CN103022483A - Preparation method for positive electrode material of power lithium ion battery - Google Patents
Preparation method for positive electrode material of power lithium ion battery Download PDFInfo
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- CN103022483A CN103022483A CN2012105198166A CN201210519816A CN103022483A CN 103022483 A CN103022483 A CN 103022483A CN 2012105198166 A CN2012105198166 A CN 2012105198166A CN 201210519816 A CN201210519816 A CN 201210519816A CN 103022483 A CN103022483 A CN 103022483A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method for a positive electrode material of a power lithium ion battery. The preparation method comprises the following concrete steps: preparing a graphite oxide solution, then preparing a nanometer FeF3 particle and preparing a non-supported FeF3/graphene oxide film; and subjecting the obtained non-supported FeF3/graphene oxide film to photoreduction so as to obtain the positive electrode material of the power lithium ion battery, i.e., a FeF3/graphene film. According to the invention, the phenomenon of severe polarization of a FeF3 material in cyclic process of the battery is effectively overcome; meanwhile, FeF3/graphene oxide is innovatively reduced by using a latest photoreduction method so as to overcome the disadvantages of production of Fe and agglomeration of nanometer particles in reduction of FeF3 by using a traditional high temperature reduction method, and specific capacity of the positive electrode material of the power lithium ion battery is substantially improved. The preparation method provided by the invention is simple; the prepared FeF3/graphene film can be directly used as the positive electrode material of the power lithium ion battery, and addition of other conductive additives and binders is avoided; and the positive electrode material has good ductility and flexible processability and is suitable for industrial large-scale production.
Description
Technical field:
The present invention relates to the preparation method of power lithium-ion battery positive electrode, relate in particular to a kind of power lithium-ion battery positive electrode three and fluoridize iron-graphite alkene composite manufacture method, belong to the preparation method of high power capacity, high efficiency power lithium-ion battery positive electrode.
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.Lithium ion battery has performance good as high performance green energy-storing device, safety, and cost is low, and the characteristics such as environmental friendliness become the first-selection of the large-sized power field of power supplies such as pure electric vehicle (EV), hybrid electric vehicle (HEV) and Aero-Space.Anode material for lithium-ion batteries is the important component part of battery, and the performance of positive electrode is restricting power and the energy density of lithium ion battery, along with the development of large capacity energy storage device is had higher requirement to the power type lithium-ion battery anode material.To the research of power lithium-ion battery positive electrode, be mainly spinel lithium manganate (LiMn at present
2O
4), LiFePO 4 (LiF
4PO
4) and nickel-cobalt-manganese ternary be Li(Ni, Co, Mn) O
2Although the research to these materials has obtained great progress, it is that theoretical capacity is all excessively low that there is most important defective in these materials, and its extensive use in the large-sized power field of power supplies is very restricted.Become the in recent years focus of research so explore the positive electrode of high power capacity, high efficiency, good cycle and novel environment friendly.
Three ferric flouride (FeF
3) have a very high theoretical specific capacity (712mAhg
-1), be about 3 ~ 5 times of present commercialization oxide material.While FeF
3The advantages such as reduction potential is high, and the electrochemical reversible capacity is high, and security performance is good are the study hotspots of power lithium-ion battery positive electrode of new generation.But three ferric flouride (FeF
3) poorly conductive, taking off in the embedding process of lithium ion, be accompanied by serious polarization phenomena, cause in charge and discharge process capacity attenuation serious, reduced efficient and the cycle performance of battery.
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 the specific area of remarkable heat-conductivity conducting, super large, good chemical stability, wide electrochemical window, low thermal coefficient of expansion and excellent mechanical property, and Graphene itself has storage lithium characteristic, together three ferric flouride (FeF
3) carry out compoundly, effectively overcome FeF
3The shortcomings such as the poorly conductive in the application process and serious polarization.Therefore, FeF
3/ graphene composite material is expected to become high power capacity of new generation, high efficiency power lithium-ion battery positive electrode.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art, the preparation method of a kind of high power capacity, high efficiency power lithium-ion battery positive electrode is provided.
