CN108258214A - A kind of preparation method of lithium ion battery negative material silicon@graphene/carbons - Google Patents
A kind of preparation method of lithium ion battery negative material silicon@graphene/carbons Download PDFInfo
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- CN108258214A CN108258214A CN201810013795.8A CN201810013795A CN108258214A CN 108258214 A CN108258214 A CN 108258214A CN 201810013795 A CN201810013795 A CN 201810013795A CN 108258214 A CN108258214 A CN 108258214A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of preparation method of lithium ion battery negative material silicon@graphene/carbon compounds, including：A certain proportion of graphene oxide powder is taken, is dissolved in proper amount of glycol, adds suitable silicon tetrachloride, treats to dry to obtain silica@graphene oxide powders after reaction；Silica@graphene oxide powders are placed in crucible, it is calcined, after isothermal holding, it is cooled to room temperature, obtain silica@graphene powders, after silica@graphene powders after drying are mixed, calcined according to certain mass ratio with magnesium powder, calcined product is washed, dries to obtain precursor silicon@graphene powders.Then using acetylene as cracking gas, carbon coating is carried out to precursor using chemical vapour deposition technique, obtains silicon@graphene/carbons.Negative material cyclical stability prepared by method using the present invention is good, and high rate performance is excellent.
Description
Technical field
The invention belongs to new materials and electrochemical field, and in particular to and a kind of lithium ion battery negative material silicon@graphenes/
The preparation method of carbon.
Technical background
The research hotspot of current lithium ion battery negative material is the electrode material with height ratio capacity.Silicon is as a kind of
Electrode material with height ratio capacity starts to be paid close attention to by researcher, and alloying reaction life occurs in charge and discharge process for silicon
Into Li3.75Si, the specific capacity shown（3589 mAh g-1）For the current explored highest lithium cell negative pole material of specific capacity
Material is significantly larger than commercialized graphite cathode material at present（372 mAh g-1）.But the specific capacity of superelevation is along with removal lithium embedded mistake
Huge volume expansion in journey, this so that silicon particle cracks in cyclic process, and pole piece comes off, and cycle performance is deteriorated.In addition, silicon material
The intrinsic conductivity of material is very low, greatly influences the performance of its capacity.
Factors above significantly limits the performance and its development and application in the future of the chemical property of material.It is born for silicon
Pole material there are the problem of, at present mainly by improving the compound of silicon materials and other high electronic conductances is compound in research
Its chemical property.Bulk effect of the silicon in charge and discharge process can effectively be reduced by carrying out composited processing to silicon materials, together
When can introduce the small active or nonactive buffering matrix of good conductivity, bulk effect, prepare multiphase composite negative pole material, pass through
Volume compensation increases the long-term cycle stability that the modes such as electric conductivity improve material.
The Zhao seminar of Xiamen University is compound by commercialized nano silicon particles and carbon nanotube and amorphous carbon, prepares
Going out Si/CNT/C composite negative pole materials, the presence of carbon nanotube and amorphous carbon substantially increases the electronic conduction ability of material,
So as to effectively enhance the electric conductivity of Si materials, Si/CNT/C materials shows go out good cycle performance, 100 are recycled under 0.1C
The mAh g of reversible capacity ~ 800 after secondary-1M, capacity retention ratio 97.1%.This has benefited from the space that CNT and amorphous carbon construct
Network structure provides good electron-transport network for Si materials, enhances its electric conductivity.It is steady that material shows good cycle
It is qualitative.（Journal of Power Sources 315 (2016) 236-241）；Wang of Canadian University of Waterloo (CA) Waterloo, Ontario, N2L3GI Canada etc.
People prepares carbon nanotube-graphene-silicon composite cathode material, by by the CNTs of business silicon nanoparticle and high electronic conductance
It is compound with the graphene with space conductive network, effectively promote the cyclical stability of Si（J. Mater. Chem. A,
2015, 3, 3962）.
As it can be seen that the above method is to promote the electrochemistry capacitance of material by improving material electronics conductance and improve material
Electrochemical stability, still, due to being all compound using the progress of commercialized silicon particle, silicon particle does not can be uniformly dispersed attached
It on high electronic conductance matrix, forms uniform compound, form the difference of chemical property between different zones.
