CN109360962A - A kind of lithium battery high stability silicon-carbon cathode material and preparation method thereof - Google Patents
A kind of lithium battery high stability silicon-carbon cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to electrochemical field, it is related to a kind of lithium battery high stability silicon-carbon cathode material and preparation method thereof.It the described method comprises the following steps: (1) nano-silicon and substrate carbon material being sufficiently mixed at normal temperature, obtain raw material A；(2) asphalt powder being mechanically pulverized using graininess asphalt or coal tar pitch is raw material B；(3) raw material A, raw material B, carbon nanotube and hard carbon presoma are sufficiently mixed, obtain raw material C；(4) raw material C is carried out to low temperature softening pre-coated under gas shield, the block obtained after cooling crushes, and screening obtains raw material D；(5) raw material D is uniformly mixed at normal temperature with raw material B, the high temperature sintering under gas shield, obtained block is crushed, sieved, and finally obtains high stability silicon-carbon cathode material.Present invention process is simple, highly-safe, and the silicon-carbon cathode material of preparation has the advantages such as first effect is high, stability and high rate performance are excellent, is suitable for industrialized production.
Description
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of lithium battery high stability silicon-carbon cathode material and its preparation
Method.
Background technique
With the fast development of new-energy automobile industry, there is an urgent need to develop the height of capacity out, the lithium battery of good cycle
To improve its course continuation mileage.2 months 2017, the Ministry of Industry and Information Technology, State Development and Reform Commission, the Department of Science and Technology, Ministry of Finance's joint publication " promoted
Into automobile power cell developing activity scheme (2017) " it is distinctly claimed the year two thousand twenty, the monomer ratio of Novel lithium ion power battery
Energy is more than 300 Wh/kg.It realizes this target, needs to develop the novel cathode of lithium battery that capacity is high, has excellent performance
Material.
Lithium cell cathode material is most widely used at present or graphite, but its theoretical capacity is relatively low, it is difficult to meet vehicle
With the demand of power battery high-energy density, pass through the progress of improvement battery process also difficult making a breakthrough property.Silicon has very high
Theoretical capacity is expected to become next-generation lithium cell cathode material, receives extensive concern and the research of material circle and industrial circle.But
Be silicon in practical applications the main problems are as follows: (1) huge volume expansion；(2) electrode surface generates unstable
SEI film；(3) semiconductor silicon conductivity is lower.Carbon material such as graphite, carbonaceous mesophase spherules, soft carbon, hard carbon, nanotube, graphene
It is considered most promising with the compound Si-C composite material of preparing of silicon etc. electric conductivity with good stability and excellent
Push one of the method for silicon industrial application.Carbon material can be used as buffer matrix, and it is swollen to buffer volume of the silicon in charge and discharge process
It is swollen.It is found that improve the defect of silica-base material, key is to design reasonable composite construction, thus in charge and discharge process
The middle structural stability for guaranteeing material both macro and micro, and stablize quick ion and electron-transport path.
CN105932245A discloses a kind of preparation method and applications of high compacted density silicon-carbon cathode material, material by
Core layer and core layer external coating composition, core layer is by being spray-dried and forging after nano-silicon, graphite and additive wet-mixing
Burning obtains, and calcining obtains the negative electrode material with clad after then mixing with covering liquid phase, is spray-dried and calcines twice
Technique overall cost is higher, and liquid phase mixed process needs to have larger pollution using organic solvent, is unfavorable for industrial production.
CN103730644B disclose it is a kind of by silicon, Si oxide and graphite carry out high-energy ball milling, then coated with organic carbon source
The method for preparing silicon-carbon cathode with high temperature cabonization, the spheric granules tap density which obtains is high, and circulation and stability are preferable,
But particle surface only one layer of indefiniteness carbon-coating of this method preparation, the silicon in material are easy to exposure in the electrolytic solution, it is difficult to shape
At stable SEI film, lead to that material efficiency for charge-discharge is low, capacity attenuation trend is more apparent.
