CN108365208A - A kind of preparation method of nano silicon composite cathode material for lithium ion battery - Google Patents
A kind of preparation method of nano silicon composite cathode material for lithium ion battery Download PDFInfo
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- CN108365208A CN108365208A CN201810279226.8A CN201810279226A CN108365208A CN 108365208 A CN108365208 A CN 108365208A CN 201810279226 A CN201810279226 A CN 201810279226A CN 108365208 A CN108365208 A CN 108365208A
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The present invention relates to a kind of nano silicon composite cathode material for lithium ion battery, the composite negative pole material is " egg " model structure, yolk is graphite matrix, is dispersed in the nano silicon material on graphite matrix inside and its surface, albumen is the graphene for being dispersed in graphite matrix and nanometer silicon face, and eggshell is conductive carbon coating layer.The present invention combines nano combined, surface modified and surface coating technology, is prepared for the silicon alloy negative material with " egg " model structure, has height ratio capacity, high first charge-discharge efficiency and excellent cyclical stability.Preparation process of the present invention is simple, environmental-friendly pollution-free.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of lithium ion battery nano silicon composite cathode material
Material and preparation method thereof, and the lithium ion battery that is prepared using the negative material.
Background technology
Now with the continuous deterioration in short supply with climatic environment of global petroleum resources, develop the new energy vapour of clean energy-saving
Vehicle is paid much attention to by countries in the world.The development of new-energy automobile, key is in its electrical source of power.Currently, commercialized lithium from
Sub- battery mainly uses graphite negative electrodes material, but its theoretical specific capacity is only 372mAh/g, cannot be satisfied the following lithium ion
Demand of the battery to high-energy density.So exploitation high-performance novel electrode material becomes research emphasis.
Silicon has the theoretical specific capacity of superelevation（4200mAh/g）With lower de- lithium current potential（<0.5V）, and the voltage of silicon is flat
Platform is slightly above graphite, and in charging, difficulty causes surface to analyse lithium, and security performance is more preferable, and silicon becomes the carbon-based cathode of lithium ion battery and regenerates
One of the potential selection of richness, but silicon also has disadvantage as lithium ion battery negative material：（1）Silicon materials are in charge and discharge process
In be easy to happen volume expansion, lead to conductive network avalanche, influence electric cycle performance；（2）Silicon is semi-conducting material, the electricity of itself
Conductance is relatively low, and during charge and discharge cycles, the deintercalation of lithium ion can lead to volume expansion and the receipts of 300% or more material generation
Contracting, to cause the destruction and dusting of material structure, causes capacity to decay rapidly, and cycle performance deteriorates.（3）Silicon materials are recycling
It is perishable in the process, capacity attenuation；（4）Due to the bulk effect of silicon materials, it is difficult to form stable solid-state electricity in the electrolytic solution
Solve matter interface（SEI）Film constantly forms new SEI films in the silicon face exposed, exacerbates along with the destruction of electrode structure
The corrosion of silicon and capacity attenuation.
Think silicon materials during removal lithium embedded volume expansion shrink it is larger be to cause material damage and crushing, be to lead
The main reason for causing capacity attenuation very fast.As CN 103474667A disclose a kind of silicon-carbon composite cathode material, including nanometer
Silicon/graphite particle, the first carbon coating layer and organic cleaving layer, wherein nano-silicon/graphite particle are using graphite as kernel, and cladding is received
Rice silicon particle layer, spherical or near-spherical the composite particles of formation.
CN 104617269 discloses a kind of silicon alloy composite negative pole material, uses graphite and the silicon for being coated in graphite surface
Alloy is kernel, and shell is cracking carbon, in conjunction with nano combined, surface be modified and coating modification technology, is prepared for nucleocapsid knot
The silicon alloy composite negative pole material of structure, negative material compacted density is high, processing performance is good, electric conductivity is high, first charge discharge efficiency is high, follows for this
Ring superior performance.But the composite material metals content impurity that this method is prepared is higher, and self discharge, and high temperature storage easily occurs
Difference.
105070894 A of CN disclose a kind of lithium ion battery porous silicon-base composite negative pole material, the cathode material
Material is capsule structure, and capsule-core is noncrystalline, porous silicon, and cyst wall is conductive carbon material, and the grain size of noncrystalline, porous silicon is 10-
The aperture of 300nm, noncrystalline, porous silicon are 0.5~100nm, and the thickness of the cyst wall is 0.5-10 μm, and prepared by this method answers
Condensation material specific capacity is high, and expansion is low, and processing performance is excellent.But the composite inner hole that this method is prepared is more, jolt ramming
Density is relatively low, and volume energy density is not high.
