CN109524641A - Lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method - Google Patents
Lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of lithium ion battery flexible self-supporting silicon/graphene negative electrode material, this method comprises: one, disperse silicon nanoparticle in heated in mixed solution after clean and be centrifuged；Two, it disperses centrifugal sediment in polydiallyldimethyl ammonium chloride solution and obtains positively charged silicon nanoparticle；Three, silicon/graphene composite thin film is filtered to obtain after silicon nanoparticle solution being added drop-wise in graphene oxide solution；Four, silicon/graphene composite thin film is subjected to high-temperature heat treatment and obtains flexible self-supporting silicon/graphene negative electrode material.Positively charged silicon nanoparticle and negatively charged graphene oxide are obtained the flexible self-supporting negative electrode material that mechanical flexibility can be excellent by electrostatic self-assembled by the present invention, the electrode of lithium ion battery can be directly prepared into it is not necessary that binder and conductive black is added, avoiding addition binder leads to the problem of reducing chemical property, and the service life of lithium ion battery is extended while guaranteeing lithium ion cell high-capacity.
Description
Technical field
The invention belongs to lithium ion battery negative material preparation technical fields, and in particular to a kind of lithium ion battery flexibility from
Support silicon/graphene negative electrode material preparation method.
Background technique
As earth energy crisis and environment are worsening, research high-efficiency cleaning is utilized, sustainable development source becomes mesh
The emphasis of preceding energy development, wherein the development of flexible lithium ion battery causes great concern.But commercial Li-ion batteries
The theoretical capacity (372mAh/g) of graphite cathode is extremely restricted, and is not able to satisfy the demand applied in high-power component.
Silicon (Si) is considered as a kind of up-and-coming lithium-ion electric because it is with highest theoretical capacity (4200mAh/g)
Pond negative electrode material.Since silicon generates great volume expansion (> 300%) in lithium ion battery charge and discharge process, thus itself
Generation dusting is broken and silicon face is exposed to the SEI film being formed continuously in electrolyte, leads to capacity fast decay, serious to limit
The business application of silicon-based anode is made.In the report of numerous lithium ion battery negative materials, usually by addition binder with
Keep composite material tight adhesion on a current collector, but this greatly hinders ion transmission, reduces chemical property.Therefore, it grinds
The flexible electrode material for studying carefully self-supporting and more efficient energy density and power density has become urgent problem to be solved.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of lithium-ion electric
Pond flexible self-supporting silicon/graphene negative electrode material preparation method.This method by positively charged silicon nanoparticle with it is negatively charged
Electrostatic self-assembled occurs between lotus graphene oxide, after heat treatment obtains the flexible self-supporting cathode material that mechanical flexibility can be good
Material, can be directly prepared into the electrode of lithium ion battery it is not necessary that binder and conductive black is added, and avoid and hinder caused by additive
Ion transmission, the problem of reducing chemical property, while avoiding the fast decay of lithium ion battery negative material capacity,
While guaranteeing lithium ion cell high-capacity, the service life of lithium ion battery is extended.
In order to solve the above technical problems, technical solution provided by the invention are as follows: lithium ion battery flexible self-supporting silicon/graphite
The preparation method of alkene negative electrode material, which is characterized in that method includes the following steps:
Step 1: dispersing silicon nanoparticle in the mixed solution of boiling and heating, after then being cleaned with deionized water
It is centrifuged；The hydrogen peroxide and water that ammonium hydroxide that the mixed solution is 25% by mass concentration, mass concentration are 20% are according to 1:
1:(4~6) volume ratio be formulated；
Step 2: it is molten to disperse polydiallyldimethyl ammonium chloride at room temperature for sediment centrifuged in step 1
It is ultrasonically treated in liquid, then successively cleans and be dried in vacuo using deionized water, obtain positively charged silicon nanoparticle；
Step 3: silicon nanoparticle positively charged obtained in step 2 is configured to nano-silicon solution and carries out ultrasound
Processing, is then added drop-wise in graphene oxide solution dropwise and forms mixed liquor, then mixed liquor is successively carried out to ultrasonic treatment and true
Empty pump filter, obtained filter residue are dried in vacuo to obtain silicon/graphene composite thin film；
Step 4: silicon obtained in step 3/graphene composite thin film is carried out high-temperature heat treatment, flexibility is obtained certainly
Support silicon/graphene negative electrode material.
