CN108899473A - A kind of high-performance flexible cathode plate for lithium secondary battery and preparation method thereof - Google Patents
A kind of high-performance flexible cathode plate for lithium secondary battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-performance flexible cathode plate for lithium secondary battery, positive electrode is sodium vanadate nanobelt/redox graphene nanometer sheet Na5V12O32The composite membrane of/RGO, wherein sodium vanadate nanometer strip length is 100-300 μm, and width is 0.1-1 μm, with a thickness of 8-27nm, flexible compound film is not required to be supported in aluminum foil current collector, can assemble high energy lithium secondary battery with lithium foil, can work normally after multiple fold and under reeling condition.The invention also discloses a kind of preparation methods of high-performance flexible cathode plate for lithium secondary battery, by using simple vacuum filtration Na5V12O32The method of nanobelt and RGO nanometer sheet mixing suspension is prepared for fold and being bent the flexible electrode used, and simple process is easy to industrialized production.Flexible electrode produced by the present invention has excellent chemical property, is the ideal anode for assembling high-energy density flexibility lithium secondary battery.
Description
Technical field
The present invention relates to electrochemical fields, receive more particularly to a kind of flexible positive electrode material of lithium secondary cell-sodium vanadate
Rice band/redox graphene (Na5V12O32/ RGO) combination electrode film and preparation method thereof.
Background technique
Close in energy and power currently, although lithium ion battery occupies certain status in electronic consumer markets
Degree aspect improves there has also been further, but still has shortcoming in the application of electric automobiles, and with advanced
The development of portable electronic device, demand of the mankind to portable energy source are higher and higher.
Lithium metal has the theoretical specific capacity of 3860mAh/g, and the energy of the lithium secondary battery assembled using it as cathode is close
Spend the energy density considerably beyond the lithium ion battery assembled with Carbon anode.However, most layered oxide positive electrodes
LiCoO2,LiNi1-x-yCoxMnyO2,LiFePO4Deng theoretical specific capacity be usually no more than 200mAh/g；Stratiform is lithium-rich manganese-based just
Pole material Li1.2Mn0.54Co0.13Ni0.13O2Although have up to 300mAh/g specific capacity, for the first time coulombic efficiency it is low, times
The problems such as rate performance and poor circulation, constrains its industrial use.
As more and more electronic equipments are increasingly turned to frivolous and flexibility trend development, develop folding high energy
The energy storaging product of metric density is current research hotspot.Therefore, the energy density for improving positive electrode is that lithium secondary battery is current
One of significant challenge faced.
Johnson B.A. and White R.E. are in paper (Characterization of commercially
available lithium-ion batteries,Journal of Power Sources,1998,70(1):48-50.) in
It proposes, in industrialization lithium ion battery, aluminum foil current collector accounts for the 15% of entire positive quality, and copper foil current collector is in entire cathode
In account for 40% mass fraction.And aluminium foil and copper foil are non-electroactive substances, cannot provide capacitance, this is greatly reduced
The energy density of lithium ion battery, but it is again essential as electronic conduction collector.Therefore, a kind of novel light is developed
Collector has become the target of numerous researchers in recent years.By the positive electrode of high-energy density and novel light collector group
Dress is flexible electrode, more becomes current research focus.Because of the electric conductivity of carbon material and Lightness, carbon nanotube or
Graphene is frequently used to prepare novel light collector, to meet the needs of lightening electronic equipment and flexibility.