Therefore, exploitation is a kind of simple for process, has excellent performance and the preparation of environmental-friendly nano silicon-based composite negative pole material
Method is the important research direction of field of lithium ion battery.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of nano silicon-based Compound Negatives of lithium ion battery
Pole material and preparation method thereof, the nano silicon-based composite negative pole material are " egg " model structure, and yolk is nano-silicon/graphite
Composite material, albumen are graphene, and eggshell is conductive carbon material.
A kind of preparation method of nano silicon composite cathode material for lithium ion battery, includes the following steps：
A1, by powdered graphite and nano silica fume, liquid phase is compound in alcohol system medium, obtains the first presoma；
A2, graphene is coated in first presoma surface, obtains the second presoma；
A3, second presoma is coated, is modified, is sintered, obtaining nano silicon composite cathode material；
Further, further include step A4：The composite negative pole material that step A3 is obtained crushes, sieves and remove magnetic, obtains middle grain
The nano silicon composite cathode material that diameter is 5.0~20 μm.
Preferably, in the step A1, before liquid phase is compound, powder body material surface modification method is first used to prepare nano-silicon
Powder：Silane coupling agent is added in the flask of alcohol system nano-silicon slurries, be subsequently placed into ultrasonic cleaner carry out ultrasound 4~
8h finally obtains modification nano silica fume by freeze-drying.
Preferably, the silane coupling agent is aminopropyl trimethoxysilane, isobutyl ethyl triethoxy silicane, methacryl
Oxysilane, preferably aminopropyl trimethoxysilane.The silane coupling agent addition is 1.0~10.0%.
Preferably, in the step A1, powdered graphite is added in the flask equipped with modification nano silica fume slurries, subsequent row
Celestial body grinds 1~20h, and finally spray drying obtains spherical nano-silicon/graphite composite material, i.e. the first presoma.
Preferably, in the step A2, the coating step of the graphene is：Nano-silicon/the graphite is molten in alcohol system
In agent after decentralized processing, add graphene oxide into the nano-silicon/graphite solution, mist projection granulating after evenly dispersed processing,
Obtain precursor complex.
Preferably, in step A3, the cladding is using mechanical solid phase cladding or liquid phase coating or gas phase cladding.
Preferably, in step A3, the sintering temperature is 600 DEG C~1000 DEG C, and the thermal reduction time is 10~240min.
Preferably, the thermal reduction heating rate is 0.5~15.0 DEG C/min.
A kind of lithium ion battery, which is characterized in that the lithium ion battery includes any one of 1~9 preparation method system
The nano silicon composite cathode material obtained.
Compared with prior art, the present invention has the advantages that：
（1）The present invention breaks through the prior art, and using the above novel preparation method of uniqueness, preparing has " egg " model structure
Lithium ion cell nano silicon composite cathode material, while combining existing silicon carbon material advantage, by by nano-silicon/stone
Ink is set as yolk so that its nano-silicon uniform adhesion is on graphite internal void and its surface so that it has preferably conductive
Performance, and the matrix of entire composite material is served as, by setting graphene to albumen so that composite material formation is extended in all direction
Conductive network and buffer strip, volume expansion blockage effect of the nano-silicon in charge and discharge process has been effectively relieved, has improved material
The comprehensive performance of material（Full battery recycles 800 weeks capacity retention ratios 82% or more）With coulombic efficiency for the first time（>92%）；By that will lead
Electrical carbon layer is set as eggshell so that, with lower specific surface area, can determine obtain firm " egg " model structure for it
With ideal specific capacity.
（2）Nano silicon composite cathode material for lithium ion battery specific capacity provided by the invention is high, high first charge-discharge effect
Rate, cyclical stability are excellent, preparation process is simple, environmental-friendly pollution-free.
Description of the drawings
Fig. 1 is the structure graph model of the nano silicon composite cathode material prepared using the method for the present invention.
Fig. 2 is the scanning electron microscope of the nano silicon composite cathode material prepared using the method for the present invention（SEM）Figure.
Fig. 3 is the XRD diagram of the nano silicon composite cathode material prepared using the method for the present invention.
Fig. 4 is the first charge-discharge curve of the nano silicon composite cathode material prepared using the method for the present invention.