Technical scheme of the present invention is: at first obtain nano level FeF
3, when increasing active material and lithium ion contact area, reduced the variation of the absolute volume of active material, improved the specific capacity of material.Next is to make nanometer Fe F by the self assembly mode
3Compound with Graphene " skeleton ", and adopt up-to-date photoreduction met hod reduction FeF
3/ graphene oxide generates the shortcoming of Fe to overcome the conventional high-temperature reducing process.Utilize Graphene to have fabulous conductive capability and remarkable pliability, can be compound with positive electrode, thus obtain good electrode integral electric property, avoid additionally adding conductive additive and adhesive, also overcome nanometer Fe F
3Serious polarization phenomena in charge and discharge process.
Concrete technical scheme of the present invention is: a kind of preparation method of power lithium-ion battery positive electrode, 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 0.25g/L-1g/L;
2) FeF
3The preparation of nano particle:
Prepare respectively the NH that amount of substance concentration is 1-2mol/L
4HF
2Fe (the NO of the aqueous solution and 0.1-0.5mol/L
3)
3Ethanolic solution, press NH
4HF
2And Fe (NO
3)
3Amount than 3-6:1, in the situation of stirring, with NH
4HF
2The aqueous solution joins Fe (NO
3)
3Ethanolic solution in, continue subsequently stirring reaction, washing after reaction finishes, centrifugal collecting precipitation is precipitated as (NH
4)
3FeF
6Presoma is with presoma and dry; Sample with drying is placed in the quartz boat at last, is placed in the tube furnace of atmosphere protection, keeps certain gas flow rate, and under 300-500 ℃, calcining 1-3h obtains FeF
3Nano particle;
3) FeF
3The preparation of/graphene film:
By nanometer Fe F
3Quality and the volume ratio of water be 0.005g/ml-0.05g/ml, with nanometer Fe F
3Ultrasonic being dispersed in the deionized water gets FeF
3Then dispersion liquid presses FeF
3Quality and the mass ratio of graphite oxide be 1-2:1, with FeF
3Dispersion liquid and concentration are that the graphite oxide solution of 0.25g/L-1g/L is mixed, continue ultrasonic dispersion after, the mixed liquor vacuum is filtered above the filter membrane; Natural air drying is taken off above filter membrane; Obtain the FeF of non-support
3/ graphene oxide film; FeF with the non-support that obtains
3/ graphene oxide film carries out photo-reduction, obtains power lithium-ion battery positive electrode-FeF
3/ graphene film.
The preparation of graphite oxide is the standby graphite oxide of the Hummer legal system by modification preferably, and concrete grammar is applied for a patent " a kind of method of preparing grapheme through oxidation reduction " (application (patent) number: CN201110372309.X) referring to the inventor.Characterize by XRD, Raman and FT-IR, the graphite oxide degree of oxidation of preparation is high, good dispersion in the aqueous solution.
In the preferred steps (2) with NH
4HF
2The aqueous solution joins Fe (NO
3)
3Ethanolic solution in, continuing subsequently the stirring reaction time is 2-5h; Described washing wherein adds volume and the Fe (NO of ethanol for reaction finishes the rear ethanol washing system that adds
3)
3Amount than for 8L/mol-20L/mol; Centrifugal rotating speed described in the preferred steps (2) is 3000-10000rpm; Described drying is at 50-80 ℃ of lower vacuumize 12-24h with presoma; Gas flow rate described in the preferred steps (2) is 10-90mlmin
-1Tube furnace reaction tube described in the preferred steps (2) is quartz ampoule or alundum tube.
The frequency of the ultrasonic dispersion described in the preferred steps (3) is 40-80Hz; Preparation FeF
3The time of ultrasonic dispersion is 5-60min during dispersion liquid; FeF
3Dispersion liquid mixes with graphite oxide solution, and the time of continuing ultrasonic dispersion is 1-2h.The described filter membrane of preferred steps (3) is a kind of of cellulose filter membrane, PVDF filter membrane, anodization alumite or Anodisc inoranic membrane.
Preferred described photo-reduction is the FeF with non-support
3/ graphene oxide paper cuts into little band shape, and be exposed to window size and be under the photoflash lamp of digital camera of 10mm * 20mm, be 0.5-2mm apart from the distance of photoflash lamp, open photoflash lamp, flash time is at the 1-2 millisecond.
Beneficial effect:
The FeF of the present invention's preparation
3/ graphene composite material has overcome the key issue of the existence of positive electrode current Material Field, the 3-5 that the capacity of positive electrode is brought up to present conventional oxide material doubly, lithium ion battery efficient, cyclical stability and fail safe have been improved greatly simultaneously, technique is simple simultaneously, preparation efficiency is high, with low cost, is easy to the large-scale production of industry.