Summary of the invention
The invention proposes a kind of lithium battery high stability silicon-carbon cathode materials and preparation method thereof, by constructing multilayer
Structure provides repeatedly effectively buffering for the volume expansion of silicon, by constructing micro conductive network around nano-silicon, it is conductive to improve silicon
Property difference disadvantage, while designing effective protection aquiclude, avoid directly contacting for silicon and electrolyte.
It realizes the technical scheme is that a kind of lithium battery high stability silicon-carbon cathode material, the composite material
For three layers of clad structure；Composite inner is substrate carbon material, and middle layer is by nano-silicon, carbon nanotube, soft carbon and/or hard carbon
Composition, composite material outer layer are the soft carbon layers formed after pitch is sintered.
On the basis of composite material gross mass, the weight percent of each substance are as follows: substrate carbon material 75 ~ 90%, nano-silicon 4 ~
12%, carbon nanotube 0.5 ~ 2%, soft carbon 1 ~ 4%, hard carbon 0 ~ 4%, outer layer 1 ~ 5%.
The substrate carbon material is one of natural graphite, artificial graphite, carbonaceous mesophase spherules, soft carbon and hard carbon or two
Kind.
The nano-silicon granularity is that D50 is 50 ~ 500nm, purity > 97%.
The lithium battery preparation method of high stability silicon-carbon cathode material, steps are as follows:
(1) nano-silicon and substrate carbon material are sufficiently mixed uniformly at normal temperature, obtain raw material A；
(2) graininess asphalt or coal tar pitch is mechanically pulverized, screening obtains raw material B；
(3) raw material A, raw material B, carbon nanotube, hard carbon presoma are sufficiently mixed at normal temperature, obtain raw material C；
(4) raw material C is carried out to low temperature softening pre-coated under gas shield, the block obtained after cooling crushes, screening obtains
Raw material D；
(5) raw material D is uniformly mixed at normal temperature with raw material B, the high temperature sintering under gas shield, obtained block crushes,
Screening obtains high stability silicon-carbon cathode material.
It is one of asphalt, coal tar pitch or mixture in raw material B in the step (2), wherein pitch is medium temperature
Or one of hard pitch, granularity are 2 ~ 20 μm.
In the step (3) hard carbon presoma be glucose, sucrose, starch, polyvinyl alcohol, phenolic resin, epoxy resin,
One of glycan alcohol or cellulose.
Protective gas in the step (4) and step (5) is one of high pure nitrogen, argon gas, helium；Step
(4) cryogenic conditions in are 100 ~ 500 DEG C, and heating rate is 5 ~ 15 DEG C of min-1, softening stress-displacement stage soaking time is 1 ~ 3h.
Step (5) the high temperature sintering temperature is 700 ~ 1000 DEG C, and heating rate is 10 ~ 25 DEG C of min-1, soaking time
2~6h。
The beneficial effects of the present invention are: silicon-carbon cathode material of the present invention is formed with three parts, respectively internal
Substrate carbon material, the soft carbon protective layer and soft, hard carbon, conductive network of carbon nanotubes and nano-silicon shape formed after external pitch sintering
At middle layer.The structure has close structure, the high advantage of tap density.It is mutual that soft or hard carbon phase combination can either form advantage
It mends, the middle layer that cladding nano-silicon is formed can provide good buffer platform, this layer of carbon nanotube institute also for the volume expansion of silicon
The conductive network of formation also compensates for the disadvantage of silicon poorly conductive.The soft carbon layer of outer layer avoids the direct of nano-silicon and electrolyte
Contact, plays good shielding action.The silicon-carbon cathode that the preparation method obtains has high first effect, stability and high rate performance
Good advantage is suitable for power battery cathode, and simple process, has industrialization prospect.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is scanning electron microscope (SEM) photograph of the obtained silicon-carbon cathode material of embodiment 1 under 1.50k enlargement ratio.
