CN107895782A - A kind of preparation method of composite cathode material for lithium ion cell - Google Patents
A kind of preparation method of composite cathode material for lithium ion cell Download PDFInfo
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- CN107895782A CN107895782A CN201711037470.5A CN201711037470A CN107895782A CN 107895782 A CN107895782 A CN 107895782A CN 201711037470 A CN201711037470 A CN 201711037470A CN 107895782 A CN107895782 A CN 107895782A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：Step 1：Graphene oxide solution and nano silicasol are taken in methanol, methyl methacrylate and azodiisobutyronitrile is added, is stirred under the atmosphere of nitrogen, Primary product GO/Si/PMMA is made；Step 2：Take pyrroles to be dissolved in methanol, form chromium solution；Preliminary composite GO/Si/PMMA made from step 1 is stirred by ultrasonic, the chromium solution is then added and is put into ice-water bath and stir, centrifugation is stirred after adding oxidant, and centrifugation product is dried in vacuo, combination product PPy/G/Si/PMMA is made；Step 3：Combination product PPy/G/Si/PMMA made from step 2 is calcined under the atmosphere of nitrogen, final composite negative pole material G/Si/C is made.
Description
【Technical field】
The present invention relates to battery material technical field, more particularly to a kind of preparation side of composite cathode material for lithium ion cell
Method.
【Background technology】
Lithium ion battery is because having the extensive use in each type electric tool of higher energy density and long-life.At present, often
Negative electrode of lithium ion battery is graphite, and the limited storage lithium ability (372mAh/g) of graphite cathode causes using graphite as negative pole
Lithium ion battery people can not be met to the higher and higher requirement of energy density.
Silica-base material has preferably theoretical storage lithium ability (3579mAh/g), can form Li15Si4Alloy, and it is cheap,
Security is good, turns into the brand-new material of negative electrode of lithium ion battery.However, during lithium ion deintercalation, silica-base material it is swollen
Swollen rate is up to 300%, causes material disintegrating, and the connectivity between particle and particle, between particle and collector is deteriorated, and causes to hold
Measure rapid decay.
In consideration of it, it is real be necessary to provide a kind of preparation method of new composite cathode material for lithium ion cell with overcome with
Upper defect.
【The content of the invention】
It is an object of the invention to provide one kind can effectively suppress volumetric expansion, silicon is distributed on graphene, it is porous to have
Structure and larger specific surface area, the lithium-ion electric with excellent reversible capacity, high chemical property and cyclical stability
The preparation method of pond composite negative pole material.
To achieve these goals, the present invention provides a kind of preparation method of composite cathode material for lithium ion cell, including
Following steps：Step 1：Graphene oxide solution and nano silicasol are taken in methanol, adds methyl methacrylate and azo two
Isobutyronitrile, stirred under the atmosphere of nitrogen, Primary product GO/Si/PMMA is made；Step 2：Take pyrroles to be dissolved in methanol, formed
Chromium solution；Preliminary composite GO/Si/PMMA made from step 1 is stirred by ultrasonic, it is molten then to add the pyrroles
Liquid and being put into ice-water bath is stirred, and centrifugation is stirred after adding oxidant, and centrifugation product is dried in vacuo, and compound production is made
Thing PPy/G/Si/PMMA；Step 3：Combination product PPy/G/Si/PMMA made from step 2 is calcined under the atmosphere of nitrogen,
Final composite negative pole material G/Si/C is made.
In a preferred embodiment, the graphite oxide in the nano-silicon and graphene oxide solution in the step 1
The mass ratio of alkene is 20：1~60：1.
In a preferred embodiment, the quality of the graphene oxide in the graphene oxide solution in the step 1
Fraction is 5%.
In a preferred embodiment, the mass ratio of the quality of the pyrroles in the step 2 and oxidant be 17%~
24%.
In a preferred embodiment, the oxidant in the step 2 is FeCl3·6H2O or Fe2O3。
In a preferred embodiment, the vacuum drying drying temperature in the step 2 is 80 DEG C, vacuum drying
Time is 12h.
In a preferred embodiment, the time being stirred by ultrasonic in the step 2 is 10~30min.