The present invention first converts hydrophily SiNPs for silicon nanoparticle (SiNPs), and it is poly- to be then dispersed in strong cation
In electrolyte polydiallyldimethyl ammonium chloride solution (PDDA), positively charged SiNPs is obtained, then to be added drop-wise to graphene oxide molten
It is negatively charged due to containing the functional groups such as a large amount of carboxyl, hydroxyl in surface of graphene oxide in liquid, it is positively charged
Electrostatic self-assembled occurs between SiNPs and negatively charged graphene oxide, forms silicon/oxidation of high bond strength, space gap
Graphene composite film after heat treatment obtains the flexible self-supporting negative electrode material that mechanical flexibility can be good, can be directly prepared into lithium
Slurry is made coated in electricity is made on copper foil it is not necessary that binder and conductive black is added by traditional handicraft in the electrode of ion battery
The problem of pole avoids and hinders ion transmission caused by addition binder, reduces chemical property, simplifies preparation process,
The fast decay for avoiding lithium ion battery negative material capacity simultaneously extends while guaranteeing lithium ion cell high-capacity
The service life of lithium ion battery.
Above-mentioned lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method, which is characterized in that step
The size of silicon nanoparticle described in one is 50nm~100nm；The time of the heating is 40min.It is received using size is lesser
Rice silicon particle increases the specific surface area of negative electrode material, shortens lithium ion transport distance, is conducive to the increasing in reactivity site
Add.
Above-mentioned lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method, which is characterized in that step
The hydrogen peroxide and water that ammonium hydroxide that mixed solution described in one is 25% by mass concentration, mass concentration are 20% are according to 1:1:5's
Volume ratio is formulated.The mixed solution of above-mentioned optimum ratio is conducive to silicon nanoparticle surface generating hydroxyl, is converted into parent
Water nano silicon particle, it is easier to be dissolved into water.
Above-mentioned lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method, which is characterized in that step
The time of ultrasonic treatment described in two is 1h；The vacuum drying temperature is 80 DEG C.Make nano-silicon by controlling ultrasonic time
The positive charge that powder surface is evenly distributed.
Above-mentioned lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method, which is characterized in that step
The concentration of nano-silicon solution described in three is 1mg/mL, and the concentration of graphene oxide solution is 2mg/mL, is received in the mixed liquor
The mass ratio of rice silicon particle and graphene oxide is 1:1.It is quiet that above-mentioned technological parameter can guarantee that nano-silicon occurs with graphene oxide
Electric self assembly forms silicon/graphene composite thin film.
Above-mentioned lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method, which is characterized in that step
The time of the ultrasonic treatment of mixed liquor described in three is 1h~2h.By controlling the ultrasonic time of mixed liquor, increase silicon/graphite oxide
The mechanical stability of alkene laminated film more preferably maintains product flexibility self-supporting silicon/graphene negative electrode material integrality.
Above-mentioned lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method, which is characterized in that step
The detailed process of high-temperature heat treatment described in four are as follows: first rise to 450 DEG C with 3 DEG C/min~5 DEG C/min heating rate, then exist
Constant temperature 2h~4h in argon atmosphere.The oxidation stone in silicon/graphene composite thin film is restored by above-mentioned high-temperature heat treatment
Black alkene forms flexible self-supporting silicon/graphene negative electrode material, improves the mechanical flexibility of negative electrode material and ensure that cathode material
The stable electrochemical property of material.