Fig. 2 is scanning electron microscope (SEM) photograph of the silicon-carbon cathode material obtained in embodiment 1 under 8.00k enlargement ratio.
Fig. 3 is the surface-element distribution in region shown in silicon-carbon cathode material Fig. 2 scanning electron microscope (SEM) photograph obtained in embodiment 1
Figure.
Fig. 4 is the transmission electron microscope picture of silicon carbon material obtained in embodiment 1.
Fig. 5 is the scanning electron microscope (SEM) photograph under silicon-carbon cathode material 20.0k enlargement ratio obtained in comparative example 1.
Fig. 6 is the charge and discharge cycles curve graph of silicon-carbon cathode material obtained in embodiment 1.
Fig. 7 is the high rate performance figure of silicon-carbon cathode material obtained in embodiment 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
In following embodiment, the microcosmic shape of prepared sample is measured using Hitachi S-3400N scanning electron microscope
Looks.The battery for the model LANHE CT2001A that battery performance test is produced using Wuhan Land Electronic Co., Ltd.
Test macro.
Silicon-carbon cathode material prepared by the present invention is being made with conductive agent carbon black and binder according to mass ratio for 8:1:1
Slurry is uniformly coated on drying on copper foil and electrode is made, and wherein binder is CMC and SBR and additive according to mass ratio 1:1:1
Ratio be formulated.Electrolyte selects 1.0 mol L-1LiPF6Mixed organic solvents, solvent is that mass ratio is 1:1:1
EC:DEC:DMC, additive be 10% FEC.Diaphragm is microporous polypropylene membrane, just extremely lithium piece, is processed into CR2025 button
Formula battery.First circle discharge test 0.2C multiplying power discharging to 0.01V, 0.02C are discharged to 0.005 V, and charging is charged to 0.2C
2.0V.Cycle performance test carries out constant current charge-discharge test with 0.5C, and charging/discharging voltage range is 0.005 ~ 2V, 25 DEG C of constant temperature items
It is tested under part.High rate performance test condition is that 0.2C is discharged to 0.01V, and 0.02C is discharged to 0.005 V, and charging is charged with 0.2C
To 2.0V two weeks, then respectively in 10 circle of 0.2C, 0.5C, 1C, 2C and 5C test, and restore to 0.5C to test, charging/discharging voltage
Range is 0.005 ~ 2V.
Embodiment 1
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 6.75g D50 is 200nm is uniformly mixed at normal temperature with 87.25g artificial graphite, obtains raw material A；(2) machine
Tool grinding particulate medium temperature asphalt, screening obtains the raw material B asphalt powder that D50 is about 5 μm, spare；(3) by raw material A with
1g single-walled carbon nanotube, 15.6 raw material B are uniformly mixed at normal temperature, obtain raw material C；(4) under nitrogen protection by raw material C, it presses
According to 5 DEG C of min-1Heating rate is warming up to 150 DEG C and carries out softening pre-coated, keeps the temperature 1.5h, and cooled to room temperature crushes, mistake
Sieve, obtains raw material D；(5) raw material D is uniformly mixed at normal temperature with 15.6g raw material B, is heated up under nitrogen protection according to 10 DEG C
min-1Heating rate is warming up to 800 DEG C, keeps the temperature 2h, and cooled to room temperature crushes, sieving, obtains high stability silicon-carbon cathode
Material.
