of a man's arms type three-dimensional network-like structure for both hands, The Si-C composite material includes multiple " bands using carbon network transition layer as substrate, in each hand-type structure of carbon network transition layer Have double palms of finger and double wrists " component units of shape and " the double palm balls filled the span of a man's arms " shape, phosphorus content is 30 ~ 80% in the component units （wt）, surplus is silicon.
- 2. the preparation method of Si-C composite material described in a kind of claim 1, it is characterised in that comprise the following steps：S1. aqueous solution is obtained in deionized water using dissolved organic matter as carbon source dissolving, aqueous solution is atomized, must be had Machine thing mist pearl；S2., organic matter mist pearl has been pre-placed to the reactor of substrate by being loaded into, has made organic matter mist pearl at 200 ~ 400 DEG C First time vapour deposition is carried out, forms carbon network transition layer；S3. using dissolved organic matter as carbon source, it is blended in dissolving in deionized water with soluble silicon source and forms aqueous solution, by water Solution is atomized to obtain mixing fog pearl, and mixing fog pearl is loaded into reactor, and carbon network is formed in step S2 at 600 ~ 1200 DEG C Carry out being vapor-deposited for second in the substrate of transition zone, deposit complete postcooling to room temperature, obtain both hands in matrix surface and fill the span of a man's arms The Si-C composite material of type three-dimensional network-like structure；Wherein：The substrate is more than the metal or alloy for the temperature that is vapor-deposited twice for fusing point, and step S1 to S3 is whole to be kept Atmosphere of inert gases.
- 3. the preparation method of Si-C composite material according to claim 2, it is characterised in that carbon source described in step S1 is ice One or more mixing in acetic acid, benzoic acid, squaric acid, ethanedioic acid, ethylene glycol, glycerine, methanol and formaldehyde, step S3 institutes The carbon source stated is hydro carbons, one or more mixing in alkene, alkane, ketone, alcohols, aldehydes, aromatic hydrocarbon, wherein, step S1 It is different from carbon source in step S3.
- 4. the preparation method of Si-C composite material according to claim 2, it is characterised in that aqueous solution described in step S1 Mass percentage concentration is 0.5 ~ 50%.
- 5. the preparation method of Si-C composite material according to claim 2, it is characterised in that what step S1 and S3 atomization used It is one kind of the atomising device to be worked using ultrasonic atomizatio, compression atomizing, net formula atomizing principles, preferably using ultrasonic atomizatio Device, the ultrasonic atomizatio frequency range are 10000 ~ 50000Hz.
- 6. the preparation method of Si-C composite material according to claim 2, it is characterised in that first time, gas phase was sunk in step S2 The product time is 0.1 ~ 10h.
- 7. the preparation method of Si-C composite material according to claim 2, it is characterised in that second of gas phase is sunk in step S3 The product time is 0.5 ~ 24h.
- 8. the preparation method of Si-C composite material according to claim 3, it is characterised in that silicon source is trimethyl in step S3 One or more in chlorosilane, tetramethylsilane, dimethyldichlorosilane, silicon tetrachloride；Carbon source and silicon described in step S3 Source mass percentage concentration is respectively 1% ~ 99%, 99%-1%.
- 9. the preparation method of Si-C composite material according to claim 2, it is characterised in that the inert gas is nitrogen It is one or more in gas, argon gas, helium.
- 10. the Si-C composite material conduct that the preparation method of any one of claim 2 ~ 9 Si-C composite material is prepared The application of cell negative electrode material, the battery electrode material are lithium ion battery negative material, the substrate is copper foil, titanium foil or Platinum foil etc. can be used for the material for preparing anode plate for lithium ionic cell, and the surface deposition has copper foil, the titanium foil of Si-C composite material Or platinum foil can direct slicing prepare anode plate for lithium ionic cell.
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| CN111293274A (en) * | 2018-12-10 | 2020-06-16 | 广州汽车集团股份有限公司 | Negative pole piece, preparation method thereof and lithium ion battery |
| CN111313002A (en) * | 2020-02-27 | 2020-06-19 | 桂林电子科技大学 | Composite negative electrode, and preparation method and application thereof |
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| CN106848268A (en) * | 2017-04-11 | 2017-06-13 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of carbon-silicon composite material, Preparation Method And The Use |
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| WO2014144862A3 (en) * | 2013-03-15 | 2014-12-18 | Ndsu Research Foundation | Synthesis of silicon containing materials using liquid hydrosilane compositions through direct injection |
| CN106784743A (en) * | 2017-02-28 | 2017-05-31 | 山东泰纳新材料科技有限公司 | A kind of low thermal expansion porous silicon/graphite combination electrode material and preparation method thereof |
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