In a preferred embodiment, the temperature calcined in a nitrogen atmosphere in the step 3 is 400 DEG C and 700
DEG C, for the PPy in combination product PPy/G/Si/PMMA made from the step 2 and PMMA to be pyrolyzed.
Compared to prior art, the preparation method of composite cathode material for lithium ion cell provided by the invention, preparation is answered
The carbon skeleton that condensation material adulterates for the N of loose structure, effectively inhibits volumetric expansion, has larger specific surface area, reversible appearance
Amount is big；Elementary silicon is distributed on graphene film so that material has good electric conductivity, and the battery of preparation has good electricity
Chemical property and cyclical stability.
【Brief description of the drawings】
Fig. 1 is the surface sweeping electron microscope of the Primary product GO/Si/PMMA prepared by (1) in embodiment 1 provided by the invention；
Fig. 2 is the transmission electron microscope picture of the Primary product GO/Si/PMMA prepared by (1) in embodiment 1 provided by the invention；
Fig. 3 is the surface sweeping Electronic Speculum of the combination product PPy/G/Si/PMMA prepared by (2) in embodiment 1 provided by the invention
Figure；
Fig. 4 is the transmission electron microscope of the combination product PPy/G/Si/PMMA prepared by (2) in embodiment 1 provided by the invention
Figure；
The surface sweeping electricity that Fig. 5 is the final composite negative pole material G/Si/C prepared by (3) in embodiment 1 provided by the invention
Mirror figure；
Fig. 6 is the synthesis step figure of the preparation method of composite cathode material for lithium ion cell provided by the invention；
Fig. 7 is the charging and discharging curve figure of 1~6 week of test battery corresponding to embodiment 1 provided by the invention；
Fig. 8 is the cycle performance figure of test battery corresponding to embodiment 1 provided by the invention.
【Embodiment】
In order that the purpose of the present invention, technical scheme and advantageous effects become apparent from understanding, below in conjunction with accompanying drawing and
Embodiment, the present invention will be described in further detail.It should be appreciated that the specific implementation described in this specification
Mode is not intended to limit the present invention just for the sake of explaining the present invention.
The present invention provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
Step 1：Graphene oxide (GO) solution and nano silicasol are taken in methanol, adds methyl methacrylate (MMA)
And azodiisobutyronitrile (ABIN), stirred under the atmosphere of nitrogen, Primary product GO/Si/PMMA is made；
Step 2：Take pyrroles (Py) to be dissolved in methanol, form chromium solution；By preliminary composite made from step 1
GO/Si/PMMA is stirred by ultrasonic, and is then added the chromium solution and is put into ice-water bath and stirs, and is stirred after adding oxidant
Centrifugation is mixed, and centrifugation product is dried in vacuo, combination product PPy/G/Si/PMMA is made；
Step 3：Combination product PPy/G/Si/PMMA made from step 2 is calcined under the atmosphere of nitrogen, is made final
Composite negative pole material G/Si/C.
Specifically, the mass ratio of the graphene oxide in nano-silicon and graphene oxide solution in the step 1 is
20：1~60：1；The mass fraction of the graphene oxide in graphene oxide solution in the step 1 is 5%.
Specifically, the quality of pyrroles and the mass ratio of oxidant in the step 2 are 17%~24%；The step
Oxidant in two is FeCl3·6H2O or Fe2O3.Vacuum drying drying temperature in the step 2 is 80 DEG C, and vacuum is done
The dry time is 12h.The time being stirred by ultrasonic in the step 2 is 10~30min.
Specifically, the temperature calcined in a nitrogen atmosphere in the step 3 is 400 DEG C and 700 DEG C, for by the step
PPy and PMMA pyrolysis in combination product PPy/G/Si/PMMA made from rapid two, after PMMA pyrolysis, still retain its original C
Skeleton structure.