As anode material for lithium-ion batteries, barium oxide is because of its changeable valence state (+2 to+5) and more insertion
Site shows very high specific capacity.Wherein, stratiform V2O5When material is used as positive electroactive substance, there is 440mAh/g
Theoretical capacity, but high rate performance and cycle performance are still barely satisfactory.And stratiform sodium vanadate (Na5V12O32) it is used as barium oxide
One of classification has and is different from V2O5Unique layer structure of material, i.e.,：Sodium ion is previously embedded in V3O8Crystal interlayer,
Play skeletal support, so that Na5V12O32Crystal structure of material during charge and discharge (insertion-abjection lithium ion) is steady
It is fixed, improve its cycle performance；The material interlamellar spacing of sodium ion support expands, and is conducive to Li+Insertion and abjection, improve material
High rate performance.But 10-2The electronic conductivity of S/cm and 10-10cm2s-1The Li of rank+Ionic diffusion coefficient, insufficient for
Na5V12O32Meet the requirement of fast charging and discharging.
It is well known that nano material has huge specific surface area, extremely short ion diffusion length spreads system in lithium ion
Under conditions of number is so low, by the other size of electrode material synthesis nano, the solid phase of lithium ion in the material can be effectively shortened
Transition time.And the nano material of synthesis is combined with each other with electronic conductive material again, accelerate the transfer of electronics so that lithium from
Son and electronics can provide simultaneously on electrode material【Chen C.C.,Maier J.,Decoupling electron and ion
storage and the path from interfacial storage to artificial electrodes,Nature
Energy,2018,3:102-108.】, so as to improve the fast charging and discharging ability of electrode material.Monodimension nanometer material (nano wire,
Nanofiber, nanometer rods, nanobelt etc.) compound with two-dimension nano materials (nanometer sheet), good soft of available mechanical property
Property electrode material, this electrode do not need metal collector, conductive agent and binder, substantially increase the energy density of electrode,
The manufacturing cost of electrode is reduced, Devoting Major Efforts To Developing and popularization are worth.
Therefore, studying a kind of high-performance flexible cathode plate for lithium secondary battery and preparation method thereof is that those skilled in the art need
It solves the problems, such as.
Summary of the invention
In view of this, the present invention provides a kind of high-performance flexible cathode plate for lithium secondary battery.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of high-performance flexible cathode plate for lithium secondary battery, which is characterized in that the high-performance flexible cathode plate for lithium secondary battery
By sodium vanadate nanobelt with redox graphene is compound constitutes, the sodium vanadate nanobelt is woven into redox graphene
Flexible electrode film, wherein the molecular formula of sodium vanadate is Na5V12O32,, electroactive substance Na in the flexible electrode film5V12O32
Mass fraction be 91%-96%.
Preferably, the length of the sodium vanadate nanobelt is 100-300 μm, and width is 0.1-1 μm, with a thickness of 8-27nm.
By using above-mentioned technical proposal, beneficial effects of the present invention are as follows：
1, graphene can increase substantially material compared to other conductive materials as a kind of novel conductive material
Electronic conductivity；Increase the contact area of composite material；Further promote the mechanical strength of composite material.
2, membranaceous Na5V12O32/ RGO composite construction, on the one hand because eliminating binder, electroactive substance and stone
Black alkene direct combination, not only reduces the electromigration resistance of electrode material, also inhibits electrode material in the electrolytic solution molten
Solution, so as to improve the chemical property of electrode film.The film material being interwoven is conducive to the infiltration of electrolyte, accelerates lithium ion
Diffusion rate, improve the high rate performance of electrode film.
3, membranaceous Na5V12O32/ RGO composite construction, not only can be with the swollen of volume of the padded coaming in charge and discharge process
Variation that is swollen and shrinking, plays a very good protection, is also prevented from material material in cyclic process and reunites, to make
The cycle performance of electrode film is further promoted.
4, membranaceous Na5V12O32/ RGO composite construction, compared to the Na of no composite graphite alkene5V12O32Electrode film, it is compound
The mechanical performance of electrode film has very big improvement, and flexibility is more preferable, and the state before still being restored to after bending does not have
Have and expendable deformation occurs.