Fig. 5 is the cycle performance curve of the nano silicon composite cathode material prepared using the method for the present invention.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of nano silicon composite cathode material for lithium ion battery, includes the following steps：
A1, aminopropyl trimethoxysilane is added to the nano silica fume flask that the middle grain size being scattered in alcohol solvent is 100nm
Middle mixing, mixing quality ratio are 1:20, it is subsequently placed into progress ultrasound 4h, supersonic frequency in ultrasonic cleaner and is adjusted to 40kHZ,
Nano-silicon slurries after being modified.
A2, the artificial graphite powder that middle grain size is 10 μm is added to nano-silicon slurries mixing after modification, mixing quality ratio
It is 1:1, it is fitted into after mixing in the planetary ball mill of 5L stainless cylinder of steel, is passed through argon gas protective gas, be 200r/min items in rotating speed
High-energy ball milling 10h under part, then spray drying treatment, obtains nano-silicon/graphite presoma.
A3, the nano-silicon/graphite in alcohol solvent is dispersed with stirring 1h, the graphene oxide that the number of plies is 50 layers is added
Enter and is mixed in the nano-silicon/graphite solution, mixed proportion 2：8, persistently stir 10h, then mist projection granulating obtain nano-silicon/
Graphite composite material.
A4, the pitch in mass ratio 9 for being 3 μm by nano-silicon/graphite composite particles and grain size:1 is matched,
It is uniformly mixed and is placed in VC mixing machines, adjusting frequency is 35HZ, mixes 1h, is subsequently placed in crucible, is carried out in retort
Charing process uses nitrogen as protection gas, and heating rate is 5 DEG C/min, 900 DEG C of heat preservation 4h postcoolings to room temperature.Then 400 mesh
Screening obtains finished product nano silicon composite cathode material.Grain size is 16 μm in " egg " nano silicon composite cathode material；" egg
Huang " nano-silicon/graphite composite material grain size is 12 μm, and " albumen " graphene thickness is 3 μm, and " eggshell " conduction carbon thickness is 1 μm.
Fig. 1 is the structure graph model of nano silicon composite cathode material of the present invention, and Fig. 2 is that nano-silicon prepared by embodiment 1 is multiple
Close the scanning electron microscope of negative material（SEM）Figure, Fig. 3 are the XRD of nano silicon composite cathode material prepared by embodiment 1
Figure, Fig. 4 are the first charge-discharge curve of nano silicon composite cathode material prepared by embodiment 1, and as seen from the figure, which fills for the first time
Discharge capacity is higher.
Embodiment 2
A kind of preparation method of nano silicon composite cathode material for lithium ion battery, includes the following steps：
A1, silane coupling agent is added to the middle grain size being scattered in alcohol solvent to be mixed in the nano silica fume flask of 100nm, mixed
It is 1 to close mass ratio:15, it is subsequently placed into progress ultrasound 6h, supersonic frequency in ultrasonic cleaner and is adjusted to 40kHZ, is modified
Nano-silicon slurries afterwards.
A2, the artificial graphite powder that middle grain size is 10 μm is added to nano-silicon slurries mixing after modification, mixing quality ratio
It is 2:1, it is fitted into after mixing in the planetary ball mill of 5L stainless cylinder of steel, is passed through argon gas protective gas, be 200r/min items in rotating speed
High-energy ball milling 20h under part, then spray drying treatment, obtains nano-silicon/graphite.
A3, the nano-silicon/graphite is dispersed with stirring 1h in alcohol solvent, the graphene oxide for being 100 layers by the number of plies
It is added in the nano-silicon/graphite solution and mixes, mixed proportion 1：9,10h is persistently stirred, then mist projection granulating obtains nanometer
Silicon/graphite composite material；
A4, the pitch in mass ratio 8 for being 3 μm by nano-silicon/graphite composite particles and grain size:2 are matched, mixing
It is uniformly placed in VC mixing machines, adjusting frequency is 35HZ, mixes 1h, is subsequently placed in crucible, is carbonized in retort
Processing uses nitrogen as protection gas, and heating rate is 5 DEG C/min, 800 DEG C of heat preservation 4h postcoolings to room temperature.Then 400 mesh sieve
Obtain finished product nano silicon composite cathode material；Grain size is 15 μm in " egg " nano silicon composite cathode material；" yolk " is received
Rice silicon/graphite composite material grain size is 11 μm, and " albumen " graphene thickness is 2 μm, and " eggshell " conduction carbon thickness is 2 μm.