The present invention adopts FeF
3Active material nanometer and Graphene Composite unite use, utilize the heat-conductivity conducting of Graphene brilliance, the specific area of super large, good chemical stability, low thermal coefficient of expansion and excellent mechanical property, can effectively solve FeF
3Material serious polarization phenomena in cyclic process.Simultaneously novelty utilizes up-to-date photoreduction met hod reduction FeF
3/ graphene oxide is to overcome conventional high-temperature reducing process reduction FeF
3Generate the shortcoming of Fe.The conduction property of last Graphene brilliance has been avoided other adding conductive additive and binding agent, the FeF of preparation
3/ Graphene paper can directly as the positive pole of battery, without any need for post-processed, have been simplified the preparation technology of anode.
Description of drawings:
Fig. 1 is FeF
3The synthetic schematic diagram of/graphene film;
Fig. 2 is FeF
3/ graphene oxide film and FeF
3The pictorial diagram of/graphene film;
Fig. 3 is the graphite of embodiment 1 usefulness, the Graphene of preparation and the XRD figure of graphite oxide;
Fig. 4 is the (NH of embodiment 1 preparation
4)
3FeF
6Presoma, FeF
3And FeF
3The XRD figure of/graphene film;
Fig. 5 is the FeF of embodiment 1 preparation
3The FeF of the surface scan electromicroscopic photograph (a) of/graphene oxide film, embodiment 1 preparation
3The FeF of the TEM photo (b) of/graphene film, examples of implementation 1 usefulness photo-reduction preparation
3The profile scanning electromicroscopic photograph (c) of/graphene film, the FeF of examples of implementation 1 preparation
3The profile scanning electromicroscopic photograph (d) of/graphene oxide film
The FeF of Fig. 6 embodiment 1 preparation
3(black initial point) and photo-reduction (red triangle) FeF
3-GO nano composite material is at 100mAg
-1Specific capacity and coulombic efficiency curve during charge and discharge cycles under the condition.
Embodiment:
Below in conjunction with drawings and Examples the present invention is described in further detail.The preparation of graphite oxide is applied for a patent " a kind of method of preparing grapheme through oxidation reduction " (application (patent) number: CN201110372309.X) referring to the inventor in following examples.FeF
3The synthetic schematic diagram of/graphene film as shown in Figure 1.
Embodiment 1:
1) preparation of graphite oxide:
Get the 1g(8000 order) natural flake graphite and 47ml mass concentration be after 98% sulfuric acid mixes, and adds 1.7g potassium nitrate, adds fast 5.2g potassium permanganate in 7 ℃ water-bath, mixes, the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 50 ℃, then reaction 1.5h adds 70ml water, simultaneously system is warming up to 90 ℃ of reaction 13min, adds 160ml distilled water cessation reaction again, and centrifuge washing is that 6,70 ℃ of vacuumizes obtain oxidation graphite solid to pH.XRD characterizes such as Fig. 3, and the interfloor distance of graphite oxide is 0.863nm, 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) FeF
3The preparation of nano particle:
Preparation amount of substance concentration is the NH of 1mol/L
4HF
2Fe (the NO of the aqueous solution and 0.2mol/L
3)
3Ethanolic solution, get 10ml NH
4HF
2The aqueous solution dropwise joins the Fe (NO of 10ml
3)
3In the ethanolic solution, adition process keeps stirring, and continues subsequently to stir 2h.After reaction finishes, add the ethanol washing system of 16ml, centrifugal collecting precipitation under the rotating speed of 5000rpm, with the sample collected at 60 ℃ of lower vacuumize 24h.Sample with drying is placed in the quartz boat at last, is placed in the quartz tube furnace that atmosphere is pure Ar gas, and gas flow rate is 90ml.min
-1, under 400 ℃, calcining 2h obtains FeF
3Nano particle.XRD characterizes such as Fig. 4, can clearly find out (the NH that has synthesized pure phase
4)
3FeF
6Presoma and FeF
3, do not have impurity peaks to occur.Fig. 5 b is FeF
3/ graphene film TEM figure can be clearly seen that mono-dispersed nano three ferric flourides, and size is about 20-30nm.