Embodiment 2
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 11.25g D50 is 100nm is uniformly mixed at normal temperature with 76.75g natural graphite, obtains raw material A；(2)
Graininess medium temperature asphalt is mechanically pulverized, screening obtains the raw material B asphalt powder that D50 is about 5 μm, spare；(3) by raw material A
It is uniformly mixed at normal temperature with 2g single-walled carbon nanotube, 25g raw material B, 6.25g glucose, obtains raw material C；(4) raw material C is existed
Under nitrogen protection, according to 5 DEG C of min-1Heating rate is warming up to 150 DEG C and carries out softening pre-coated, keeps the temperature 1.5h, naturally cools to
Room temperature crushes, sieving, obtains raw material D；(5) raw material D is uniformly mixed at normal temperature with 31.25g raw material B, under nitrogen protection
Heating is according to 5 DEG C of min-1Heating rate is warming up to 700 DEG C, keeps the temperature 2h, and cooled to room temperature crushes, sieving, obtains high steady
Qualitative silicon-carbon cathode material.
Embodiment 3
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 11g D50 is 50nm is uniformly mixed at normal temperature with 80g natural graphite, obtains raw material A；(2) it is mechanically pulverized
Graininess coal tar pitch, screening obtains the raw material B asphalt powder that D50 is about 2 μm, spare；(3) by raw material A and 1g multi wall carbon
Nanotube, 12.5g raw material B, 12.5g sucrose are uniformly mixed at normal temperature, obtain raw material C；(4) under protection of argon gas by raw material C,
According to 10 DEG C of min-1Heating rate is warming up to 250 DEG C and carries out softening pre-coated, keeps the temperature 2h, and cooled to room temperature crushes, mistake
Sieve, obtains raw material D；(5) raw material D is uniformly mixed at normal temperature with 25g raw material B, is heated up under protection of argon gas according to 15 DEG C
min-1Heating rate is warming up to 800 DEG C, keeps the temperature 3h, and cooled to room temperature crushes, sieving, obtains high stability silicon-carbon cathode
Material.
Embodiment 4
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 6.88g D50 is 200nm is mixed at normal temperature with 85.62g natural graphite and artificial graphite (mass ratio 1:1)
It closes uniformly, obtains raw material A；(2) graininess high temperature asphalt is mechanically pulverized, screening obtains the raw material B drip that D50 is about 10 μm
Green powder, it is spare；(3) by raw material A and 0.75g single-walled carbon nanotube, 0.75g multi-walled carbon nanotube, 6.25g raw material B, 12.5g
Phenolic resin is uniformly mixed at normal temperature, obtains raw material C；(4) by raw material C under helium protection, according to 15 DEG C of min-1Heating speed
Rate is warming up to 200 DEG C and carries out softening pre-coated, keeps the temperature 3h, and cooled to room temperature crushes, sieving, obtains raw material D；It (5) will be former
Material D is uniformly mixed at normal temperature with 18.75g raw material B, and heating is according to 25 DEG C of min under helium protection-1Heating rate is warming up to
1000 DEG C, 2h is kept the temperature, cooled to room temperature crushes, sieving, obtains high stability silicon-carbon cathode material.
Embodiment 5
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 4.71g D50 is 300nm is uniformly mixed at normal temperature with 89.00g soft carbon, obtains raw material A；(2) mechanical powder
Broken particle shape high temperature asphalt, screening obtains the raw material B asphalt powder that D50 is about 20 μm, spare；(3) by raw material A and 1g
Single-walled carbon nanotube, 6.24g raw material B, 9.36g glycan alcohol are uniformly mixed at normal temperature, obtain raw material C；(4) by raw material C in nitrogen
Under gas shielded, according to 15 DEG C of min-1Heating rate is warming up to 500 DEG C and carries out softening pre-coated, keeps the temperature 1.5h, naturally cools to room
Temperature crushes, sieving, obtains raw material D；(5) raw material D is uniformly mixed at normal temperature with 15.6g raw material B, is risen under nitrogen protection
Temperature is according to 25 DEG C of min-1Heating rate is warming up to 800 DEG C, keeps the temperature 4h, and cooled to room temperature crushes, sieving, obtains high stable
Property silicon-carbon cathode material.
