CN104916823A - Silicon/graphene oxide anode material for lithium battery and preparation method thereof - Google Patents
Silicon/graphene oxide anode material for lithium battery and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/058—Construction or manufacture
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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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Abstract
The present invention discloses a silicon/graphene oxide anode composite material for a lithium battery and a preparation method thereof. The anode composite material is formed by uniformly adsorbing nano silicon to the surface of graphene oxide. According to the preparation method, graphene oxide powder is ultrasonically dispersed in mixed solution of water and ethylene glycol to obtain dispersion liquid; the nano silicon and a dispersing agent are added into the dispersion liquid; ball milling is carried out until the nano silicon is completely dispersed; and drying is carried out to obtain the anode composite material with the sheet-like morphology, of which the nano silicon is uniformly adsorbed to the surface of the graphene oxide. The composite material can be used for preparing the lithium ion battery with the characteristics of high specific discharge capacity, excellent rate capability, long cycle life and the like; and the preparation method is simple and reliable, is good in process repeatability, has high operability, is low in cost and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of silicon for lithium ion battery/graphene oxide negative material and preparation method thereof, belong to field of lithium ion battery.
Background technology
Since nineteen ninety Sony corporation of Japan take the lead in succeeding in developing lithium ion battery and by its commercialization since, lithium ion battery obtains fast development.Nowadays lithium ion battery has been widely used in civilian and military every field.Along with the continuous progress of science and technology, the performance of people to battery proposes more higher requirements: the miniaturization of electronic equipment and individualized development, and the specific energy needing battery to have less volume and Geng Gao exports; Aero-Space energy requirements battery has cycle life, the security performance of better low temperature charge-discharge performance and Geng Gao; Electric automobile needs the battery of Large Copacity, low cost, high stability and security performance.
The negative material of lithium ion battery has material with carbon element, intermetallic compound, silicon base compound etc.What current commercial Li-ion battery negative material adopted is graphite-like material with carbon element, and having lower lithium embedding/deintercalation current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, is more satisfactory lithium ion battery negative material.But its theoretical specific capacity only has 372mAh/g, thus limit the further raising of lithium ion battery specific energy, the demand of growing high-energy Portable power source can not be met.In various Novel anode material, silicon-based anode has unique advantage and potential.Silicium cathode material is in charge and discharge process, the alloys such as Li12Si7, L i13Si4, L i7Si3, L i15Si4, L i22Si5 can be formed with lithium, have high power capacity (Li22Si5, the highest 4200mAh/g), removal lithium embedded voltage low, with electrolyte reactivity is low, security performance is good etc. advantage.But violent volumetric expansion (0 ~ 300%) can occur silicon in removal lithium embedded course of reaction, thus causes destruction and the efflorescence of material structure, causes capacity to be decayed rapidly, cycle performance worsens.In addition, also there is the defects such as conductivity is low, and high rate performance is not good enough, and coulombic efficiency is lower in silicium cathode.
Graphene, as a kind of novel two-dimension nano materials, is the Two Dimensional Free state atomic crystal of the unique existence found at present.Since finding from 2004, Graphene not only receives very big concern in pure science, and the nanostructure special due to it and the physical and chemical performance of excellence and show at electronics, optics, magnetics, biomedicine, catalysis, energy storage and sensor numerous areas and have huge application potential, cause showing great attention to of scientific circles and industrial circle.Countries in the world one after another using Graphene and application technology thereof as long-range strategy developing direction, to being active and first chance in the new round Industrial Revolution caused by Graphene.
Graphene is also that the thinnest (0.335nm) is the hardest nano material also in the world at present, it is almost completely transparent, absorptivity is only 2.3%, conductive coefficient is up to 5300W/mK, higher than the material with carbon element such as carbon nano-tube and diamond, the electron conduction of Graphene is good, and under normal temperature, its electron mobility is higher than 15000cm2/Vs, and resistivity is only 10-6 Ω cm, it is the material that resistivity is minimum in the world at present.