3) FeF
3The preparation of/graphene film:
Take by weighing 0.05g FeF
3Nano powder, under the 80Hz frequency, ultrasonic 5min is dispersed in the 1ml deionized water, then with FeF
3Dispersion liquid is that the graphite oxide solution of 0.5g/L is mixed with the concentration of 100ml, continues ultrasonic 1.5h, then with the mixed liquor vacuum filtration above cellulose filter membrane.Be FeF with the upper strata
3The filter membrane of/graphene oxide film behind the natural air drying, is taken off above filter membrane in air, obtains the FeF of non-support
3/ graphene oxide film.Film being cut into little band shape, be exposed to window size and be under the photoflash lamp of digital camera of 10mm * 20mm, is 0.5mm apart from the distance of photoflash lamp, opens photoflash lamp, and flash time obtains anode material for lithium-ion batteries-FeF at 2 milliseconds
3/ graphene film.Fig. 2 is FeF
3/ graphene oxide can see that material shows burgundy.Fig. 5 a is FeF
3The surperficial SEM photo of/graphene oxide film can see that from 10 microns yardsticks the surface is very smooth, and 1 micron yardstick can be clearly seen that, graphene oxide is wrapped in nanometer Fe F
3The structure of particle, composite effect is good.Fig. 5 d is FeF
3/ graphene oxide film SEM section photo can be seen the regular lamellar structure of film clearly, and size is about 8 microns.XRD characterizes such as Fig. 4, FeF
3It is fine that the Graphene of/grapheme material is peeled off effect, do not have obvious graphite characteristic peak to occur, and illustrates that Graphene exists with unordered structure in material.Fig. 5 b is FeF
3The TEM photo of/graphene film can be clearly seen that equally distributed nanometer Fe F
3Particle further specifies FeF
3Good with the composite effect of Graphene.Fig. 5 c is the FeF after the photo-reduction
3The SEM sectional drawing of/graphene film and is compared before the reduction, and it is mixed and disorderly that structure becomes, size is increased to about 20 present μ m by 8 original μ m, the efficient that photo-reduction is described is high, and the distance between the lamella that the energy that moment produces and steam have enlarged Graphene has formed desirable FeF
3/ graphene composite structure.FeF
3/ graphene oxide film and FeF
3The pictorial diagram of/graphene film as shown in Figure 2.
4) battery Integration Assembly And Checkout:
With nanometer Fe F
3, superconduction carbon black and PVDF be that 50:35:15 is dissolved in the nmp solvent according to mass ratio, evenly is coated on the aluminium foil, prepares pure FeF
3Positive plate.In being full of the glove box of argon gas, take metal lithium sheet as negative pole, be assembled into button cell.In the voltage range of 1-4.5V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 100mAh/g, circulate 100 times.
With FeF
3/ Graphene paper is placed on and makes positive plate on the aluminium foil, in the glove box of atmosphere protection, take metal lithium sheet as negative pole, is assembled into button cell.In the voltage range of 1-4.5V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 50-100mAh/g, circulate 100 times.Fig. 6 is pure nanometer Fe F
3And FeF
3Battery charge and discharge cycles curve under the 100mAh/g condition of/graphene film assembling.Pure FeF
3The first discharge capacity of positive electrode is 587mAh/g, and after 10 weeks of circulating, capacity is less than 100mAh/g, and capacity attenuation is serious.FeF
3The first discharge capacity of/graphene film positive electrode is about 700mAh/g, and after 10 weeks of circulating, reserve capacity is about 580mAh/g, and after 50 weeks, reserve capacity is 225mAh/g, and reserve capacity is 200mAh/g after 100 weeks.FeF is described
3/ graphene film is compared pure nanometer Fe F
3, capacity improves a lot, and has good cycle performance.
Embodiment 2:
1) preparation of graphite oxide:
Get the 1g(8000 order) natural flake graphite and 56ml mass concentration be after 92% sulfuric acid mixes, and adds 1.2g potassium nitrate, adds fast 5.8g potassium permanganate in 11 ℃ water-bath, mixes, the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 50 ℃, then reaction 2h adds 60ml water, simultaneously system is warming up to 75 ℃ of reaction 25min, adds 200ml distilled water cessation reaction again, and centrifuge washing is that 5,65 ℃ of vacuumizes obtain oxidation graphite solid to pH.Consistent with embodiment 1 characterization result, the interfloor distance of graphite oxide is 0.85nm, and than initial graphite, interfloor distance has obvious increase, illustrates that the graphite oxide oxidation effectiveness is fine.