Compared with the prior art, the present invention has the following advantages:
1, the present invention first converts hydrophily SiNPs for silicon nanoparticle (SiNPs), is then dispersed in strong cation
In polyelectrolyte polydiallyldimethyl ammonium chloride solution (PDDA), positively charged SiNPs is obtained, then be added drop-wise to graphene oxide
It is negatively charged due to containing the functional groups such as a large amount of carboxyl, hydroxyl in surface of graphene oxide in solution, it is positively charged
SiNPs and negatively charged graphene oxide between occur electrostatic self-assembled, form silicon/oxygen of high bond strength, space gap
Graphite alkene laminated film after heat treatment obtains the flexible self-supporting negative electrode material that mechanical flexibility can be good, can be directly prepared into
Slurry is made coated in electricity is made on copper foil it is not necessary that binder and conductive black is added by traditional handicraft in the electrode of lithium ion battery
The problem of pole avoids and hinders ion transmission caused by addition binder, reduces chemical property；In the negative electrode material structure
Graphene oxide flexible is sufficiently wrapped in around silicon nanoparticle, to inhibit silicon in lithium ion battery charge and discharge process
Middle to generate great volume expansion, the dusting for avoiding negative electrode material is broken, promotes the diffusion and transmission of lithium ion and electronics,
In addition, the graphene in the negative electrode material structure effectively prevents silicon nanoparticle to contact with the direct of electrolyte, reduce silicon
Surface is exposed to the SEI film formed in electrolyte, and then avoids the fast decay of lithium ion battery negative material capacity, is protecting
While demonstrate,proving lithium ion cell high-capacity, the service life of lithium ion battery is extended.
2, the present invention using ultrasonic treatment further enhance positively charged SiNPs and negatively charged graphene oxide it
Between mechanical force combination, and with electrostatic self-assembled collective effect, the space gap structure of formation reduces silicon nanoparticle
Internal stress, enhance the specific area of negative electrode material, promote the diffusion and transmission of lithium ion and electronics, and be lithium-ion electric
Pond electrochemical reaction provides more active sites.
3, the present invention restores the graphene oxide in silicon/graphene composite thin film by high-temperature heat treatment, is formed soft
Property self-supporting silicon/graphene negative electrode material, improves the mechanical flexibility of negative electrode material.
4, flexible self-supporting of the invention silicon/graphene negative electrode material combines under the action of electrostatic self-assembled and mechanical force
Film forming, prepares in electrode process without adding binder and conductive black, without copper foil as collector can self film, keep away
Exempt from the problem of hindering ion transmission caused by addition binder, reducing chemical property, simplifies preparation process.
5, silicon prepared by the present invention/graphene negative electrode material has excellent cyclical stability and high rate performance.
Below by drawings and examples, the present invention is described in further detail.
Detailed description of the invention
Fig. 1 is preparation reaction mechanism figure of the invention.
Fig. 2 is silicon/graphene negative electrode material scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1.
Fig. 3 is silicon/graphene negative electrode material XRD diagram prepared by the embodiment of the present invention 1.
Fig. 4 is that silicon/constant current of the graphene negative electrode material under 0.2A/g current density prepared by the embodiment of the present invention 1 fills
Discharge curve.
Fig. 5 is silicon/cycle performance of the graphene negative electrode material under 0.2A/g current density prepared by the embodiment of the present invention 1
Curve graph.
Fig. 6 is silicon/graphene negative electrode material high rate performance curve graph prepared by the embodiment of the present invention 1.
Specific embodiment
Silicon nanoparticle (SiNPs) first turns the preparation reaction mechanism figure of 1~embodiment of the embodiment of the present invention 4 as shown in Figure 1:
Hydrophily SiNPs is turned to, then hydrophily SiNPs is dispersed in polydiallyldimethyl ammonium chloride solution (PDDA), is obtaining band just
The SiNPs of charge；It is negatively charged containing the functional groups such as a large amount of carboxyl, hydroxyl in surface of graphene oxide, when will be positively charged
When the SiNPs of lotus and negatively charged graphene oxide contact, electrostatic self-assembled occurs for the two, forms high bond strength, space empty
Silicon/graphene composite thin film of gap.