Embodiment 1：
(1) 6mg graphene oxide water solutions (wherein, the mass fraction 5% of graphene oxide), 8mg nano silicasol are taken
In 7mL methanol, 4ml methyl methacrylates and 30mg azodiisobutyronitriles are added, 60 DEG C of stirring 1h under the atmosphere of nitrogen,
Primary product GO/Si/PMMA is made；
(2) take 50mg pyrroles to be dissolved in 1ml methanol, form chromium solution；By preliminary composite GO/Si/ made from (1)
PMMA carries out ultrasonic agitation 15min, then adds the chromium solution and is put into ice-water bath and stirs 1h, adds
241.7mgFeCl3·6H2Centrifugation is stirred after O, and centrifugation product is dried in vacuo 12h in 80 DEG C of baking boxs, combination product is made
PPy/G/Si/PMMA；
(3) combination product PPy/G/Si/PMMA made from (2) is forged under the atmosphere of 400 DEG C and 700 DEG C of nitrogen respectively
Burn, final composite negative pole material G/Si/C is made.
Embodiment 2：
(1) 6mg graphene oxide water solutions (wherein, the mass fraction 5% of graphene oxide), 12mg nano silicasol are taken
In 7mL methanol, 4ml methyl methacrylates and 30mg azodiisobutyronitriles are added, 60 DEG C of stirring 1h under the atmosphere of nitrogen,
Primary product GO/Si/PMMA is made；
(2) take 50mg pyrroles to be dissolved in 1ml methanol, form chromium solution；By preliminary composite GO/Si/ made from (1)
PMMA carries out ultrasonic agitation 15min, then adds the chromium solution and is put into ice-water bath and stirs 1h, adds
241.7mgFeCl3·6H2Centrifugation is stirred after O, and centrifugation product is dried in vacuo 12h in 80 DEG C of baking boxs, combination product is made
PPy/G/Si/PMMA；
(3) combination product PPy/G/Si/PMMA made from (2) is forged under the atmosphere of 400 DEG C and 700 DEG C of nitrogen respectively
Burn, final composite negative pole material G/Si/C is made.
Fig. 1 is the surface sweeping electron microscope of the Primary product GO/Si/PMMA prepared by (1) in embodiment 1 provided by the invention；
Fig. 2 is the transmission electron microscope picture of the Primary product GO/Si/PMMA prepared by (1) in embodiment 1 provided by the invention；By Fig. 1 and figure
2 as can be seen that GO/PMMA spherical particle diameters are about 300nm, and PMMA is oxidized graphene film cladding, Si nano-particles point
Cloth is on graphene oxide sheet, and therefore, Si is uniformly distributed in PMMA particle surfaces, almost without discovery silicon inside PMMA particles
Particle, this shows there is good interaction between silicon and graphene oxide sheet, and Si is all distributed on graphene oxide sheet.
Fig. 3 is the surface sweeping Electronic Speculum of the combination product PPy/G/Si/PMMA prepared by (2) in embodiment 1 provided by the invention
Figure；Fig. 4 is the transmission electron microscope picture of the combination product PPy/G/Si/PMMA prepared by (2) in embodiment 1 provided by the invention；By
Fig. 3 and Fig. 4 understands that the Py of addition is after polymerization, and due to polypyridine PPy around G/Si/PMMA be present, grain diameter has increased
(300~500nm) greatly, polypyridine PPy are not infiltrated into inside PMMA, but are deposited on its surface.
The surface sweeping electricity that Fig. 5 is the final composite negative pole material G/Si/C prepared by (3) in embodiment 1 provided by the invention
Mirror figure；As shown in Figure 5, under nitrogen atmosphere, the network structure of the PMMA and PPy porous N doped carbons of pyrolysis generation, GO warps under high temperature
Py reduces to form G.
Specific synthesis step, referring to Fig. 6, Fig. 6 is the system of composite cathode material for lithium ion cell provided by the invention
The synthesis step figure of Preparation Method.
The final composite negative pole material G/Si/C prepared using the embodiment of the present invention 1, prepare test battery；To test electricity
Pond carries out electrochemical property test, and test electric current is 0.14A/g, and test voltage is 0.01~1V.
Fig. 7 is the charging and discharging curve figure of 1~6 week of test battery corresponding to embodiment 1 provided by the invention；Can by Fig. 7
Know, in first time discharge curve (1st) in, there are two gentle 0.8V and 0.1V voltage platforms, be corresponding to 0.8V platforms
The formation of composite material surface SEI films, platform long 0.1V are the processes that monocrystalline silicon and lithium ion form silicon lithium alloy.