2) FeF
3The preparation of nano particle:
Preparation amount of substance concentration is the NH of 1.5mol/L
4HF
2Fe (the NO of the aqueous solution and 0.5mol/L
3)
3Ethanolic solution, get 10ml NH
4HF
2The aqueous solution dropwise joins the Fe (NO of 10ml
3)
3In the ethanolic solution, adition process keeps stirring, and continues subsequently to stir 3h.After reaction finishes, add the ethanol washing system of 50ml, centrifugal collecting precipitation under the rotating speed of 6000rpm, with the sample collected at 70 ℃ of lower vacuumize 18h.Sample with drying is placed in the quartz boat at last, and being placed on atmosphere is in the corundum tube furnace of pure Ar gas, and gas flow rate is 88ml.min
-1, under 300 ℃, calcining 3h obtains FeF
3Nano particle.
3) FeF
3The preparation of/graphene film:
Get the oxidation graphite solid among the embodiment 1, compound concentration is that the GO solution of 0.25g/L claims.Take by weighing 0.025g FeF
3Nano powder, under the 70Hz frequency, ultrasonic 15min is dispersed in the 5ml deionized water, then with FeF
3Dispersion liquid is that the graphite oxide solution of 0.25g/L is mixed with the concentration of 80ml, continues ultrasonic 2h, then with the mixed liquor vacuum filtration above the PVDF filter membrane.Natural air drying in air is FeF with the upper strata
3The filter membrane of/graphene oxide film behind the natural air drying, is taken off above filter membrane in air, obtains the FeF of non-support
3/ graphene oxide film.Film being cut into little band shape, be exposed to window size and be under the photoflash lamp of digital camera of 10mm * 20mm, is 1mm apart from the distance of photoflash lamp, opens photoflash lamp, and flash time obtains anode material for lithium-ion batteries-FeF at 1.5 milliseconds
3/ graphene film.
4) battery Integration Assembly And Checkout:
With FeF
3/ graphene film is placed on and makes positive plate on the aluminium foil, in the glove box of atmosphere protection, take metal lithium sheet as negative pole, is assembled into button cell.In the voltage range of 1-4.5V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 100mAh/g, circulate 100 times.The first discharge specific capacity of thin-film material is 682mAh/g, circulate 100 times be 212mAh/g for reserve capacity afterwards.
Embodiment 3:
1) preparation of graphite oxide:
Get the 1g(8000 order) natural flake graphite and 43ml mass concentration be after 96% sulfuric acid mixes, and adds 2g potassium nitrate, adds fast 6g potassium permanganate in 10 ℃ 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 60ml water, simultaneously system is warming up to 85 ℃ of reaction 20min, adds 120ml distilled water cessation reaction again, and centrifuge washing is that 7,50 ℃ of vacuumizes obtain oxidation graphite solid to pH.Consistent with embodiment 1 characterization result, the interfloor distance of graphite oxide is 0.845nm, and than initial graphite, interfloor distance has obvious increase, illustrates that the graphite oxide oxidation effectiveness is fine.
2) FeF
3The preparation of nano particle:
Preparation amount of substance concentration is the NH of 2mol/L
4HF
2Fe (the NO of the aqueous solution and 0.1mol/L
3)
3Ethanolic solution, get 9ml NH
4HF
2The aqueous solution dropwise joins the Fe (NO of 30ml
3)
3In the ethanolic solution, adition process keeps stirring, and continues subsequently to stir 5h.After reaction finishes, add the ethanol washing system of 60ml, centrifugal collecting precipitation under the rotating speed of 8000rpm, with the sample collected at 75 ℃ of lower vacuumize 14h.Sample with drying is placed in the quartz boat at last, is placed in the quartz tube furnace that atmosphere is pure Ar gas, and gas flow rate is 82ml.min
-1, under 500 ℃, calcining 1h obtains FeF
3Nano particle.