Connection in Graphene between each carbon atom is very pliable and tough, and when applying external mechanical force, carbon atom face with regard to flexural deformation, thus makes carbon atom need not rearrange to adapt to external force, also just maintains Stability Analysis of Structures.The research group of Columbia Univ USA is through lot of experiments, find that Graphene is the material that intensity is maximum in the world up to now, if make according to measuring and calculating Graphene the film (thickness about 100 nanometer) that thickness is equivalent to bread and cheese plastic packaging bag thickness, so it can bear the pressure of about two tons of heavy articles, and be unlikely to fracture.Meanwhile, Graphene is the material that mankind's known strength is the highest, also harder than diamond, taller upper 100 times of the iron and steel that strength ratio is best in the world.
At present, effectively slowing down silicon as the method for negative material capacity rapid decay is generally active material and other basis material are carried out compound or synthesizes the active material of specific morphology.And up to the present, also without any technology composite material being prepared by graphene oxide and Si compound, more there is no related compound material as the relevant report of lithium cell cathode material.
Summary of the invention
For the defect that existing lithium ion battery material exists, the object of the invention is to be to provide a kind of structure of nano-silicon uniform adsorption in surface of graphene oxide with sheet-like morphology, can be used for preparing the silicon/graphene oxide anode material of the lithium ion battery with features such as high specific discharge capacity, excellent high rate performance and long circulation lifes.
Another object of the present invention is that to be to provide a kind of technique simple, reproducible, with low cost, the eco-friendly method preparing silicon/graphene oxide anode material.
The invention provides a kind of silicon for lithium ion battery/graphene oxide anode material, this composite material is made up of in surface of graphene oxide nano-silicon uniform adsorption.
In preferred silicon/graphene oxide anode material, the quality of nano-silicon accounts for 5 ~ 10% of nano-silicon and graphene oxide gross mass.
In preferred silicon/graphene oxide anode material, nano-silicon pattern is sheet, and lamellar spacing is 5 ~ 20nm.The pattern of nano-silicon is even, and thickness can regulate and control in suitable scope.
In preferred silicon/graphene oxide anode material, nano-silicon is adsorbed on surface of graphene oxide by the mode of ball milling to obtain further.
Preferred silicon/graphene oxide anode material specific area is 200 ~ 600m
2/ g.
Present invention also offers a kind of method preparing silicon/graphene oxide anode material, the method is by graphene oxide powder and nano-silicon by a certain percentage, adds solvent and dispersant, pass through ball milling, disperse completely to nano-silicon, centrifugal solid-liquid is separated, and is drying to obtain.
The method preparing silicon/graphene oxide anode material of the present invention also comprises following preferred version:
In preferred scheme, the mass ratio of silicon and graphene oxide is 0.05 ~ 0.5:1.
In preferred scheme, solvent is the mixed solution of water and ethylene glycol further.
In preferred scheme, dispersant is at least one in softex kw (CTAB), dodecyl sodium sulfonate lithium (PVP), polyvinylpyrrolidone (SDS) further.
Most preferred scheme is: graphene oxide powder ultrasonic disperse standby for the Hummers legal system of improvement is obtained dispersion liquid in the mixed solution of water and ethylene glycol, add in gained dispersion liquid dispersant, nano-silicon and ball milling mixing 10 ~ 24h, centrifugal solid-liquid is separated, then, after drying, silicon/graphene oxide composite material is obtained.
In preferred scheme, drying is dry in the vacuum drying chamber of 60 ~ 90 DEG C further.
Graphene oxide of the present invention is that the Hummers method by improving prepares: flaky graphite purity being not less than 99.5% joins in the mixed solution of the concentrated sulfuric acid and phosphoric acid, after abundant dispersion, maintain mixed solution temperature between 0 ~ 5 DEG C, divide many batches and add potassium permanganate, and stir 2 ~ 4h, at room temperature stir 12 ~ 24h again, at 75 ~ 85 DEG C, stir 0.5 ~ 1h further, obtain mixture; Under condition of ice bath, slowly add deionized water and dilute, carry out oxidation reaction simultaneously in mixture, add hydrogen peroxide removing potassium permanganate after having reacted, Separation of Solid and Liquid, drying, namely obtain graphene oxide powder.
Described flaky graphite and the mass ratio of potassium permanganate are 1:1 ~ 6.
The described concentrated sulfuric acid and the volume ratio of phosphoric acid are 7 ~ 5:1.