The present invention further discloses a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of preparation method of high-performance flexible cathode plate for lithium secondary battery, specific step is as follows：
Step 1: preparing redox graphene RGO
Graphene oxide GO is added in deionized water, obtains brown suspension after ultrasonic disperse 7-8h；
Sodium hydroxide is added in this suspension, stirs, is then transferred into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene
Reaction is cooled to after room temperature and obtains the suspension of black, and the mass ratio of the sodium hydroxide and graphene oxide GO are 1:20-
30；
It filters, is filtered resulting filter residue and be washed with deionized to neutrality, then with ethanol wash, finally deployed with ethyl alcohol
The suspension of the graphene oxide RGO tentatively restored in ethanol；
Step 2: preparing sodium vanadate nanobelt
Vanadium pentoxide powder is weighed, it is rear that 0.02M oxalic acid solution is added, 05-1h is stirred, blue solution is obtained；Described five
Ratio between V 2 O powder and 0.02M oxalic acid solution is specially 1:0.2-0.3.
Then sodium salt is added to continue to stir, mixed liquor is transferred in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and is reacted, it is cold
But the sodium vanadate Na of nano strip is obtained after5V12O32Material, precipitating, with distilled water dispensing laundry；
Then it filters, then obtains suspension with distillation water dispersion, be eventually adding a certain proportion of aminopropyl-triethoxy silicon
After alkane APTES ultrasound 30min, obtain sodium vanadate suspension, concentration 17mg/mL, the propyl-triethoxysilicane APTES with
The ratio of 0.02M oxalic acid solution is 16.5-33.5:1；
Step 3: preparation Na5V12O32/ RGO presoma
By the volume ratio 1 of RGO and sodium vanadate suspension:The ratio of 10-20 measures the above-mentioned RGO and sodium vanadate being prepared
Suspension is stirred by ultrasonic 20-40min after mixing, obtains Na5V12O32The mixed liquor of/RGO, suction filtration obtain membranaceous Na5V12O32/
RGO composite material；
It is subsequently placed in vacuum oven and dries, obtain membranaceous Na5V12O32/ RGO presoma；
Step 4: the Na of preparation5V12O32/ RGO combination electrode film
By the membranaceous Na of gained in step 35V12O32/ RGO presoma is placed in tube-type atmosphere furnace, after being passed through inert gas, slowly
Speed heating calcine by steps, and cooled down at a slow speed with furnace, obtain Na flexible5V12O32/ RGO combination electrode film.
By using above-mentioned preparation process, the beneficial effects of the present invention are：
In the present invention, by selecting graphene oxide as raw material, redox graphene is obtained after hydro-thermal reaction
(RGO), the surface for allowing for RGO in this way generates many flaws, is conducive to RGO and is uniformly dispersed in the solution, with conjunction
At nanobelt material can carry out well it is compound.
Preferably, the hydrothermal reaction condition in the step 1 is：Reaction time is 10-24h, reaction temperature 120-
200℃。
Preferably, the sodium salt in the step 2 is one of sodium nitrate, sodium sulphate, sodium chloride or sodium acetate, institute
Stating aminopropyl triethoxysilane APTES is coating material, model KH550.
Preferably, the hydrothermal reaction condition in the step 2 is：Reaction time is 8-15h, reaction temperature 160-240
℃。
Preferably, Na in the step 45V12O32The segmentation of/RGO presoma the calcining manners that heat up at a slow speed are：First in air
In with 0.2 DEG C/min rate be warming up to 280 DEG C, keep 3h；400 DEG C of sintering are warming up to 0.2 DEG C/min rate in nitrogen again
3h is cooled to room temperature at a slow speed with furnace.
Preferably, the drying temperature of flexible compound electrode film is 50-80 DEG C in the step 4.
Preferably, the content of redox graphene RGO is 0- in the flexible compound electrode film obtained in step 4
15%.
Preferably, the content of redox graphene RGO is in the flexible compound electrode film obtained in step 4
9%.