Embodiment 6
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 4.6g D50 is 500nm is uniformly mixed at normal temperature with 89.9g artificial graphite, obtains raw material A；(2) mechanical
Grinding particulate coal tar pitch and asphalt, screening and 1:1 in mass ratio are mixed to get the raw material B that D50 is 10 μm respectively
Asphalt powder, it is spare；(3) raw material A is mixed at normal temperature with 0.5g multi-walled carbon nanotube, 6.24g raw material B, 9.36g cellulose
Uniformly, raw material C is obtained；(4) under protection of argon gas by raw material C, according to 5 DEG C of min-1Heating rate is warming up to 200 DEG C and is softened
Pre-coated, keeps the temperature 3h, and cooled to room temperature crushes, sieving, obtains raw material D；(5) by raw material D and 15.6g raw material B in room temperature
It is lower to be uniformly mixed, it is heated up under nitrogen protection according to 20 DEG C of min-1Heating rate is warming up to 700 DEG C, keeps the temperature 6h, naturally cools to
Room temperature crushes, sieving, obtains high stability silicon-carbon cathode material.
Embodiment 7
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 5.24g D50 is 100nm is uniformly mixed at normal temperature with 87.26g artificial graphite, obtains raw material A；(2) machine
Tool grinding particulate medium temperature coal pitch, screening obtains the raw material B asphalt powder that D50 is about 5 μm, spare；(3) by raw material A with
1.5g multi-walled carbon nanotube, 9.38g raw material B, 9.38g glucose are uniformly mixed at normal temperature, obtain raw material C；(4) by raw material C
Under nitrogen protection, according to 5 DEG C of min-1Heating rate is warming up to 100 DEG C and carries out softening pre-coated, keeps the temperature 3h, naturally cools to
Room temperature crushes, sieving, obtains raw material D；(5) raw material D is uniformly mixed at normal temperature with 18.75g raw material B, under nitrogen protection
Heating is according to 10 DEG C of min-1Heating rate is warming up to 800 DEG C, keeps the temperature 4h, and cooled to room temperature crushes, sieving, obtains high steady
Qualitative silicon-carbon cathode material.
Embodiment 8
Lithium battery high stability silicon-carbon cathode material in the present embodiment the preparation method is as follows:
(1) silicon that 5.18g D50 is 200nm is uniformly mixed at normal temperature with 87.8g hard carbon, obtains raw material A；(2) mechanical powder
Broken particle shape high temperature asphalt, screening obtains the raw material B asphalt powder that D50 is about 5 μm, spare；(3) raw material A and 1g is mono-
Wall carbon nano tube, 6.25g raw material B, 18.75g sucrose are uniformly mixed at normal temperature, obtain raw material C；(4) raw material C is protected in nitrogen
Under shield, according to 10 DEG C of min-1Heating rate is warming up to 250 DEG C and carries out softening pre-coated, keeps the temperature 2h, cooled to room temperature, powder
Broken, sieving, obtains raw material D；(5) raw material D is uniformly mixed at normal temperature with 12.5g raw material B, heat up under protection of argon gas according to
20℃ min-1Heating rate is warming up to 800 DEG C, keeps the temperature 5h, and cooled to room temperature crushes, sieving, obtains high stability silicon-carbon
Negative electrode material.
Comparative example 1
Si-C composite material is prepared by method substantially the same manner as Example 1, detailed process is as follows:
(1) silicon that 6.75g D50 is 200nm is uniformly mixed at normal temperature with 87.25g artificial graphite, obtains raw material A；(2) machine
Tool grinding particulate medium temperature asphalt, screening obtains the raw material B asphalt powder that D50 is about 5 μm, spare；(3) by raw material A with
1g single-walled carbon nanotube, 15.6 raw material B are uniformly mixed at normal temperature, obtain raw material C；(4) under nitrogen protection by raw material C, it presses
According to 5 DEG C of min-1Heating rate is warming up to 150 DEG C and carries out softening pre-coated, 1.5h is kept the temperature, then according to 10 DEG C of min-1Heating speed
Rate is warming up to 800 DEG C, keeps the temperature 2h, and cooled to room temperature crushes, sieving, obtains high stability silicon-carbon cathode material.