Described flaky graphite and the solid-to-liquid ratio of the concentrated sulfuric acid are 1 ~ 5g:100 ~ 350mL.
Described hydrogen peroxide and the mass ratio of potassium permanganate are 0.5:1.
The silicon that the present invention obtains/graphene oxide negative material prepares negative pole: silicon/graphene oxide negative material and conductive black conductive agent and PVDF binding agent and a small amount of water are thoroughly mixed to form uniform pastel through grinding, to be coated on Copper Foil matrix as test electrode, to make button cell using lithium metal as to electrode.
Beneficial effect of the present invention: nano-silicon is adsorbed on surface of graphene oxide by first passage physics ball-milling method of the present invention, form composite material, in this composite material, the pattern of silicon is uniform sheet, and thickness is controlled, can be used for preparing the lithium ion battery with high specific discharge capacity, excellent high rate performance and long circulation life.Hinge structure, the beneficial effect that technical solution of the present invention is brought:
The preparation method of 1, silicon/graphene oxide anode material is simple, is synthesized by ball-milling method, reproducible, with low cost, and environmental friendliness is applicable to suitability for industrialized production;
2, using the graphene oxide of high conductivity and mechanical strength, bigger serface agent and porosity as basis material, due to dispersion and the carrying effect of graphene oxide, silicon is uniformly dispersed, there is laminated structure, and thickness is 5 ~ 20nm, the laminated structure of suitable thickness makes composite material have higher specific area, can provide larger reaction interface, the volumetric expansion of material can be alleviated again simultaneously, thus effectively improve its cyclical stability in charge and discharge process;
3, the graphene oxide of layer structure and silicon perfect adaptation, the special construction of graphene oxide effectively can alleviate the change in volume of composite material in charge and discharge process caused by silicium cathode, composite electrode capacity attenuation can be avoided too fast, simultaneous oxidation Graphene can increase material conductivity, compensate for the deficiency of single silicon electrode;
4, silicon/graphene oxide anode material, during as lithium ion battery negative material, has high specific discharge capacity and good cycle performance.
Embodiment
Following examples are intended to be described in further details content of the present invention; And the protection range of the claims in the present invention does not limit by embodiment.
Embodiment 1
Take the flaky graphite of 5g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.3g GO, add 20mL deionized water and 40mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.170g CTAB successively, 0.015g Si, then ball milling mixing 24h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain silicon of the present invention/graphene oxide negative material.
Take the above-mentioned obtained silicon/graphene oxide anode material of 0.4g, add 0.05g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.
Adopt the electrode that silicon/graphene oxide anode material is made, at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 450mAh/g; Show good cycle performance.
Embodiment 2
Take the flaky graphite of 3g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 18g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 9g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.3g GO, add 40mL deionized water and 80mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.170g CTAB successively, 0.03g Si, then ball milling mixing 12h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain silicon of the present invention/graphene oxide anode material.
Take the above-mentioned obtained silicon/graphene oxide anode material of 0.35g, add 0.1g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 430mAh/g; Show good cycle performance.
Embodiment 3
Take the flaky graphite of 5g purity 99.5%, join containing 300mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.1g GO, add 30mL deionized water and 60mL ethylene glycol ultrasonic disperse 3h formation suspension-turbid liquid, then under agitation, add 0.100g PVP successively, 0.01g Si, then ball milling mixing 24h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain silicon of the present invention/graphene oxide anode material.
Take the above-mentioned obtained silicon/graphene oxide anode material of 0.35g, add 0.1g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 430mAh/g; Show good cycle performance.
Embodiment 4
Take the flaky graphite of 5g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.2g GO, add 40mL deionized water and 80mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.170g SDS successively, 0.016g Si, then ball milling mixing 24h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain silicon of the present invention/graphene oxide anode material.
Take the above-mentioned obtained silicon/graphene oxide anode material of 0.4g, add 0.05g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 420mAh/g; Show good cycle performance.