Invention content
To solve the above-mentioned problems, it is an object of the invention to provide a kind of electronic conductance for improving material, material is promoted
Electrochemistry capacitance while improving the electrochemical stability of material, solves active silicon particle and is uniformly attached to high electronic conductance
The preparation method of the lithium ion battery negative material silicon@graphene/carbons of problem in composite matrix.
The technical scheme is that：A kind of preparation method of lithium ion battery negative material silicon@graphene/carbons, including
Following steps：
Step（1）A certain proportion of graphene oxide powder and silicon tetrachloride are taken, graphene oxide powder is dissolved in a certain amount of
It in alcohol, stirs to graphene oxide and is completely dissolved, obtain mixed liquor A.Silicon tetrachloride is added in the mixed liquor A, waits to react
After, product is dried, grind after obtain intermediate product silica@graphene oxide powders；
Step（2）The silica@graphene oxide powders are placed in crucible, are calcined under inert gas shielding, are kept the temperature
After several hours, furnace cooling to room temperature obtains intermediate product silica@graphene powders；
Step（3）The silica@graphene powders and metal magnesium powder are weighed, and the two is uniformly mixed by certain mass ratio
It is placed in crucible, is calcined under inert gas shielding, after keeping the temperature several hours, product is used in furnace cooling to room temperature
After dilute hydrochloric acid washs several hours, it is neutrality to be washed with deionized to pH value, after drying, obtains intermediate product silicon@graphenes
Powder；
Step（4）The silicon@graphene powders are placed in crucible, using a certain proportion of argon gas/acetylene gaseous mixture as cracking gas,
After keeping the temperature some time at a certain temperature, room temperature is cooled to, obtains final product silicon@graphene/carbons.
Further, step（1）A certain proportion of graphene oxide powder and silicon tetrachloride are：Graphene oxide powder
The solid-to-liquid ratio of end and silicon tetrachloride is 1：0.01 ~0.1g/mL.
Further, step（1）The alcohol be in one or more of the ethylene glycol containing hydroxyl, glycerine, butanol.
Further, step（1）The volume ratio of the silicon tetrachloride and alcohol is 1：0.5~1：3.
Further, step（1）The drying mode of the product is：
It is dried in the constant temperature convection oven for being 70 ~ 150 DEG C in temperature；
Further, the drying temperature can also be 80 ~ 120 DEG C.
Further, step（2）The temperature of the calcining is 300 ~ 900 DEG C；Soaking time is 0.5 ~ 5 hour；
Further, the soaking time can also be 1-3 hours.
Further, step（3）The mass ratio of the silica@graphene powders and metal magnesium powder is=1：0.7~1：
1.3 。
Further, step（3）The temperature of the calcining is 650 ~ 750 DEG C, and soaking time is 0.5 ~ 3 hour, preferably
1-2 hours.
Further, step（4）The argon gas and the volume ratio of acetylene are 7：1~9：1.
Further, step（4）The temperature of the calcining be 400 ~ 900 DEG C, soaking time be 5 ~ 30 minutes, preferably 10
~ 20 minutes.
The beneficial effects of the invention are as follows：Due to the adoption of the above technical scheme, it is compound to prepare silicon@graphene/carbons by the present invention
Negative material.Using silicon tetrachloride as silicon source, graphene oxide is dissolved in alcohol, reacts generation oxidation with alcoholic solvent using silicon tetrachloride
The principle of silicon, so as to achieve the purpose that adhere to silica dioxide granule in graphene oxide on piece growth in situ, in sequential reduction mistake
Reducing silica is silicon in journey, forms [email protected] additional subsequent chemical vapour deposition technique of combination carries out carbon coating, most
Silicon@graphene/carbons are obtained eventually.It can prepare that composite effect is good with this preparation method, the silicon of electrochemical performance is compound
Electrode.
Description of the drawings
Fig. 1 is the X-ray diffraction spectra schematic diagram of the silicon@graphene/carbon composite negative pole materials of embodiment 1.
Fig. 2 is the microscopic appearance figure of the silicon@graphene/carbon composite negative pole materials of embodiment 1.
Fig. 3 is the circulation volume figure of the silicon@graphene/carbon combination electrode materials of embodiment 1.
Specific embodiment
Technical scheme of the present invention is described further with reference to specific embodiment.