Embodiment 1
The preparation method of the present embodiment the following steps are included:
Step 1: dispersing 200mg silicon nanoparticle in the mixed solution of 250mL boiling and heating 40min, then use
Deionized water is centrifuged after cleaning 3 times；The size of the silicon nanoparticle is 50nm~100nm；The mixed solution is by matter
Amount concentration be 25% ammonium hydroxide, mass concentration be 20% hydrogen peroxide and water be formulated according to the volume ratio of 1:1:5；
Step 2: it is molten to disperse polydiallyldimethyl ammonium chloride at room temperature for sediment centrifuged in step 1
Ultrasonic treatment 1h is carried out in liquid, is then successively cleaned 5 times using deionized water, is dried in vacuo under conditions of 80 DEG C, obtains band
The silicon nanoparticle of positive charge；
Step 3: it is receiving for 1mg/mL that silicon nanoparticle positively charged obtained in step 2, which is configured to 20mL concentration,
Rice silicon solution is simultaneously ultrasonically treated, and is then added drop-wise to be formed in the graphene oxide solution that 10mL concentration is 2mg/mL dropwise and be mixed
Liquid is closed, then mixed liquor is successively carried out to ultrasonic treatment 2h and vacuum filtration, it is dry that obtained filter residue is put into progress vacuum in culture dish
It is dry to obtain silicon/graphene composite thin film；
It is carried out at high warm Step 4: silicon/graphene composite thin film obtained in step 3 is placed in tube furnace
Reason, obtains flexible self-supporting silicon/graphene negative electrode material；The detailed process of the high-temperature heat treatment are as follows: first with the liter of 5 DEG C/min
Warm rate rises to 450 DEG C, then the constant temperature 2h in argon atmosphere.
Fig. 2 is silicon manufactured in the present embodiment/graphene negative electrode material scanning electron microscope (SEM) photograph, figure it is seen that this implementation
The graphene film containing nano Si particle and fold in silicon/graphene negative electrode material of example preparation, and nano Si particle point
Cloth is uniform, forms with a kind of tulle chondritic.
Fig. 3 is silicon manufactured in the present embodiment/graphene negative electrode material XRD diagram, from figure 3, it can be seen that oxygen reduction fossil
Black alkene corresponds to graphite (002) crystal face in 25 ° of diffraction maximums, shows that graphene oxide is successfully reduced to graphene, silicon/graphene is negative
The XRD diffraction maximum position of pole material is consistent with nano Si and graphene resultant peak, shows that nano Si particle is effectively embedded to
In graphene layer.
Detection can be carried out to flexible self-supporting silicon/graphene negative electrode material electrochemistry that the present embodiment is prepared,
Detailed process are as follows: in water and oxygen content all in the 0.1ppm glove box below full of argon gas, with flexible self-supporting silicon/stone
Black alkene negative electrode material is cathode, and lithium piece is to electrode, with polypropylene screen (Celgard 2400) for diaphragm, with 1mol/L hexafluoro phosphorus
Sour lithium (LiPF6) to be dissolved in ethylene carbonate (EC) that volume ratio is 1:1 and the mixed solution of dimethyl carbonate (DMC) be to be electrolysed
Liquid is assembled to form button cell, carries out electro-chemical test after standing 12h at room temperature, as a result as shown in Figure 4, Figure 5 and Figure 6.
Fig. 4 is silicon manufactured in the present embodiment/constant current charge-discharge of the graphene negative electrode material under 0.2A/g current density
Curve graph, Fig. 5 are cycle performance curve of the silicon manufactured in the present embodiment/graphene negative electrode material under 0.2A/g current density
Figure, as can be seen from Figure 4 and Figure 5, silicon manufactured in the present embodiment/graphene negative electrode material under the current density of 0.2A/g,
First charge-discharge specific capacity is respectively 1515mAh/g and 1986.5mAh/g, and coulombic efficiency is 76.26% for the first time, second of charge and discharge
Electric specific capacity is respectively 1453.2mAh/g and 1463.3mAh/g, and second of coulombic efficiency is 99.31%, the 5th charge and discharge ratio
Capacity is respectively 1442.24mAh/g and 1444.1mAh/g, and the 5th coulombic efficiency is 99.86%, with the increasing of cycle-index
Add, charging and discharging curve has good repeatability, illustrates that silicon manufactured in the present embodiment/graphene negative electrode material has and fills well
Discharge cycles stability.
