CN103050672A - Preparation method of silicon-graphene composition material for lithium ion battery negative pole - Google Patents
Preparation method of silicon-graphene composition material for lithium ion battery negative pole Download PDFInfo
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Abstract
The invention relates to a preparation method of a silicon-graphene composition material for a lithium ion battery negative pole. The preparation method comprises the following steps of: mixing a silicon solution and a graphite oxide solution which is prepared through a modified Hummer method, carrying out ultrasonic dispersion, and pumping and filtering a mixed liquor on a filter membrane under vacuum condition; and carrying out natural air drying on the upper-layer filter membrane in the air, and taking the upper-layer membrane and calcining, thus obtaining the silicon-graphene composition material for the lithium ion battery negative pole. The preparation method provided by the invention fully utilizes the preeminent properties of high electric conduction, superior mechanical property and the like of graphene, can effectively solve the problem that the volume of a nanometer silicon material in a battery cyclical process is seriously changed, and simultaneously can greatly improve the specific capacity and security of a negative pole material; and the preparation method provided by the invention has the advantages that the preparation process is simple, a prepared silicon/graphene film can directly serve as the lithium ion battery negative pole material, an electric conduction addition agent and a binding agent do not need to be added, and the preparation method is suitable for large-scale industrial production.
Description
Technical field:
The present invention relates to the preparation method of lithium ion battery negative material, relate in particular to a kind of preparation method of used as negative electrode of Li-ion battery silicon-graphene composite material, belong to the preparation method of cathode material for high capacity lithium ion battery.
Background technology:
Along with the day by day deflation of oil, coal equal energy source, human society is being faced with more and more serious energy crisis.In the process of using traditional energy, produced pollution gas has brought huge destruction to environment, and therefore, exploitation cleaning and regenerative resource are to affect one of economic key technology area of future world.The lithium ion battery lithium ion battery becomes the first-selection of portable electric appts and following energy storage and automobile-used light high-energy electrokinetic cell with its high energy and power density, high working voltage, long circulation life, memory-less effect and the unique advantage such as pollution-free.At present, it is negative material that the lithium ion battery of production and application mainly adopts graphitized carbon, but the lithium storage content of graphite type material is not high, and the electrochemical theory capacity of business-like carbon negative pole material only has 372mAh/g, obviously can not satisfy the requirement of high-energy-density.Therefore, the high performance lithium ion battery material of Development of New Generation has become the problem that researcher is needed solution badly.
Silicon based anode material (can form Li owing to have very high theoretical capacity
4.4Si, theoretical capacity 4200mAh/g), embedding lithium current potential is low, and the electrochemical reversible capacity is high, and security performance is good, and the advantages such as aboundresources are the study hotspots of lithium ion battery material of new generation.But silica-base material is the same with other metal_based materials, taking off in the embedding process of lithium ion, is accompanied by serious bulk effect, the powder of detached that causes active material in charge and discharge process, capacity attenuation is serious, has reduced efficient and the cycle performance of battery, and has serious potential safety hazard.
At present, the absolute volume that mainly utilizes the nanometer of active material to reduce in the reversible process changes; Utilize simultaneously the Composite of active material, utilize the change in volume of other materials constraint active material in cyclic process.Graphene becomes the focus of international scientific research because having special construction and performance.The Two-dimensional Carbon material of this monolayer carbon atomic thickness has excellent mechanics, electricity and thermal property, the tall and big 2600m of specific area
2/ g, electron mobility reaches 15000cm
2/ (Vs), simultaneously Graphene also has storage lithium ability, can with the silicium cathode material carry out compoundly, effectively overcome the shortcoming in the silicium cathode material application process.Therefore silicon/graphene composite material is expected to become the high performance lithium ion battery negative material of a new generation.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of used as negative electrode of Li-ion battery silicon-graphene composite material is provided.