It can be seen via above technical scheme that compared with prior art, beneficial effects of the present invention are as follows：The present invention discloses
A kind of high-performance flexible cathode plate for lithium secondary battery preparation method, redox graphene RGO and vanadium are prepared with hydro-thermal method first
Sour sodium nanobelt, it is then that the RGO being prepared and sodium vanadate nanobelt is compound, obtain Na5V12O32/ RGO presoma, finally exists
Na is calcined in inert atmosphere5V12O32/ RGO presoma makes the further carbon of change graphene oxide GO being not yet reduced in presoma
Change, while the crystallinity of sodium vanadate nanobelt is also improved, and obtains Na5V12O32/ RGO combination electrode film.The present invention is by adopting
Water intaking thermal method prepares redox graphene RGO and sodium vanadate nanobelt, can directly obtain the powder of well-crystallized, high without making
Warm calcination processing, avoids the powder reuniting being likely to form during calcination, simple process, and Modulatory character is strong.And in water
After heat treatment, by using simple vacuum filtration Na5V12O32The method of nanobelt and RGO nanometer sheet mixing suspension, preparation
The flexible electrode used can be folded and be bent, simple process is easy to industrialized production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the XRD spectra and its refine spectrogram of sodium vanadate nanometer band electrode film prepared by the present invention.
Fig. 2 is pure Na5V12O32Electrode film, Na5V12O32/ 4%RGO combination electrode film and Na5V12O32/ 9%RGO compound electric
The XRD spectra of pole film.
Fig. 3 is the SEM photograph that the present invention prepares electrode film；
Fig. 4 is Na5V12O32The TEM photo of/9%RGO combination electrode film.
Fig. 5 is pure Na prepared by the present invention5V12O32Electrode film, Na5V12O32/ 4%RGO combination electrode film and Na5V12O32/
First charge-discharge curve of the 9%RGO combination electrode film under 35mA/g current density.
Fig. 6 is Na5V12O32Charging and discharging curve of/9%RGO combination electrode the film under different discharge-rates.
Fig. 7 is Na prepared by the present invention5V12O32The cycle performance curve of/9%RGO combination electrode film under 5C multiplying power.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a kind of high-performance flexible cathode plate for lithium secondary battery, by sodium vanadate nanobelt and oxygen reduction
The compound composition of graphite alkene, the sodium vanadate nanobelt and redox graphene are woven into flexible electrode film, wherein sodium vanadate
Molecular formula be Na5V12O32, electroactive substance Na in the flexible electrode film5V12O32Mass fraction be 91%-
96%.
Preferably, the length of sodium vanadate nanobelt is 100-300 μm, and width is 0.1-1 μm, with a thickness of 8-27nm.
The invention discloses a kind of preparation methods of high-performance flexible cathode plate for lithium secondary battery.
A kind of preparation method of high-performance flexible cathode plate for lithium secondary battery, specific step is as follows：
Step 1: preparing redox graphene RGO
Graphene oxide GO is added in deionized water, obtains brown suspension after ultrasonic disperse 7-8h；
Sodium hydroxide is added in this suspension, stirs, is then transferred into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene
Reaction is cooled to after room temperature and obtains the suspension of black, and the mass ratio of sodium hydroxide and graphene oxide GO are 1:20-30；
It filters, is filtered resulting filter residue and be washed with deionized to neutrality, then with ethanol wash, finally deployed with ethyl alcohol
The suspension of the graphene oxide RGO tentatively restored in ethanol, concentration 3.3mg/mL；
Step 2: preparing sodium vanadate nanobelt
Vanadium pentoxide powder is weighed, it is rear that 0.02M oxalic acid solution is added, 05-1h is stirred, blue solution is obtained；Described five
Ratio between V 2 O powder and 0.02M oxalic acid solution is specially 1:0.2-0.3.
Preferably, the ratio between the vanadium pentoxide powder and 0.02M oxalic acid solution is specially 1:0.275.