A kind of preparation method of lithium ion battery negative material silicon@graphene/carbons of the present invention, can include：
Step（1）A certain proportion of graphene oxide powder and silicon tetrachloride are taken, graphene oxide powder is dissolved in a certain amount of
It in alcohol, stirs to graphene oxide and is completely dissolved, obtain mixed liquor A.Silicon tetrachloride is added in the mixed liquor A, waits to react
After, product is dried, grind after obtain intermediate product silica@graphene oxide powders；
Step（2）The silica@graphene oxide powders are placed in crucible, are calcined under inert gas shielding, are kept the temperature
After several hours, furnace cooling to room temperature obtains intermediate product silica@graphene powders；
Step（3）The silica@graphene powders and metal magnesium powder are weighed, and the two is uniformly mixed by certain mass ratio
It is placed in crucible, is calcined under inert gas shielding, after keeping the temperature several hours, product is used in furnace cooling to room temperature
After dilute hydrochloric acid washs several hours, it is neutrality to be washed with deionized to pH value, after drying, obtains intermediate product silicon@graphenes
Powder；
Step（4）The silicon@graphene powders are placed in crucible, using a certain proportion of argon gas/acetylene gaseous mixture as cracking gas,
After keeping the temperature some time at a certain temperature, room temperature is cooled to, obtains final product silicon@graphene/carbons.
Graphene oxide powder is weighed first, and measures silicon tetrachloride, wherein, silicon tetrachloride and graphene oxide powder
Ratio is 1 ml：（0.01~0.1）G, inventor have found that the matter of rational silicon and graphene can be obtained according to such ratio
Ratio is measured, conducive to the raising and reinforcing material electrode cycle stability for taking into account composite material specific capacity.
Described alcohol refers to the organic compound ethylene glycol containing hydroxyl, glycerine, one kind in butanol or several in molecule
Kind.Hydroxyl in organic compound can react generation silica with silicon tetrachloride, and then be conducive to form subsequent active material
Silicon.
When silicon tetrachloride is added in above-mentioned mixed liquor A, the mode rapidly joined may be used, rapidly join refer to by
The silicon tetrachloride being contained in graduated cylinder is directly all poured into mixed liquor A.Do so the silica dioxide granule for enabling to generation
Graphene oxide on piece can be uniformly attached to, forms uniform compound.It, can after silicon tetrachloride is added in above-mentioned mixed liquor A
To be stirred, silicon tetrachloride can be made substantially more to be mixed with alcohol in this way, and reacted, specific mixing time can root
Factually border it needs to be determined that, stirring to reaction stops, for example, half an hour, 40 minutes, 50 minutes etc., not doing herein specific
It limits.
Next in above-mentioned steps（2）In, it can be by step（1）In the silica@graphene oxide powder that is prepared
End is placed in crucible, is calcined under inert gas shielding, generally, be passed through in calcination process inert gas under high temperature not with two
The gas that silica graphene oxide powder reacts can be one or more of argon gas, nitrogen, helium.Indifferent gas
Being passed through for body can effectively prevent silica@graphene oxide powders to occur to go bad because of gas componant.In addition, calcination temperature can
Think 300 ~ 900 DEG C, soaking time can be 0.5 ~ 5 hour, preferably 1 ~ 3 hour.Such calcination temperature and duration can be with
The impurity such as the organic matter in silica@graphene oxide powders is enabled fully to decompose and remove moisture, are conducive to subsequently prepare silicon@
Graphene powder.
Then silica@graphene powders and metal magnesium powder are weighed by certain mass ratio, and after the two is uniformly mixed
It is placed in crucible, is calcined under inert gas shielding, generally, mixed uniformly purpose is so that silica@Graphene powders
End and metal magnesium powder can more come into full contact with, conducive to the complete progress of reaction, so as to generate the product of homogenization.
In addition, the inert gas being passed through in calcination process can be not occur under high temperature with silica graphene powder
The gas of reaction, for example, can be one or more of argon gas, nitrogen, helium.Being passed through for inert gas can be effectively prevent
Silica@graphene powders occur rotten.In addition, calcination temperature can be 650 ~ 750 DEG C, soaking time is 0.5 ~ 3 hour,
Preferably 1-2 hours.Such calcination temperature and duration can enable silica@graphene powders and metal magnesium powder fully anti-
Should, generate silicon@graphene powders.Above-mentioned dilute hydrochloric acid wash time can be 2 ~ 5 hours, be specifically as follows and add in product
In dilute hydrochloric acid, it is stirred continuously and is washed, wherein, the concentration of dilute hydrochloric acid can be 0.5 ~ 2mol/L.It is washed using dilute hydrochloric acid
Wash the acid soluble impurities phase that can fully remove in product, such as magnesia and Si-Mg alloy etc..Be washed with deionized to
PH value is neutrality, it is therefore an objective to remove the hydrochloric acid in solution.