Technical scheme of the present invention is: a kind of preparation method of used as negative electrode of Li-ion battery silicon-graphene composite material, and its concrete steps are as follows:
1) preparation of graphite oxide solution:
By the standby graphite oxide of the Hummer legal system of modification; Then compound concentration is the graphite oxide solution of 0.01-1g/L;
2) preparation of silicon/graphene film:
Getting in advance a certain amount of nano silica fume is exposed in the air, be 0.001-0.05g/ml by the quality of nano silica fume and the volume ratio of water, be dispersed in the deionized water nano silica fume is ultrasonic, then be 0.1-4:1 by the quality of nano silica fume and the mass ratio of graphite oxide, be that the graphite oxide solution of 0.01-1g/L is mixed with the concentration of silicon dispersion liquid and step 1) preparation, after continuing ultrasonic dispersion, the mixed liquor vacuum is filtered above the filter membrane; Be that the filter membrane of silicon-graphene oxide behind the natural air drying, is taken off silicon-graphene oxide film in air above filter membrane with the upper strata; Be placed in the quartz boat, in the tube furnace of argon hydrogen gaseous mixture, the control gas flow rate, under 550-850 ℃, calcining 1-3h obtains used as negative electrode of Li-ion battery silicon-graphene composite material.
The standby graphite oxide of Hummer legal system by modification, concrete grammar is referring to (the application (patent) number: CN201110372309.X) of the patent " a kind of method of preparing grapheme through oxidation reduction " of this seminar application.Characterize by XRD, Raman and FT-IR, the graphite oxide degree of oxidation of preparation is high, good dispersion in the aqueous solution.
Preferred nano silica fume grain size is at 20-50nm; It is 12-20h that preferred nano silica fume is exposed to the airborne time.
The frequency of the ultrasonic dispersion described in the preferred steps (2) is for being 40-80Hz; Be 5-60min with the ultrasonic ultrasonic time that is dispersed in the deionized water of nano silica fume; Continuing ultrasonic jitter time after the silicon dispersion liquid mixes with graphite oxide solution is 1-2h.
The described filter membrane of preferred steps (2) is a kind of of cellulose filter membrane, PVDF filter membrane, anodization alumite and Anodisc inoranic membrane.
Argon hydrogen gaseous mixture described in the preferred steps (2) is that the volume fraction of hydrogen is 5%-10%, the volume fraction 90-95% of argon gas.
Tube furnace reaction tube described in the preferred steps (2) is quartz ampoule or alundum tube.
Beneficial effect:
1, the silicon/graphene composite material of the present invention's preparation has overcome the key issue in present negative material field, capacity, efficient, cyclical stability and the fail safe of lithium ion battery negative material have been improved greatly, technique is simple simultaneously, preparation efficiency is high, with low cost, is easy to the large-scale production of industry.
2, the present invention adopts the use of uniting of silicon active material nanometer and Composite, can effectively solve the change in volume of silicon materials in cyclic process.The conduction property of Graphene brilliance has been avoided other adding conductive additive and binding agent simultaneously, and the silicon of preparation/Graphene paper can directly as the negative pole of battery, without any need for post-processed, have been simplified the preparation technology of battery cathode.
Description of drawings:
Fig. 1 is the XRD figure of graphite oxide (a), silicon/graphene oxide (b), Graphene (c) and the silicon/Graphene (d) of embodiment 1 preparation
The discharging efficiency phenogram of silicon/graphene film under different charge-discharge magnifications of Fig. 2 embodiment 1,3 preparations.
Embodiment:
Below in conjunction with drawings and Examples the present invention is described in further detail.
The described graphite oxide preparation of the following example of the present invention is by the Hummer method of modification; Concrete grammar is referring to (the application (patent) number: CN201110372309.X) of the patent " a kind of method of preparing grapheme through oxidation reduction " of this seminar application.Characterize by XRD, Raman and FT-IR, the graphite oxide degree of oxidation of preparation is high, good dispersion in the aqueous solution.
Embodiment 1:
1) preparation of graphite oxide:
Get the 1g(200 order) natural flake graphite and 42ml mass concentration be after 94% sulfuric acid mixes, and adds 1.8g potassium nitrate, adds fast 5.3g potassium permanganate in 13 ℃ water-bath, mixes, the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 55 ℃, then reaction 2h adds 60ml water, simultaneously system is warming up to 90 ℃ of reaction 16min, adds 150ml distilled water cessation reaction again, and centrifuge washing is that 6,55 ℃ of vacuumizes obtain oxidation graphite solid to pH.XRD characterizes such as Fig. 1 a, can be 0.81nm in the hope of the interfloor distance of graphite oxide, compares the interlamellar spacing 0.34nm of initial graphite, has greatly increased, and illustrates that the effect of intercalation graphite oxide is very good.