Fig. 6 is silicon manufactured in the present embodiment/graphene negative electrode material high rate performance curve graph, from fig. 6, it can be seen that this
Silicon/graphene negative electrode material high rate performance of embodiment preparation is excellent, and small electricity is especially then returned to after high current charge-discharge
Charge and discharge are flowed, silicon/graphene negative electrode material specific capacity can restore preferable level, illustrate silicon/graphite manufactured in the present embodiment
Alkene negative electrode material has excellent high rate performance, and the charge-discharge performance under the current density of 0.2A/g is best.
Embodiment 2
The preparation method of the present embodiment the following steps are included:
Step 1: dispersing 200mg silicon nanoparticle in the mixed solution of 250mL boiling and heating 40min, then use
Deionized water is centrifuged after cleaning 3 times；Ammonium hydroxide that the mixed solution is 25% by mass concentration, mass concentration are 20%
Hydrogen peroxide and water are formulated according to the volume ratio of 1:1:4；
Step 2: it is molten to disperse polydiallyldimethyl ammonium chloride at room temperature for sediment centrifuged in step 1
Ultrasonic treatment 1h is carried out in liquid, is then successively cleaned 5 times using deionized water, is dried in vacuo under conditions of 80 DEG C, obtains band
The silicon nanoparticle of positive charge；
Step 3: it is receiving for 1mg/mL that silicon nanoparticle positively charged obtained in step 2, which is configured to 20mL concentration,
Rice silicon solution is simultaneously ultrasonically treated, and is then added drop-wise to be formed in the graphene oxide solution that 10mL concentration is 2mg/mL dropwise and be mixed
Liquid is closed, then mixed liquor is successively carried out to ultrasonic treatment 1.5h and vacuum filtration, obtained filter residue, which is put into culture dish, carries out vacuum
It is dried to obtain silicon/graphene composite thin film；
It is carried out at high warm Step 4: silicon/graphene composite thin film obtained in step 3 is placed in tube furnace
Reason, obtains flexible self-supporting silicon/graphene negative electrode material；The detailed process of the high-temperature heat treatment are as follows: first with the liter of 5 DEG C/min
Warm rate rises to 450 DEG C, then the constant temperature 2h in argon atmosphere.
Detection can be carried out to flexible self-supporting silicon/graphene negative electrode material electrochemistry that the present embodiment is prepared,
The flexible self-supporting silicon being prepared in detailed process and embodiment 1/graphene negative electrode material chemical property detection process phase
Together, as the result is shown the present embodiment be prepared Si/ graphene composite material first charge-discharge specific capacity be respectively 1423mAh/g and
1876.2mAh/g, coulombic efficiency is 75.84% for the first time.
Embodiment 3
The preparation method of the present embodiment the following steps are included:
Step 1: dispersing 200mg silicon nanoparticle in the mixed solution of 250mL boiling and heating 40min, then use
Deionized water is centrifuged after cleaning 3 times；Ammonium hydroxide that the mixed solution is 25% by mass concentration, mass concentration are 20%
Hydrogen peroxide and water are formulated according to the volume ratio of 1:1:5；
Step 2: it is molten to disperse polydiallyldimethyl ammonium chloride at room temperature for sediment centrifuged in step 1
Ultrasonic treatment 1h is carried out in liquid, is then successively cleaned 5 times using deionized water, is dried in vacuo under conditions of 80 DEG C, obtains band
The silicon nanoparticle of positive charge；
Step 3: it is receiving for 1mg/mL that silicon nanoparticle positively charged obtained in step 2, which is configured to 20mL concentration,
Rice silicon solution is simultaneously ultrasonically treated, and is then added drop-wise to be formed in the graphene oxide solution that 10mL concentration is 2mg/mL dropwise and be mixed
Liquid is closed, then mixed liquor is successively carried out to ultrasonic treatment 2h and vacuum filtration, it is dry that obtained filter residue is put into progress vacuum in culture dish
It is dry to obtain silicon/graphene composite thin film；
It is carried out at high warm Step 4: silicon/graphene composite thin film obtained in step 3 is placed in tube furnace
Reason, obtains flexible self-supporting silicon/graphene negative electrode material；The detailed process of the high-temperature heat treatment are as follows: first with the liter of 3 DEG C/min
Warm rate rises to 450 DEG C, then the constant temperature 3h in argon atmosphere.