Embodiment 3
A kind of preparation method of nano silicon composite cathode material for lithium ion battery, includes the following steps：
A1, it silane coupling agent is added in the nano silica fume flask that the middle grain size that is scattered in b propanol solvent is 200nm mixes,
Mixing quality ratio is 1:20, it is subsequently placed into progress ultrasound 8h, supersonic frequency in ultrasonic cleaner and is adjusted to 40kHZ, is repaiied
Nano-silicon slurries after decorations.
A2, the artificial graphite powder that middle grain size is 15 μm is added to nano-silicon slurries mixing after modification, mixing quality ratio
It is 3:1, it is fitted into after mixing in the planetary ball mill of 5L stainless cylinder of steel, is passed through argon gas protective gas, be 500r/min items in rotating speed
High-energy ball milling 10h under part, then spray drying treatment, obtains nano-silicon/graphite.
A3, the nano-silicon/graphite is dispersed with stirring 3h in alcohol solvent, the graphene oxide for being 200 layers by the number of plies
It is added in the nano-silicon/graphite solution and mixes, mixed proportion 3：7,10h is persistently stirred, then mist projection granulating obtains nanometer
Silicon/graphite composite material.
A4, the phenolic aldehyde in mass ratio 8 for being 5 μm by nano-silicon/graphite composite particles and grain size:2 are matched,
It is uniformly mixed and is placed in VC mixing machines, adjusting frequency is 35HZ, mixes 2h, is subsequently placed in crucible, is carried out in retort
Charing process uses nitrogen as protection gas, and heating rate is 2 DEG C/min, 950 DEG C of heat preservation 4h postcoolings to room temperature.Then 400 mesh
Screening obtains finished product nano silicon composite cathode material；Grain size is 22 μm in " egg " nano silicon composite cathode material；" egg
Huang " nano-silicon/graphite composite material grain size is 17 μm, and " albumen " graphene thickness is 3 μm, and " eggshell " conduction carbon thickness is 2 μm.
Embodiment 4
A kind of preparation method of nano silicon composite cathode material for lithium ion battery, includes the following steps：
A1, it silane coupling agent is added in the nano silica fume flask that the middle grain size that is scattered in b propanol solvent is 50nm mixes,
Mixing quality ratio is 1:20, it is subsequently placed into progress ultrasound 8h, supersonic frequency in ultrasonic cleaner and is adjusted to 40kHZ, is repaiied
Nano-silicon slurries after decorations.
A2, the artificial graphite powder that middle grain size is 18 μm is added to nano-silicon slurries mixing after modification, mixing quality ratio
It is 1:1, it is fitted into after mixing in the planetary ball mill of 5L stainless cylinder of steel, is passed through argon gas protective gas, be 500r/min items in rotating speed
High-energy ball milling 10h under part, then spray drying treatment, obtains nano-silicon/graphite.
A3, the nano-silicon/graphite is dispersed with stirring 3h in b propanol solvent, the graphene oxide for being 20 layers by the number of plies
It is added in the nano-silicon/graphite solution and mixes, mixed proportion 3：7,10h is persistently stirred, then mist projection granulating obtains nanometer
Silicon/graphite composite material.
A4, after dissolving 5 μm of phenolic aldehyde with alcohol, nano-silicon/graphite composite particles and novolac solution are pressed into matter
Measure ratio 8:2 are matched, and stir 10h after mixing, and rotating speed 1000r/min is spray-dried, is subsequently placed in crucible,
Charing process is carried out in retort, uses nitrogen as protection gas, and heating rate is 5 DEG C/min, and 950 DEG C of heat preservation 4h postcoolings are extremely
Room temperature.Then 400 mesh sieve to obtain finished product nano silicon composite cathode material；Grain in " egg " nano silicon composite cathode material
Diameter is 25 μm；" yolk " nano-silicon/graphite composite material grain size is 20 μm, and " albumen " graphene thickness is 3 μm, and " eggshell " is conductive
Carbon thickness is 2 μm.
Comparative example 1
Difference lies in without step A1 and step A3 with embodiment 1.
Comparative example 2
Difference lies in without step A2 with embodiment 1.
One, performance test：
The negative material that embodiment and comparative example provide is prepared into battery, the specific steps are：
By negative material, conductive agent and binder in mass ratio 94:2:4 mixed dissolutions in a solvent, control solid content 50%,
Coated in copper foil current collector, the LiPF of cathode pole piece, 1mol/L is made in vacuum drying6/EC+DMC+EMC(v/v=1:1:1)
Electrolyte, SK diaphragms, lithium piece, shell use the button cell of conventional production process assembly.