2) preparation of graphene film:
The graphite oxide dispersion liquid 100ml of configuration 1g/L, then ultrasonic 2h filters solution for vacuum above the cellulose filter membrane, and natural air drying in air is taken off above filter membrane.Be placed in the quartz boat, at argon hydrogen gaseous mixture (10%H
2And 90%Ar) in the tube furnace, gas flow rate is 83ml.min
-1, under 550 ℃, calcining 3h obtains graphene film.XRD characterizes such as Fig. 1 c, and characteristic peak appears at 26.4 °, illustrates that reduction effect is good, does not have the characteristic peak of graphite oxide to occur.
3) preparation of graphene composite material:
Get in advance a certain amount of nano-silicon (grain size leaves the glove box under the atmosphere protection at 20-50nm) and be exposed to 18h in the air.Take by weighing the 0.05g silica flour, under the 80Hz frequency, ultrasonic 60min is dispersed in the 1ml deionized water, is that the graphite oxide solution of 0.5g/L is mixed with the silicon dispersion liquid with the concentration of 100ml then, continues ultrasonic 2h, then the mixed liquor vacuum is filtered above the cellulose filter membrane.Natural air drying in air is taken off above filter membrane, has just obtained silicon/graphene oxide film.Be placed in the quartz boat, at argon hydrogen gaseous mixture (10%H
2And 90%Ar) in the tube furnace, gas flow rate is 89ml.min
-1, under 550 ℃, calcining 3h obtains the used as negative electrode of Li-ion battery graphene composite material.XRD characterizes such as Fig. 1 b and d, occurs the characteristic peak of graphite oxide and the characteristic peak of silicon in the spectrogram, does not have other impurity peaks, illustrates that silicon and graphene oxide composite effect are good.The XRD characteristic peak of silicon/Graphene paper can significantly be found out the characteristic peak of Graphene and nano-silicon, illustrate that silicon and Graphene composite effect are very good, angle is characteristic peak that obvious diffraction maximum is graphite of 26.5 ° of appearance simultaneously, the graphite-structure that has crystal formation in the Graphene is described, forms desirable sandwich structure.
4) electrical performance testing:
Graphene composite material is placed on makes positive plate on the Copper Foil, in the glove box of atmosphere protection, take metal lithium sheet as negative pole, be assembled into button cell.Under the room temperature, in the voltage range of 0.02-1.5V, under the room temperature, carry out the charge and discharge cycles test with the charge-discharge magnification of 100mAh/g, circulate 120 times.Fig. 2 open circles curve is battery charge and discharge cycles curve under the 100mAh/g condition of graphene composite material assembling.The first discharge capacity of graphene composite material is about 2082mAh/g, and reserve capacity is 592mAh/g after 120 weeks of circulation.Illustrate that graphene composite material has very high specific capacity, and have good cycle performance.
Embodiment 2:
1) preparation of graphite oxide:
Get the 1g(200 order) natural flake graphite and 48ml mass concentration be after 97% sulfuric acid mixes, and adds 1.3g potassium nitrate, adds fast 5g potassium permanganate in 16 ℃ water-bath, mixes, the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 45 ℃, then reaction 2.5h adds 65ml water, simultaneously system is warming up to 80 ℃ of reaction 26min, adds 100ml distilled water cessation reaction again, and centrifuge washing is that 6,65 ℃ of vacuumizes obtain oxidation graphite solid to pH.Consistent with embodiment 1 characterization result, the interfloor distance of graphite oxide is 0.785nm, and than initial graphite, interfloor distance has obvious increase, illustrates that the graphite oxide oxidation effectiveness is fine.
2) preparation of graphene composite material:
Get in advance a certain amount of nano-silicon (grain size leaves the glove box under the atmosphere protection at 20-50nm) and be exposed to 12h in the air.Get step 1) and make oxidation graphite solid, compound concentration is graphite oxide (GO) solution of 0.01g/L.Take by weighing the 0.03g silica flour, under the 60Hz frequency, ultrasonic 5min is dispersed in the 28ml deionized water, is that 0.01g/L graphene oxide solution mixes with the silicon dispersion liquid with the concentration of 750ml then, continue ultrasonic 1h, then the mixed liquor vacuum is filtered above the Anodisc inoranic membrane.Natural air drying in air is taken off above filter membrane.Cut into little band shape, be placed in the quartz boat, at argon hydrogen gaseous mixture (5%H
2And 95%Ar) in the tube furnace, gas flow rate is 88ml.min
-1, under 700 ℃, calcining 2h obtains the used as negative electrode of Li-ion battery graphene composite material.