3) FeF
3The preparation of/graphene film:
Get the oxidation graphite solid among the embodiment 1, compound concentration is that the GO solution of 1g/L claims.Get 0.04g FeF
3Nano powder, under the 60Hz frequency, ultrasonic 60min is dispersed in the 2ml deionized water, then with FeF
3Dispersion liquid is that the graphene oxide solution of 1g/L mixes with the concentration of 20ml, continues ultrasonic 2.5h, then with the mixed liquor vacuum filtration above the Anodisc inoranic membrane.Natural air drying in air is taken off above filter membrane.Be FeF with the upper strata
3The filter membrane of/graphene oxide film behind the natural air drying, is taken off above filter membrane in air, obtains the FeF of non-support
3/ graphene oxide film.Film being cut into little band shape, be exposed to window size and be under the photoflash lamp of digital camera of 10mm * 20mm, is 0.8mm apart from the distance of photoflash lamp, opens photoflash lamp, and flash time obtains anode material for lithium-ion batteries-FeF at 1 millisecond
3/ graphene film.
4) battery Integration Assembly And Checkout:
With FeF
3/ graphene film is placed on the aluminum substrates, makes positive plate, in the glove box of atmosphere protection, take metal lithium sheet as negative pole, is assembled into button cell.In the voltage range of 1-4.5V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 100mAh/g, circulate 100 times.The first discharge specific capacity of thin-film material is 652mAh/g, and circulating, reserve capacity is 193mAh/g after 100 times.
Embodiment 4:
1) preparation of graphite oxide:
Get the 5g(8000 order) natural flake graphite and 210ml mass concentration be after 94% sulfuric acid mixes, and adds 5.5g potassium nitrate, adds fast 29g 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 55 ℃, then reaction 3h adds 350ml water, simultaneously system is warming up to 95 ℃ of reaction 15min, use the excessive potassium permanganate of 300ml distilled water and 30ml hydrogen peroxide (30wt%) reduction, centrifuge washing is that 6,60 ℃ of vacuumizes obtain oxidation graphite solid to pH again.Consistent with embodiment 1 characterization result, the interfloor distance of graphite oxide is 0.815nm, and than initial graphite, interfloor distance has obvious increase, illustrates that the graphite oxide oxidation effectiveness is fine.
2) FeF
3The preparation of nano particle:
Preparation amount of substance concentration is the NH of 1.2mol/L
4HF
2Fe (the NO of the aqueous solution and 0.5mol/L
3)
3Ethanolic solution, get 50ml NH
4HF
2The aqueous solution dropwise joins the Fe (NO of 30ml
3)
3In the ethanolic solution, adition process keeps stirring, and continues subsequently to stir 4h.After reaction finishes, add the ethanol washing system of 200ml, centrifugal collecting precipitation under the rotating speed of 10000rpm, with the sample collected at 80 ℃ of lower vacuumize 12h.Sample with drying is placed in the quartz boat at last, and being placed on atmosphere is in the corundum tube furnace of pure Ar gas, and gas flow rate is 79ml.min
-1, under 3500 ℃, calcining 2.5h has just obtained FeF
3Nano particle.
3) FeF
3The preparation of/graphene film:
Get the oxidation graphite solid among the embodiment 1, compound concentration is that the GO solution of 0.35g/L claims.Get 0.035gFeF
3Nano powder, under the 40Hz frequency, ultrasonic 30min is dispersed in the 4ml deionized water, then with FeF
3Dispersion liquid is the graphene oxide solution mixing of 0.35g/L with the concentration of 100ml, continues ultrasonic 1h, then arrives the mixed liquor vacuum filtration above the anodization alumite.Be FeF with the upper strata
3The filter membrane of/graphene oxide film behind the natural air drying, is taken off above filter membrane in air, obtains the FeF of non-support
3/ graphene oxide film.Film being cut into little band shape, be exposed to window size and be under the photoflash lamp of digital camera of 10mm * 20mm, is 2mm apart from the distance of photoflash lamp, opens photoflash lamp, and flash time obtains anode material for lithium-ion batteries-FeF at 1.5 milliseconds
3/ graphene film.
4) battery Integration Assembly And Checkout:
With FeF
3/ graphene film is placed on and makes positive plate on the aluminium foil, in being full of the glove box of argon gas, take metal lithium sheet as negative pole, is assembled into button cell.In the voltage range of 1-4.5V, under the room temperature, carry out the charge and discharge cycles test with the electric current of 100mAh/g, circulate 100 times.The first discharge capacity of thin-film material is 667mAh/g, and circulating, reserve capacity is 223mAh/g after 100 times.