In above-mentioned steps（4）In, silicon@graphene powders can be placed in crucible, be mixed with a certain proportion of argon gas/acetylene
Conjunction gas is cracking gas, after keeping the temperature some time at a certain temperature, is cooled to room temperature, obtains final product silicon@graphene/carbons.
A certain proportion of argon gas mentioned here/acetylene mixed pyrolysis gas can be argon gas：Acetylene is（7~9）:1, such ratio can
So that acetylene be present in it is explosion-proof within the scope of, ensure safe preparation process carry out.
In addition, above-mentioned steps（4）In calcination temperature can be 400 ~ 900 DEG C, soaking time can be 5 ~ 30 minutes, it is excellent
It is selected as 10 ~ 20 minutes, such calcination temperature can ensure to obtain suitable Carbon deposition amount, i.e., Carbon deposition amount is the wt of 5wt% ~ 15
%.Wherein, heat preserving mode can be to be kept the temperature in tube furnace, and the type of cooling can be to cool to room temperature with the furnace.
It should be noted that above-mentioned, the modes of operation such as to weigh, stir, calcine, keep the temperature and cool down be this field routine
Technological means, those skilled in the art can be operated according to actual needs, herein no longer specific restriction and explanation.
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is described, is shown
So, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based on the reality in the present invention
Apply example, those of ordinary skill in the art's all other embodiments obtained without making creative work all belong to
In the scope of protection of the invention.
Embodiment 1：
The graphene oxide powder for weighing 0.01 g is dissolved in the ethylene glycol of 0.5 ml, and stirring a moment obtains mixed liquor A.By 1
The silicon tetrachloride of ml is rapidly joined in mixed liquor A, treats after reaction, product to be transferred in constant temperature convection oven and is dried,
Drying temperature is set as 70 DEG C.Intermediate product silica@graphene oxides are obtained after the product of drying is ground.
Silica@graphene oxides are placed in silica crucible, in the case where inertia protects argon gas atmosphere, with 300 DEG C of temperature
Lower heat preservation 0.5 hour, furnace cooling to room temperature obtains intermediate product silica@graphenes.
By silica@graphenes and metal magnesium powder with 1g：The ratio uniform mixing of 0.7 g is placed in silica crucible,
In the case where argon gas protects gas, to keep the temperature 0.5 hour at a temperature of 650 DEG C, furnace cooling to room temperature.By the dilute salt of the product after calcining
After acid elution 2 hours, then it is neutrality to be washed with deionized water to pH value, and then drying obtains intermediate product silicon@graphenes.
Silicon@graphene powders are placed in silica crucible, using argon gas/acetylene ratio as 7:1 gaseous mixture as cracking gas,
It is kept the temperature at 400 DEG C after five minutes, cools to room temperature with the furnace, obtain final product silicon@graphene/carbons.
XRD testers by Japan factory Rigaku productions, model D/max-A, testing conditions for Cu Ka, l=
1.5406 Å.Scanning electron microscope is produced for Zeiss producers of Germany, model SUPRA55, and amplification factor is 20,000 times.
XRD is carried out to prepared silicon@graphene/carbons（X-ray diffraction, X-ray diffraction）Detection, detection knot
Fruit is as shown in Figure 1, it is seen then that main object is mutually elementary silicon in silicon graphene/carbon.Graphene and carbon because its amorphous state and
Fail detected.
SEM is carried out to prepared silicon@graphene/carbons（Scanning electron microscope, scanning electron microscopy）
Observation, testing result are as shown in Figure 2, it is seen then that uniformly adhere to silicon nanoparticle on graphene film, particle surface is coated with without fixed
Shape carbon-coating.