Fig. 8 is the cycle performance figure of test battery corresponding to embodiment 1 provided by the invention；As seen from Figure 8,
Coulombic efficiency is maintained at 100% or so after two weeks, and specific discharge capacity can still keep 740mAh/g after 125 weeks, has well
Cycle performance.
The preparation method of composite cathode material for lithium ion cell provided by the invention, the composite of preparation is loose structure
N doping carbon skeleton, effectively inhibit volumetric expansion, there is larger specific surface area, reversible capacity is big；Elementary silicon is distributed in
On graphene film so that material has good electric conductivity, and the battery of preparation has good chemical property and circulation steady
It is qualitative.
The present invention is not restricted to described in specification and embodiment, therefore for the personnel of familiar field
Additional advantage and modification is easily achieved, therefore in the essence of the universal limited without departing substantially from claim and equivalency range
In the case of refreshing and scope, the present invention is not limited to specific details, representational equipment and shown here as the diagram with description
Example.
Claims (8)
- A kind of 1. preparation method of composite cathode material for lithium ion cell, it is characterised in that：Comprise the following steps：Step 1：Graphene oxide solution and nano silicasol are taken in methanol, adds methyl methacrylate and the isobutyl of azo two Nitrile, stirred under the atmosphere of nitrogen, Primary product GO/Si/PMMA is made；Step 2：Take pyrroles to be dissolved in methanol, form chromium solution；By preliminary composite GO/Si/PMMA made from step 1 It is stirred by ultrasonic, then adds the chromium solution and be put into ice-water bath and stir, centrifugation is stirred after adding oxidant, and will Centrifugation product is dried in vacuo, and combination product PPy/G/Si/PMMA is made；Step 3：Combination product PPy/G/Si/PMMA made from step 2 is calcined under the atmosphere of nitrogen, is made final and answers Close negative material G/Si/C.
- 2. the preparation method of composite cathode material for lithium ion cell as claimed in claim 1, it is characterised in that：The step 1 In nano-silicon and graphene oxide solution in graphene oxide mass ratio be 20：1~60：1.
- 3. the preparation method of composite cathode material for lithium ion cell as claimed in claim 2, it is characterised in that：The step 1 In graphene oxide solution in graphene oxide mass fraction be 5%.
- 4. the preparation method of composite cathode material for lithium ion cell as claimed in claim 3, it is characterised in that：The step 2 In pyrroles quality and oxidant mass ratio be 17%~24%.
- 5. the preparation method of composite cathode material for lithium ion cell as claimed in claim 4, it is characterised in that：The step 2 In oxidant be FeCl3·6H2O or Fe2O3。
- 6. the preparation method of composite cathode material for lithium ion cell as claimed in claim 5, it is characterised in that：The step 2 In vacuum drying drying temperature be 80 DEG C, vacuum drying time 12h.
- 7. the preparation method of composite cathode material for lithium ion cell as claimed in claim 6, it is characterised in that：The step 2 The time of middle ultrasonic agitation is 10~30min.
- 8. the preparation method of composite cathode material for lithium ion cell as claimed in claim 7, it is characterised in that：The step 3 In the temperature calcined in a nitrogen atmosphere be 400 DEG C and 700 DEG C, for by combination product PPy/G/ made from the step 2 PPy and PMMA pyrolysis in Si/PMMA.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878834A (en) * | 2018-06-28 | 2018-11-23 | 重庆大学 | A kind of preparation method of graphene/silicon/carbon compound cathode materials |
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2017
- 2017-10-30 CN CN201711037470.5A patent/CN107895782A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| WALID ALKARMO等: ""Nanostructured 3D porous hybrid network of N-doped carbon, graphene and Si nanoparticles as an anode material for Li-ion batteries"", 《NEW J. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878834A (en) * | 2018-06-28 | 2018-11-23 | 重庆大学 | A kind of preparation method of graphene/silicon/carbon compound cathode materials |
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