Detection can be carried out to flexible self-supporting silicon/graphene negative electrode material electrochemistry that the present embodiment is prepared,
The flexible self-supporting silicon being prepared in detailed process and embodiment 1/graphene negative electrode material chemical property detection process phase
Together, as the result is shown the present embodiment be prepared Si/ graphene composite material first charge-discharge specific capacity be respectively 1501mAh/g and
1961.7mAh/g, coulombic efficiency is 76.46% for the first time.
Embodiment 4
The preparation method of the present embodiment the following steps are included:
Step 1: dispersing 200mg silicon nanoparticle in the mixed solution of 250mL boiling and heating 40min, then adopt
It is centrifuged after cleaning 3 times with deionized water；Ammonium hydroxide that the mixed solution is 25% by mass concentration, mass concentration 20%
Hydrogen peroxide and water be formulated according to the volume ratio of 1:1:6；
Step 2: it is molten to disperse polydiallyldimethyl ammonium chloride at room temperature for sediment centrifuged in step 1
Ultrasonic treatment 1h is carried out in liquid, is then successively cleaned 5 times using deionized water, is dried in vacuo under conditions of 80 DEG C, obtains band
The silicon nanoparticle of positive charge；
Step 3: it is receiving for 1mg/mL that silicon nanoparticle positively charged obtained in step 2, which is configured to 20mL concentration,
Rice silicon solution is simultaneously ultrasonically treated, and is then added drop-wise to be formed in the graphene oxide solution that 10mL concentration is 2mg/mL dropwise and be mixed
Liquid is closed, then mixed liquor is successively carried out to ultrasonic treatment 1h and vacuum filtration, it is dry that obtained filter residue is put into progress vacuum in culture dish
It is dry to obtain silicon/graphene composite thin film；
It is carried out at high warm Step 4: silicon/graphene composite thin film obtained in step 3 is placed in tube furnace
Reason, obtains flexible self-supporting silicon/graphene negative electrode material；The detailed process of the high-temperature heat treatment are as follows: first with the liter of 4 DEG C/min
Warm rate rises to 450 DEG C, then the constant temperature 4h in argon atmosphere.
Detection can be carried out to flexible self-supporting silicon/graphene negative electrode material electrochemistry that the present embodiment is prepared,
The flexible self-supporting silicon being prepared in detailed process and embodiment 1/graphene negative electrode material chemical property detection process phase
Together, as the result is shown the present embodiment be prepared Si/ graphene composite material first charge-discharge specific capacity be respectively 1326mAh/g and
1886.2mAh/g, coulombic efficiency is 75.84% for the first time.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (7)
1. lithium ion battery flexible self-supporting silicon/graphene negative electrode material preparation method, which is characterized in that this method include with
Lower step:
Step 1: dispersing silicon nanoparticle in the mixed solution of boiling and heating, carried out after then being cleaned with deionized water
Centrifugation；The hydrogen peroxide and water that ammonium hydroxide that the mixed solution is 25% by mass concentration, mass concentration are 20% are according to 1:1:(4
~6) volume ratio is formulated；
Step 2: dispersing sediment centrifuged in step 1 in polydiallyldimethyl ammonium chloride solution at room temperature
It is ultrasonically treated, then successively cleans and be dried in vacuo using deionized water, obtain positively charged silicon nanoparticle；
Step 3: silicon nanoparticle positively charged obtained in step 2 is configured to nano-silicon solution and carries out ultrasonic place
Reason, is then added drop-wise in graphene oxide solution dropwise and forms mixed liquor, then mixed liquor is successively carried out to ultrasonic treatment and vacuum
It filters, obtained filter residue is dried in vacuo to obtain silicon/graphene composite thin film；
Step 4: silicon obtained in step 3/graphene composite thin film is carried out high-temperature heat treatment, flexible self-supporting is obtained
Silicon/graphene negative electrode material.
2. the preparation method of lithium ion battery flexible self-supporting silicon/graphene negative electrode material according to claim 1, special
Sign is that the size of silicon nanoparticle described in step 1 is 50nm~100nm；The time of the heating is 40min.