Then sodium salt is added to continue to stir, mixed liquor is transferred in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and is reacted, it is cold
But the sodium vanadate Na of nano strip is obtained after5V12O32Material, precipitating, with distilled water dispensing laundry；
Then it filters, then obtains suspension with distillation water dispersion, be eventually adding a certain proportion of aminopropyl-triethoxy silicon
After alkane APTES ultrasound 30min, obtain sodium vanadate suspension, concentration 17mg/mL, the propyl-triethoxysilicane APTES with
The ratio of 0.02M oxalic acid solution is 16.5-33.5:1.
Step 3: preparation Na5V12O32/ RGO presoma
By the volume ratio 1 of RGO and sodium vanadate suspension:The ratio of 10-20 measures the above-mentioned RGO and sodium vanadate being prepared
Suspension is stirred by ultrasonic 20-40min after mixing, obtains Na5V12O32The mixed liquor of/RGO, suction filtration obtain membranaceous Na5V12O32/
RGO composite material；
It is subsequently placed in vacuum oven and dries, obtain membranaceous Na5V12O32/ RGO presoma；
Step 4: the Na of preparation5V12O32/ RGO combination electrode film
By the membranaceous Na of gained in step 35V12O32/ RGO presoma is placed in tube-type atmosphere furnace, after being passed through inert gas, slowly
Speed heating calcine by steps, and cooled down at a slow speed with furnace, obtain Na flexible5V12O32/ RGO combination electrode film.
Preferably, the hydrothermal reaction condition in the step 1 is：Reaction time is 10-24h, reaction temperature 120-
200℃。
Preferably, the sodium salt in the step 2 is one of sodium nitrate, sodium sulphate, sodium chloride or sodium acetate, institute
Stating aminopropyl triethoxysilane APTES is coating material, model KH550.
Preferably, the hydrothermal reaction condition in the step 2 is：Reaction time is 8-15h, reaction temperature 160-240
℃。
Preferably, the hydrothermal reaction condition in step 2：Reaction time is 12h, and reaction temperature is 200 DEG C.
Preferably, Na in the step 45V12O32The segmentation of/RGO presoma the calcining manners that heat up at a slow speed are：First in air
In with 0.2 DEG C/min rate be warming up to 280 DEG C, keep 3h；400 DEG C of sintering are warming up to 0.2 DEG C/min rate in nitrogen again
3h is cooled to room temperature at a slow speed with furnace.
Preferably, the drying temperature of flexible compound electrode film is 50-80 DEG C in the step 4.
Preferably, the drying temperature of flexible compound electrode film is 60 DEG C in the step 4.
Preferably, the content of redox graphene RGO is 0- in the flexible compound electrode film obtained in step 4
15%.
Preferably, the content of redox graphene RGO is in the flexible compound electrode film obtained in step 4
9%.
The present invention is further detailed below in conjunction with specific embodiment.