It is uniformly mixed, made with the CMC of 70 wt% silicon@graphene/carbons negative materials, the acetylene black of 15 wt%, 15 wt%
It into slurry, is coated uniformly on copper foil, circular electrode pole piece is stamped into after vacuum drying, using lithium metal as to electrode, 1 mol/L
LiPF6/DMC+DEC+EC（Volume ratio is 1:1:1）For electrolyte, Celgard 2400 is diaphragm, forms test cell.
Constant current charge-discharge test is carried out to battery, test result is as shown in figure 3, charging/discharging voltage ranging from 0.01 ~ 1.5
V, the results showed that, with preferable chemical property, 0.1 A g-1Current density under, stablize cycle 30 times after, reversible ratio
Capacity stabilization is in 900 mAh g-1。
Embodiment 2：
The graphene oxide powder for weighing 0.1 g is dissolved in the ethylene glycol of 1 ml, and stirring a moment obtains mixed liquor A.By 1 ml
Silicon tetrachloride rapidly join in mixed liquor A, treat after reaction, product to be transferred in constant temperature convection oven and is dried, dry
Dry temperature setting is 150 DEG C.Intermediate product silica@graphene oxides are obtained after the product of drying is ground.
Silica@graphene oxides are placed in silica crucible, in the case where inertia protects argon gas atmosphere, with 900 DEG C of temperature
Lower heat preservation 5 hours, furnace cooling to room temperature obtains intermediate product silica@graphenes.
By silica@graphenes and metal magnesium powder with 1g：The ratio uniform mixing of 1.3 g is placed in silica crucible,
In the case where argon gas protects gas, to keep the temperature 3 hours at a temperature of 750 DEG C, furnace cooling to room temperature.By the product dilute hydrochloric acid after calcining
After washing 5 hours, then it is neutrality to be washed with deionized water to pH value, and then drying obtains intermediate product silicon@graphenes.
Silicon@graphene powders are placed in silica crucible, using argon gas/acetylene ratio as 9:1 gaseous mixture as cracking gas,
After keeping the temperature 30 minutes at 900 DEG C, room temperature is cooled to the furnace, obtain final product silicon@graphene/carbons.
It is consistent in equipment manufacturer, model and testing conditions used in XRD and the SEM detection of the sample and embodiment 1.
It is uniformly mixed, made with the CMC of 70 wt% silicon@graphene/carbons negative materials, the acetylene black of 15 wt%, 15 wt%
It into slurry, is coated uniformly on copper foil, circular electrode pole piece is stamped into after vacuum drying, using lithium metal as to electrode, 1 mol/L
LiPF6/DMC+DEC+EC（Volume ratio is 1:1:1）For electrolyte, Celgard 2400 is diaphragm, forms test cell.To electricity
Pond carries out constant current charge-discharge test, charging/discharging voltage ranging from 0.01 ~ 1.5 V.
Embodiment 3：
The graphene oxide powder for weighing 0.1 g is dissolved in the ethylene glycol of 2 ml, and stirring a moment obtains mixed liquor A.By 1 ml
Silicon tetrachloride rapidly join in mixed liquor A, treat after reaction, product to be transferred in constant temperature convection oven and is dried, dry
Dry temperature setting is 120 DEG C.Intermediate product silica@graphene oxides are obtained after the product of drying is ground.
Silica@graphene oxides are placed in silica crucible, in the case where inertia protects argon gas atmosphere, with 600 DEG C of temperature
Lower heat preservation 3 hours, furnace cooling to room temperature obtains intermediate product silica@graphenes.
By silica@graphenes and metal magnesium powder with 1g：The ratio uniform mixing of 1 g is placed in silica crucible,
Under argon gas protection gas, to keep the temperature 2 hours at a temperature of 650 DEG C, furnace cooling to room temperature.Product after calcining is washed with dilute hydrochloric acid
After washing 4 hours, then it is neutrality to be washed with deionized water to pH value, and then drying obtains intermediate product silicon@graphenes.
Silicon@graphene powders are placed in silica crucible, using argon gas/acetylene ratio as 7:1 gaseous mixture as cracking gas,
It is kept the temperature at 800 DEG C after ten minutes, cools to room temperature with the furnace, obtain final product silicon@graphene/carbons.
It is consistent in equipment manufacturer, model and testing conditions used in XRD and the SEM detection of the sample and embodiment 1.