The present invention passes through in conjunction with FeF
3The nanometer of active material and Graphene Composite technique, utilization has the Graphene of the specific area of remarkable heat-conductivity conducting, super large, good chemical stability, wide electrochemical window, low thermal coefficient of expansion and excellent mechanical property as compound, and Graphene itself has storage lithium characteristic, effectively solving FeF
3Material in the circulating battery process in the serious polarization phenomena, novelty utilize up-to-date photoreduction met hod reduction FeF
3/ graphene oxide film is to overcome conventional high-temperature reducing process reduction FeF
3Generate the shortcoming of Fe and nanoparticle agglomerates, improved greatly the capacity of anode material for lithium-ion batteries, be about the 3-5 of at present main study hotspot positive electrode doubly.Preparation technology of the present invention is simple, the FeF of preparation
3/ graphene film 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 (7)
1. the preparation method of a power lithium-ion battery positive electrode, 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 0.25g/L-1g/L;
2) FeF
3The preparation of nano particle:
Prepare respectively the NH that amount of substance concentration is 1-2mol/L
4HF
2Fe (the NO of the aqueous solution and 0.1-0.5mol/L
3)
3Ethanolic solution, press NH
4HF
2And Fe (NO
3)
3Amount than 3-6:1, in the situation of stirring, with NH
4HF
2The aqueous solution joins Fe (NO
3)
3Ethanolic solution in, continue subsequently stirring reaction, washing after reaction finishes, centrifugal collecting precipitation is precipitated as (NH
4)
3FeF
6Presoma is with presoma and dry; Sample with drying is placed in the quartz boat at last, is placed in the tube furnace of atmosphere protection, keeps certain gas flow rate, and under 300-500 ℃, calcining 1-3h obtains FeF
3Nano particle;
3) FeF
3The preparation of/graphene film:
By nanometer Fe F
3Quality and the volume ratio of water be 0.005g/ml-0.05g/ml, with nanometer Fe F
3Ultrasonic being dispersed in the deionized water gets FeF
3Then dispersion liquid presses FeF
3Quality and the mass ratio of graphite oxide be 1-2:1, with FeF
3Dispersion liquid and concentration are that the graphite oxide solution of 0.25g/L-1g/L is mixed, continue ultrasonic dispersion after, the mixed liquor vacuum is filtered above the filter membrane; Natural air drying is taken off above filter membrane; Obtain the FeF of non-support
3/ graphene oxide film; FeF with the non-support that obtains
3/ graphene oxide film carries out photo-reduction, obtains power lithium-ion battery positive electrode-FeF
3/ graphene film.
2. preparation method according to claim 1 is characterized in that: in the step (2) with NH
4HF
2The aqueous solution joins Fe (NO
3)
3Ethanolic solution in, continuing subsequently the stirring reaction time is 2-5h; Described washing wherein adds volume and the Fe (NO of ethanol for reaction finishes the rear ethanol washing system that adds
3)
3Amount than for 8L/mol-20L/mol.
3. preparation method according to claim 1, it is characterized in that: the centrifugal rotating speed described in the step (2) is 3000-10000rpm; Described drying is at 50-80 ℃ of lower vacuumize 12-24h with presoma; Gas flow rate described in the step (2) is 10-90mlmin
-1
4. 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.
5. preparation method according to claim 1, it is characterized in that: the frequency of the ultrasonic dispersion described in the step (3) is 40-80Hz; Preparation FeF
3The time of ultrasonic dispersion is 5-60min during dispersion liquid; FeF
3Dispersion liquid mixes with graphite oxide solution, and the time of continuing ultrasonic dispersion is 1-2h.
6. preparation method according to claim 1, it is characterized in that: the described filter membrane of step (3) is a kind of of cellulose filter membrane, PVDF filter membrane, anodization alumite or Anodisc inoranic membrane.
7. preparation method according to claim 1 is characterized in that: described photo-reduction is the FeF with non-support
3/ graphene oxide paper cuts into little band shape, and be exposed to window size and be under the photoflash lamp of digital camera of 10mm * 20mm, be 0.5-2mm apart from the distance of photoflash lamp, open photoflash lamp, flash time is at the 1-2 millisecond.
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