3) electrical performance testing:
Graphene composite material is placed on makes positive plate on the aluminium foil, in the glove box of atmosphere protection, take metal lithium sheet as negative pole, be assembled into button cell.In the voltage range of 0.02-1.5V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 100mAh/g, circulate 120 times.The first discharge specific capacity of composite material is 1876mAh/g, circulate 120 times be 712mAh/g for reserve capacity afterwards.
Embodiment 3:
1) preparation of graphite oxide:
Get the 2g(200 order) natural flake graphite and 87ml mass concentration be after 98% sulfuric acid mixes, and adds 3.5g potassium nitrate, adds fast 11g potassium permanganate in 14 ℃ water-bath, mixes, the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 60 ℃, then reaction 1.5h adds 140ml water, simultaneously system is warming up to 80 ℃ of reaction 27min, adds 210ml distilled water cessation reaction again, and centrifuge washing is that 6,55 ℃ of vacuumizes obtain oxidation graphite solid to pH.Consistent with embodiment 1 characterization result, the interfloor distance of graphite oxide is 0.77nm, and than initial graphite, interfloor distance has obvious increase, illustrates that the graphite oxide oxidation effectiveness is fine.
2) preparation of graphene composite material:
Get in advance a certain amount of nano-silicon (grain size leaves the glove box under the atmosphere protection at 20-50nm) and be exposed to 20h in the air.Get the oxidation graphite solid that step 1) makes, compound concentration is the GO solution of 1g/L.Take by weighing the 0.015g silica flour, under the 50Hz frequency, ultrasonic 30min is dispersed in the 3ml deionized water, is that the graphene oxide solution of 1g/L mixes with the silicon dispersion liquid with the concentration of 100ml then, continue ultrasonic 1.5h, then the mixed liquor vacuum is filtered above the Anodisc inoranic membrane.Natural air drying in air is taken off above filter membrane.Be placed in the quartz boat, at argon hydrogen gaseous mixture (8%H
2And 92%Ar) in the tube furnace, gas flow rate is 85ml.min
-1, under 850 ℃, calcining 1h obtains the used as negative electrode of Li-ion battery graphene composite material.
3) electrical performance testing:
Graphene composite material is placed on makes positive plate on the Copper Foil, in the glove box of atmosphere protection, take metal lithium sheet as negative pole, be assembled into button cell.Under the room temperature, in the voltage range of 0.02-1.5V, under the room temperature, carry out the charge and discharge cycles test with the charge-discharge magnification of 100mAh/g, circulate 120 times.Battery charge and discharge cycles curve under the 100mAh/g condition of Fig. 2 filled circles curve graphene composite material assembling.The first discharge capacity of graphene composite material is about 1912mAh/g, and reserve capacity is 861mAh/g after 120 weeks of circulation.Illustrate that graphene composite material has very high specific capacity, reserve capacity is high, and has good cycle performance.
Embodiment 4:
1) preparation of graphite oxide:
Get the 5g(200 order) natural flake graphite and 220ml mass concentration be after 98% sulfuric acid mixes, and adds 6.0g potassium nitrate, adds fast 30g potassium permanganate in 8 ℃ water-bath, mixes, the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 45 ℃, then reaction 3h adds 300ml water, simultaneously system is warming up to 90 ℃ of reaction 30min, use the excessive potassium permanganate of 350ml distilled water and 35ml hydrogen peroxide (30wt%) reduction, centrifuge washing is that 6,50 ℃ of vacuumizes obtain oxidation graphite solid to pH again.Consistent with embodiment 1 characterization result, the interfloor distance of graphite oxide is 0.753nm, and than initial graphite, interfloor distance has obvious increase, illustrates that the graphite oxide oxidation effectiveness is fine.