It is uniformly mixed, made with the CMC of 70 wt% silicon@graphene/carbons negative materials, the acetylene black of 15 wt%, 15 wt%
It into slurry, is coated uniformly on copper foil, circular electrode pole piece is stamped into after vacuum drying, using lithium metal as to electrode, 1 mol/L
LiPF6/DMC+DEC+EC（Volume ratio is 1:1:1）For electrolyte, Celgard 2400 is diaphragm, forms test cell.To electricity
Pond carries out constant current charge-discharge test, charging/discharging voltage ranging from 0.01 ~ 1.5 V.
Embodiment 4：
The graphene oxide powder for weighing 0.05 g is dissolved in the ethylene glycol of 3 ml, and stirring a moment obtains mixed liquor A.By 1 ml
Silicon tetrachloride rapidly join in mixed liquor A, treat after reaction, product to be transferred in constant temperature convection oven and is dried, dry
Dry temperature setting is 100 DEG C.Intermediate product silica@graphene oxides are obtained after the product of drying is ground.
Silica@graphene oxides are placed in silica crucible, in the case where inertia protects argon gas atmosphere, with 700 DEG C of temperature
Lower heat preservation 2 hours, furnace cooling to room temperature obtains intermediate product silica@graphenes.
By silica@graphenes and metal magnesium powder with 1g：The ratio uniform mixing of 1.2 g is placed in silica crucible,
In the case where argon gas protects gas, to keep the temperature 3 hours at a temperature of 700 DEG C, furnace cooling to room temperature.By the product dilute hydrochloric acid after calcining
After washing 3 hours, then it is neutrality to be washed with deionized water to pH value, and then drying obtains intermediate product [email protected] silicon@stones
Black alkene powder is placed in silica crucible, using argon gas/acetylene ratio as 8:1 gaseous mixture keeps the temperature 15 as cracking gas at 600 DEG C
After minute, cool to room temperature with the furnace, obtain final product silicon@graphene/carbons.
It is consistent in equipment manufacturer, model and testing conditions used in XRD and the SEM detection of the sample and embodiment 1.
It is uniformly mixed, made with the CMC of 70 wt% silicon@graphene/carbons negative materials, the acetylene black of 15 wt%, 15 wt%
It into slurry, is coated uniformly on copper foil, circular electrode pole piece is stamped into after vacuum drying, using lithium metal as to electrode, 1 mol/L
LiPF6/DMC+DEC+EC（Volume ratio is 1:1:1）For electrolyte, Celgard 2400 is diaphragm, forms test cell.To electricity
Pond carries out constant current charge-discharge test, charging/discharging voltage ranging from 0.01 ~ 1.5 V.
Embodiment 5：
The graphene oxide powder for weighing 0.07 g is dissolved in the ethylene glycol of 1.5 ml, and stirring a moment obtains mixed liquor A.By 1
The silicon tetrachloride of ml is rapidly joined in mixed liquor A, treats after reaction, product to be transferred in constant temperature convection oven and is dried,
Drying temperature is set as 90 DEG C.Intermediate product silica@graphene oxides are obtained after the product of drying is ground.
Silica@graphene oxides are placed in silica crucible, in the case where inertia protects argon gas atmosphere, with 400 DEG C of temperature
Lower heat preservation 4 hours, furnace cooling to room temperature obtains intermediate product silica@graphenes.
By silica@graphenes and metal magnesium powder with 1g：The ratio uniform mixing of 0.7 g is placed in silica crucible,
In the case where argon gas protects gas, to keep the temperature 2.5 hours at a temperature of 720 DEG C, furnace cooling to room temperature.By the dilute salt of the product after calcining
After acid elution 4 hours, then it is neutrality to be washed with deionized water to pH value, and then drying obtains intermediate product silicon@graphenes.
Silicon@graphene powders are placed in silica crucible, using argon gas/acetylene ratio as 8:1 gaseous mixture as cracking gas,
After keeping the temperature 25 minutes at 800 DEG C, room temperature is cooled to the furnace, obtain final product silicon@graphene/carbons.
It is consistent in equipment manufacturer, model and testing conditions used in XRD and the SEM detection of the sample and embodiment 1.