Comparative example 2
Si-C composite material is prepared according to method substantially the same manner as Example 1, detailed process is as follows:
(1) silicon that 6.75g D50 is 200nm is uniformly mixed at normal temperature with 87.25g artificial graphite, obtains raw material A；(2) will
Raw material A is uniformly mixed at normal temperature with 1g single-walled carbon nanotube, obtains Si-C composite material.
Table 1 is the chemical property of lithium battery silicon-carbon cathode material obtained in case study on implementation 1 ~ 8.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of lithium battery high stability silicon-carbon cathode material, it is characterised in that: the composite material is three layers of clad structure；
Composite inner is substrate carbon material, and middle layer is made of nano-silicon, carbon nanotube, soft carbon and/or hard carbon, outside composite material
Layer is the soft carbon layer formed after pitch is sintered.
2. lithium battery according to claim 1 high stability silicon-carbon cathode material, which is characterized in that total with composite material
On the basis of quality, the weight percent of each substance are as follows: substrate carbon material 75 ~ 90%, nano-silicon 4 ~ 12%, carbon nanotube 0.5 ~ 2%,
Soft carbon 1 ~ 4%, hard carbon 0 ~ 4%, outer layer 1 ~ 5%.
3. lithium battery according to claim 1 high stability silicon-carbon cathode material, it is characterised in that: the substrate carbon materials
Material is one or both of natural graphite, artificial graphite, carbonaceous mesophase spherules, soft carbon and hard carbon.
4. lithium battery according to claim 1 high stability silicon-carbon cathode material, it is characterised in that: the nanometer silicon grain
Degree D50 is 50 ~ 500nm, purity > 97%.
5. the preparation method of claim 1-4 described in any item lithium batteries high stability silicon-carbon cathode material, feature exist
In steps are as follows:
(1) nano-silicon and substrate carbon material are sufficiently mixed uniformly at normal temperature, obtain raw material A；
(2) graininess asphalt or coal tar pitch is mechanically pulverized, screening obtains raw material B；
(3) raw material A, raw material B, carbon nanotube, hard carbon presoma are sufficiently mixed at normal temperature, obtain raw material C；
(4) raw material C is carried out to low temperature softening pre-coated under gas shield, the block obtained after cooling crushes, screening obtains
Raw material D；
(5) raw material D is uniformly mixed at normal temperature with raw material B, the high temperature sintering under gas shield, obtained block crushes,
Screening obtains high stability silicon-carbon cathode material.
6. the lithium battery according to claim 5 preparation method of high stability silicon-carbon cathode material, it is characterised in that: institute
Stating is one of asphalt, coal tar pitch or mixture in raw material B in step (2), and wherein pitch is medium temperature or hard pitch
One of, granularity is 2 ~ 20 μm.
7. the lithium battery according to claim 5 preparation method of high stability silicon-carbon cathode material, it is characterised in that: institute
Stating hard carbon presoma in step (3) is glucose, sucrose, starch, polyvinyl alcohol, phenolic resin, epoxy resin, glycan alcohol or fibre
Tie up one of element.
8. the lithium battery according to claim 5 preparation method of high stability silicon-carbon cathode material, it is characterised in that: institute
Stating the protective gas in step (4) and step (5) is one of high pure nitrogen, argon gas, helium；Low temperature in step (4)
Condition is 100 ~ 500 DEG C, and heating rate is 5 ~ 15 DEG C of min-1, softening stress-displacement stage soaking time is 1 ~ 3h.
9. the lithium battery according to claim 5 preparation method of high stability silicon-carbon cathode material, it is characterised in that: institute
Stating step (5) high temperature sintering temperature is 700 ~ 1000 DEG C, and heating rate is 10 ~ 25 DEG C of min-1, 2 ~ 6h of soaking time.
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