2) preparation of graphene composite material:
Get in advance a certain amount of nano-silicon (grain size leaves the glove box under the atmosphere protection at 20-50nm) and be exposed to 16h in the air.Get the oxidation graphite solid that step 1) makes, compound concentration is the GO solution of 0.4g/L.Take by weighing the 0.04g silica flour, under the 40Hz frequency, ultrasonic 20min is dispersed in the 4ml deionized water, is that the graphene oxide solution of 0.4g/L mixes with the silicon dispersion liquid with the concentration of 50ml then, continue ultrasonic 1.5h, then the mixed liquor vacuum is filtered above the Anodisc inoranic membrane.Natural air drying in air is taken off above filter membrane.Be placed in the quartz boat, at argon hydrogen gaseous mixture (6%H
2And 94%Ar) in the tube furnace, gas flow rate is 70ml.min
-1, under 800 ℃, calcining 1h obtains the used as negative electrode of Li-ion battery graphene composite material.
3) electrical performance testing:
Graphene composite material is placed on makes positive plate on the aluminium foil, in the glove box of atmosphere protection, take metal lithium sheet as negative pole, be assembled into button cell.In the voltage range of 0.02-1.5V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 100mAh/g, circulate 120 times.The first discharge specific capacity of composite material is 1916mAh/g, circulate 120 times be 645mAh/g for reserve capacity afterwards.
The present invention utilizes the Graphene of remarkable character such as having high conduction, mechanical performance is superior as compound by nanometer and Composite technique in conjunction with the silicon active material, has effectively solved the change in volume of nano silicon material in the circulating battery process.Preparation technology of the present invention is simple, the silicon of preparation/Graphene paper can directly be used as lithium ion battery negative material, avoid adding in addition conductive additive and binding agent, and material has good ductility and processing characteristics flexibly, is fit to large-scale industrialization production.
Claims (6)
1. the preparation method of a used as negative electrode of Li-ion battery silicon-graphene composite material, its concrete steps are as follows:
(1) preparation of graphite oxide solution:
By the standby graphite oxide of the Hummer legal system of modification; Then compound concentration is the graphite oxide solution of 0.01-1g/L;
(2) preparation of silicon/graphene film:
Getting in advance a certain amount of nano silica fume is exposed in the air, be 0.001-0.05g/ml by the quality of nano silica fume and the volume ratio of water, be dispersed in the deionized water nano silica fume is ultrasonic, then be 0.1-4:1 by the quality of nano silica fume and the mass ratio of graphite oxide, be that the graphite oxide solution of 0.01-1g/L is mixed with the concentration of silicon dispersion liquid and step (1) preparation, after continuing ultrasonic dispersion, the mixed liquor vacuum is filtered above the filter membrane; Be that the filter membrane of silicon-graphene oxide behind the natural air drying, is taken off silicon-graphene oxide film in air above filter membrane with the upper strata; Be placed in the quartz boat, in the tube furnace of argon hydrogen gaseous mixture, the control gas flow rate, under 550-850 ℃, calcining 1-3h obtains used as negative electrode of Li-ion battery silicon-graphene composite material.
2. preparation method according to claim 1, it is characterized in that: it is 12-20h that nano silica fume is exposed to the airborne time.
3. preparation method according to claim 1, it is characterized in that: the frequency of the ultrasonic dispersion described in the step (2) is for being 40-80Hz; Be 5-60min with the ultrasonic ultrasonic time that is dispersed in the deionized water of nano silica fume; Continuing ultrasonic jitter time after the silicon dispersion liquid mixes with graphite oxide solution is 1-2h.
4. preparation method according to claim 1, it is characterized in that: the described filter membrane of step (2) is a kind of of cellulose filter membrane, PVDF filter membrane, anodization alumite and Anodisc inoranic membrane.
5. preparation method according to claim 1, it is characterized in that: the argon hydrogen gaseous mixture described in the step (2) is that the volume fraction of hydrogen is 5%-10%, the volume fraction 90-95% of argon gas.
6. preparation method according to claim 1, it is characterized in that: the tube furnace reaction tube described in the step (2) is quartz ampoule or alundum tube.
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| CN117393742A (en) * | 2023-12-12 | 2024-01-12 | 青岛泰达天润碳材料有限公司 | Lithium ion battery negative electrode graphite-based material and preparation method thereof |
| CN117393742B (en) * | 2023-12-12 | 2024-03-19 | 青岛泰达天润碳材料有限公司 | Negative graphene-based material of lithium ion battery and preparation method thereof |
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