It is uniformly mixed, made with the CMC of 70 wt% silicon@graphene/carbons negative materials, the acetylene black of 15 wt%, 15 wt%
It into slurry, is coated uniformly on copper foil, circular electrode pole piece is stamped into after vacuum drying, using lithium metal as to electrode, 1 mol/L
LiPF6/DMC+DEC+EC（Volume ratio is 1:1:1）For electrolyte, Celgard 2400 is diaphragm, forms test cell.To electricity
Pond carries out constant current charge-discharge test, charging/discharging voltage ranging from 0.01 ~ 1.5 V.
As it can be seen that a kind of preparation side of lithium ion battery negative material silicon@graphene/carbons that the embodiment of the present invention is provided
Method prepares silicon@graphene/carbon composite negative pole materials.Using silicon tetrachloride as silicon source, graphene oxide is dissolved in alcohol, utilizes four
Silicon chloride reacts the principle of generation silica with alcoholic solvent, adheres to titanium dioxide in graphene oxide on piece growth in situ so as to reach
The purpose of silicon particle, reducing silica is silicon during sequential reduction, forms [email protected] combination subsequentization
It learns vapour deposition process and carries out carbon coating, finally obtain silicon@graphene/carbons.It is good that composite effect can be prepared with this preparation method
It is good, the silicon combination electrode of electrochemical performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention
It is interior.
Claims (10)
1. a kind of preparation method of lithium ion battery negative material silicon@graphene/carbons, which is characterized in that include the following steps：
Step（1）A certain proportion of graphene oxide powder and silicon tetrachloride are taken, graphene oxide powder is dissolved in a certain amount of
It in alcohol, stirs to graphene oxide and is completely dissolved, obtain mixed liquor A, then silicon tetrachloride is added in the mixed liquor A, treat anti-
Should after, product is dried, grind after obtain intermediate product silica@graphene oxide powders；
Step（2）The silica@graphene oxide powders are placed in crucible, are calcined under inert gas shielding, are kept the temperature
After several hours, furnace cooling to room temperature obtains intermediate product silica@graphene powders；
Step（3）The silica@graphene powders and metal magnesium powder are weighed, and the two is uniformly mixed by certain mass ratio
It is placed in crucible, is calcined under inert gas shielding, after keeping the temperature several hours, product is used in furnace cooling to room temperature
After dilute hydrochloric acid washs several hours, it is neutrality to be washed with deionized to pH value, after drying, obtains intermediate product silicon@graphenes
Powder；
Step（4）The silicon@graphene powders are placed in crucible, using a certain proportion of argon gas/acetylene gaseous mixture as cracking gas,
After keeping the temperature some time at a certain temperature, room temperature is cooled to, obtains final product silicon@graphene/carbons.
2. preparation method as described in claim 1, it is characterised in that：Step（1）A certain proportion of graphene oxide
Powder and silicon tetrachloride are：Graphene oxide powder and the solid-to-liquid ratio of silicon tetrachloride are 1：0.01 -0.1g/mL.
3. preparation method as described in claim 1, it is characterised in that：Step（1）The alcohol for the ethylene glycol containing hydroxyl,
One or more of glycerine, butanol.
4. preparation method as described in claim 1, it is characterised in that：Step（1）The volume ratio of the silicon tetrachloride and alcohol is
1：0.5-3.
5. preparation method as described in claim 1, it is characterised in that：Step（1）The drying mode of the product is：
It is dried in the constant temperature convection oven for being 70 ~ 150 DEG C in temperature.
6. a kind of preparation method of lithium ion battery negative material silicon@graphene/carbons as described in claim 1, feature exist
In：Step（2）The temperature of the calcining is 300 ~ 900 DEG C；Soaking time is 0.5 ~ 5 hour,.
7. a kind of preparation method of lithium ion battery negative material silicon@graphene/carbons as described in claim 1, feature exist
In：Step（3）The mass ratio of the silica@graphene powders and metal magnesium powder is=1：0.7-1.3 .
8. preparation method as described in claim 1, it is characterised in that：Step（3）The temperature of the calcining is 650 ~ 750
DEG C, soaking time is 0.5 ~ 3 hour.
9. preparation method as described in claim 1, it is characterised in that：Step（4）The argon gas and the volume ratio of acetylene
It is 7 ~ 9：1.
10. preparation method as described in claim 1, it is characterised in that：Step（4）The temperature of the calcining is 400 ~ 900
DEG C, soaking time is 5 ~ 30 minutes.
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