On Shenzhen Xin Wei Co., Ltds battery test system, test condition is：Under room temperature, 0.1C constant current charge-discharges fill
Discharge cut-off voltage 0.01V-1.5V.
Two, test result is shown in Table 1：
The performance test results of table 1 embodiment and comparative example：
Claims (10)
1. a kind of preparation method of nano silicon composite cathode material for lithium ion battery, which is characterized in that include the following steps：
A1, by powdered graphite and nano silica fume, liquid phase is compound in alcohol system medium, obtains the first presoma；
A2, graphene is coated in first presoma surface, obtains the second presoma；
A3, second presoma is coated, is modified, is sintered, obtaining nano silicon composite cathode material.
2. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 1, feature
It is, further includes step A4：The composite negative pole material that step A3 is obtained crushes, sieves and remove magnetic, obtain middle grain size be 5.0~
20 μm of nano silicon composite cathode material.
3. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 1, feature
It is：In the step A1, before liquid phase is compound, powder body material surface modification method is first used to prepare nano silica fume：By silane
Coupling agent is added in the flask of alcohol system nano-silicon slurries, is subsequently placed into progress 4~8h of ultrasound in ultrasonic cleaner, finally passes through
Freeze-drying obtains modification nano silica fume.
4. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 3, feature
It is：The silane coupling agent be aminopropyl trimethoxysilane, isobutyl ethyl triethoxy silicane, methacryloxypropyl silane,
Preferably aminopropyl trimethoxysilane；The silane coupling agent addition is 1.0~10.0%.
5. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 1, feature
It is：In the step A1, powdered graphite is added in the flask equipped with modification nano silica fume slurries, subsequent planetary ball mill 1~
20h, finally spray drying obtain spherical nano-silicon/graphite composite material, i.e. the first presoma.
6. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 1, feature
It is：In the step A2, the coating step of the graphene is：By the nano-silicon/graphite in alcohol series solvent at dispersion
It after reason, adds graphene oxide into the nano-silicon/graphite solution, mist projection granulating after evenly dispersed processing obtains presoma
Compound.
7. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 1, feature
It is：In step A3, the cladding is using mechanical solid phase cladding or liquid phase coating or gas phase cladding.
8. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 1, feature
It is：In step A3, the sintering temperature is 600 DEG C~1000 DEG C, and the thermal reduction time is 10~240min.
9. a kind of preparation method of nano silicon composite cathode material for lithium ion battery according to claim 8, feature
It is：The thermal reduction heating rate is 0.5~15.0 DEG C/min.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes that any one of 1~9 preparation method is made
Nano silicon composite cathode material.
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| CN111697218A (en) * | 2020-06-30 | 2020-09-22 | 陕西煤业化工技术研究院有限责任公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN111916718A (en) * | 2020-07-30 | 2020-11-10 | 内蒙古凯金新能源科技有限公司 | Spherical lithium ion battery surface coating material and preparation method thereof |
| CN113363479A (en) * | 2021-03-31 | 2021-09-07 | 万向一二三股份公司 | Double-layer carbon-coated silicon oxide negative electrode material and preparation method and application thereof |
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| CN109755521B (en) * | 2018-12-29 | 2020-09-29 | 湖南中科星城石墨有限公司 | SiO with three-dimensional net structure2Preparation method of/C negative electrode material |
| CN110729471A (en) * | 2019-10-24 | 2020-01-24 | 长沙晟天新材料有限公司 | Silicon @ graphene/CVD carbon composite anode material for lithium ion battery and preparation method and application thereof |
| CN110729471B (en) * | 2019-10-24 | 2021-10-26 | 湖南金硅科技有限公司 | Silicon @ graphene/CVD carbon composite anode material for lithium ion battery and preparation method and application thereof |
| CN110931756A (en) * | 2019-12-13 | 2020-03-27 | 成都爱敏特新能源技术有限公司 | High-performance silicon-carbon composite negative electrode material with adjustable particle size and preparation method thereof |
| CN111697218A (en) * | 2020-06-30 | 2020-09-22 | 陕西煤业化工技术研究院有限责任公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN111916718A (en) * | 2020-07-30 | 2020-11-10 | 内蒙古凯金新能源科技有限公司 | Spherical lithium ion battery surface coating material and preparation method thereof |
| CN113363479A (en) * | 2021-03-31 | 2021-09-07 | 万向一二三股份公司 | Double-layer carbon-coated silicon oxide negative electrode material and preparation method and application thereof |
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