Embodiment 5
Take the flaky graphite of 5g purity 99.5%, join containing 350mL mass fraction be 98% the concentrated sulfuric acid and 50mL mass fraction be in the mixed solution of the phosphoric acid of 85%, add 30g potassium permanganate to be oxidized in batches, this mixed solution is remained on 0 DEG C, stir 2h, then at room temperature stirring in water bath 12h, stirs 0.5h further, obtains mixture at 80 DEG C.In mixture, 350mL deionized water is slowly added under condition of ice bath.After 15min, then add 15g hydrogen peroxide removing potassium permanganate, mixture color becomes glassy yellow afterwards, suction filtration, then with the watery hydrochloric acid that concentration is 10% wash 3 times, suction filtration, namely obtain graphene oxide (GO) at 60 DEG C of vacuumize 48h.
Take 0.3g GO, add 20mL deionized water and 40mL ethylene glycol ultrasonic disperse 3h formation dispersion liquid, then under agitation, add 0.15g CTAB successively, 0.03g Si, then ball milling mixing 12h, obtain black solid, after suction filtration cleaning, the drying box being put in 60 DEG C is dried, and can obtain silicon of the present invention/graphene oxide anode material.
Take the above-mentioned obtained silicon/graphene oxide anode material of 0.4g, add 0.05g conductive black as conductive agent, 0.05gPVDF is as binding agent, add a small amount of NMP and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using lithium metal as to electrode, its electrolyte is the LiPF6/EC+DMC+EMC (v/v=1:1:1) of 1mol/L, and test charging and discharging currents density is 500mA/g.
The electrode of lithium cell adopting the present embodiment to prepare and lithium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 440mAh/g; Show good cycle performance.
Claims (7)
1., for silicon/graphene oxide anode material of lithium ion battery, it is characterized in that, be made up of in surface of graphene oxide nano-silicon uniform adsorption.
2. silicon according to claim 1/graphene oxide anode material, is characterized in that, the quality of described nano-silicon accounts for 5 ~ 10% of nano-silicon and graphene oxide gross mass.
3. silicon according to claim 1/graphene oxide anode material, is characterized in that, described nano-silicon pattern is sheet, and lamellar spacing is 5 ~ 20nm.
4. silicon according to claim 3/graphene oxide anode material, is characterized in that, described nano-silicon is adsorbed on surface of graphene oxide by the mode of ball milling to obtain.
5. silicon according to claim 1/graphene oxide anode material, is characterized in that, the specific area of described silicon/graphene oxide composite material is 200 ~ 600m
2/ g.
6. prepare the method for the silicon/graphene oxide anode material described in any one of Claims 1 to 5, it is characterized in that, by graphene oxide powder and nano-silicon by a certain percentage, add solvent and dispersant, by ball milling, disperse completely to nano-silicon, centrifugal solid-liquid is separated, and is drying to obtain.
7. method according to claim 6, is characterized in that, described solvent is the mixed solvent of water and ethylene glycol, and its volume ratio is 1:2 ~ 4; The mass ratio of silicon and graphene oxide is 0.05 ~ 0.5:1; Described dispersant is at least one in softex kw, dodecyl sodium sulfonate lithium, polyvinylpyrrolidone.
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| CN109873152A (en) * | 2019-02-27 | 2019-06-11 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium ion battery graphene-silicon substrate composite negative pole material and preparation method thereof |
| CN109873152B (en) * | 2019-02-27 | 2021-02-19 | 陕西煤业化工技术研究院有限责任公司 | Graphene-silicon-based composite negative electrode material for lithium ion battery and preparation method thereof |
| CN112086624A (en) * | 2019-06-12 | 2020-12-15 | 识骅科技股份有限公司 | Manufacturing method of composite carbon-silicon cathode substrate and composite carbon-silicon cathode substrate manufactured by manufacturing method |
| CN110697702A (en) * | 2019-09-29 | 2020-01-17 | 长沙理工大学 | Carbon cage type silicon-graphite composite material and preparation method thereof |
| CN111261864A (en) * | 2020-02-10 | 2020-06-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN111416110A (en) * | 2020-04-02 | 2020-07-14 | 上海电气集团股份有限公司 | Graphene modified pre-lithiated silicon negative electrode material and preparation method thereof |
| CN113363455A (en) * | 2021-06-04 | 2021-09-07 | 广东工业大学 | Composite two-dimensional micron-sized silicon wafer and preparation method thereof |
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