3. the preparation method of lithium ion battery flexible self-supporting silicon/graphene negative electrode material according to claim 1, special
Sign is, the hydrogen peroxide and water that ammonium hydroxide that mixed solution described in step 1 is 25% by mass concentration, mass concentration are 20%
It is formulated according to the volume ratio of 1:1:5.
4. the preparation method of lithium ion battery flexible self-supporting silicon/graphene negative electrode material according to claim 1, special
Sign is that the time of ultrasonic treatment described in step 2 is 1h；The vacuum drying temperature is 80 DEG C.
5. the preparation method of lithium ion battery flexible self-supporting silicon/graphene negative electrode material according to claim 1, special
Sign is that the concentration of nano-silicon solution described in step 3 is 1mg/mL, and the concentration of graphene oxide solution is 2mg/mL, described
The mass ratio of silicon nanoparticle and graphene oxide is 1:1 in mixed liquor.
6. the preparation method of lithium ion battery flexible self-supporting silicon/graphene negative electrode material according to claim 1, special
Sign is that the time of the ultrasonic treatment of mixed liquor described in step 3 is 1h~2h.
7. the preparation method of lithium ion battery flexible self-supporting silicon/graphene negative electrode material according to claim 1, special
Sign is, the detailed process of high-temperature heat treatment described in step 4 are as follows: is first risen to 3 DEG C/min~5 DEG C/min heating rate
450 DEG C, then constant temperature 2h~4h in argon atmosphere.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114725322A (en) * | 2022-04-29 | 2022-07-08 | 南京工业大学 | Preparation method of silicon-titanium dioxide-graphene flexible self-supporting electrode |
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| CN110112380A (en) * | 2019-04-08 | 2019-08-09 | 新奥石墨烯技术有限公司 | A kind of core-shell type graphene-silicon composite and preparation method thereof, electrode material and battery |
| CN110112408A (en) * | 2019-04-08 | 2019-08-09 | 新奥石墨烯技术有限公司 | A kind of graphene-silicon composite and preparation method thereof, electrode material and battery |
| CN110364687A (en) * | 2019-07-30 | 2019-10-22 | 唐山学院 | A kind of preparation method of fexible film electrode and prepared electrode and purposes |
| CN110993895B (en) * | 2019-12-04 | 2022-04-19 | 绍兴文理学院 | Preparation method of Si/graphene composite flexible electrode of lithium ion battery |
| CN110993895A (en) * | 2019-12-04 | 2020-04-10 | 绍兴文理学院 | Preparation method of Si/graphene composite flexible electrode of lithium ion battery |
| CN111081981A (en) * | 2019-12-20 | 2020-04-28 | 中国电子科技集团公司第十八研究所 | Preparation method of self-supporting double-sided silicon-graphene composite cathode |
| CN111180686A (en) * | 2019-12-29 | 2020-05-19 | 华东理工大学 | Preparation method of flexible self-supporting silicon-based lithium ion battery cathode material |
| CN111969193A (en) * | 2020-08-26 | 2020-11-20 | 中北大学 | Si @ MXene nano composite material and preparation method thereof |
| CN112186159A (en) * | 2020-09-29 | 2021-01-05 | 江苏福瑞士电池科技有限公司 | Preparation method of nitrogen-doped modified silicon/graphite/graphene composite material |
| CN112186159B (en) * | 2020-09-29 | 2022-05-10 | 江苏福瑞士电池科技有限公司 | Preparation method of nitrogen-doped modified silicon/graphite/graphene composite material |
| CN114613971A (en) * | 2022-03-31 | 2022-06-10 | 南京工业大学 | Preparation method and application of compact and stable pomegranate-shaped silicon-graphene composite electrode material |
| CN114853361A (en) * | 2022-04-14 | 2022-08-05 | 伊诺福科光学技术有限公司 | Application of water bath ultrasound in layer-by-layer self-assembly of graphene metamaterial thin film |
| CN114725322A (en) * | 2022-04-29 | 2022-07-08 | 南京工业大学 | Preparation method of silicon-titanium dioxide-graphene flexible self-supporting electrode |
| CN114725322B (en) * | 2022-04-29 | 2023-09-08 | 南京工业大学 | Preparation method of silicon-titanium dioxide-graphene flexible self-supporting electrode |
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