Embodiment 1：
A kind of preparation method of high-performance flexible cathode plate for lithium secondary battery, specific step is as follows：
Step 1: 100mg graphene oxide GO, ultrasonic disperse 8h is added in the beaker for filling 100mL deionized water,
Obtain 1mgmL-1Brown suspension；4g sodium hydroxide NaOH is added in this suspension, rapidly stirring suspension 2h, then plus
In the hydrothermal reaction kettle for entering 200mL inner liner polytetrafluoroethylene, in 160 DEG C of reaction 18h, the suspended of black is obtained after being cooled to room temperature
Liquid filters gained filter residue and is washed with deionized to neutrality, then with ethanol wash, finally deploys tentatively being restored with ethyl alcohol
The suspension of graphene oxide RGO in ethanol, concentration 3.3mg/mL；
Step 2: weighing 1g vanadic anhydride (V2O5) powder is in beaker, addition 0.02 oxalic acid (H of 100mL2C2O4) molten
Liquid stirs 1h, obtains the solution of blue, and 1.06g NaNO is then added3, continue to stir 30min, mixed solution is transferred to 200mL
In the hydrothermal reaction kettle of inner liner polytetrafluoroethylene, in 200 DEG C of reaction 12h, the sodium vanadate of nano strip is obtained after cooling
Na5V12O32Material, precipitating distilled water dispensing laundry, then filters, then obtain suspension with distillation water dispersion, is eventually adding one
After the aminopropyl triethoxysilane APTES ultrasound 30min of certainty ratio, sodium vanadate suspension, concentration 17mg/mL are obtained；
Step 3: proportionally measuring the above-mentioned 4mL RGO suspension being prepared and 60mL sodium vanadate suspension (its
In, the mass ratio of RGO and sodium vanadate is 9：91) 30min, is stirred by ultrasonic after mixing, obtains Na5V12O32The mixed liquor of/RGO is taken out
Filter obtains membranaceous Na5V12O32/ RGO composite material is subsequently placed in 60 DEG C of drying in vacuum oven, obtains membranaceous
Na5V12O32/ RGO presoma；
Step 4: by gained Na in step 35V12O32/ RGO presoma is placed in tube-type atmosphere furnace, after leading to nitrogen, at a slow speed
Heat up calcine by steps, and cools down at a slow speed with furnace, obtains Na flexible5V12O32/ RGO composite material film.Through thermogravimetic analysis (TGA), electrode
Electroactive substance Na in film5V12O32Mass fraction be 91%.
In order to prove the Na of the invention being prepared5V12O32/ RGO combination electrode film have good effect, the present invention into
Further verifying is gone.
Na prepared by embodiment 15V12O32/ RGO combination electrode film is cut into the thin rounded flakes that diameter is 12mm, with it
For anode, button cell is assembled with cathode of lithium and 2400 perforated membrane of Celgard, electrolyte is the LiPF of 1mol/L6Carbonic acid second
(mass ratio of the two is 1 for enester (EC) and dimethyl carbonate (DMC) solution:1).
Above-mentioned button cell is tested using constant current charge-discharge technology, test temperature is 25 DEG C, charging termination electricity
Pressure is 4V, final discharging voltage 1.5V.When with 0.1C (35mA/g), 0.2C, 0.5C, 1C, 2C, 5C and 10C charge and discharge, put
Capacitance is respectively 331,308,270,233,197,158 and 121mAh/g, be respectively relative to 52.7,49.0,43.1,37.1,
31.3,25.2 and 19.3mAh/cm3Volume and capacity ratio；The charge and discharge under 5C multiplying power, the capacity retention ratio point after recycling 500 times
It Wei 93.7%.
Embodiment 2
As described in Example 1, change the content of graphene, synthesize Na5V12O32/ RGO combination electrode film.Through thermal weight loss point
It analyses, the electroactive substance Na in electrode film5V12O32Mass fraction be 96%.
Na is tested as described in Example 15V12O32The chemical property of/RGO composite material.In 1.5-4.0V voltage range
It is interior, with charge and discharge under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C multiplying power, first discharge specific capacity is respectively 311,285,
251,211,183,132 and 84mAh/g is respectively relative to 49.5,45.4,40.0,33.6,29.0,21.0 and 13.4mAh/cm3
Volume and capacity ratio.Under 2C multiplying power, after circulation 200 times, specific discharge capacity conservation rate is 93.5%.
For the embodiment of the present invention 1-2, will be further analyzed in conjunction with Figure of description.
In embodiment 1, the electroactive substance Na in electrode film5V12O32Mass fraction be 91%；
In example 2, the electroactive substance Na in electrode film5V12O32Mass fraction be 96%.
As shown in Figure 1, Fig. 1 is XRD spectra and its refine of sodium vanadate nanometer band electrode film prepared by the embodiment of the present invention 1
Spectrogram.
As seen from the figure, the sodium vanadate nanobelt of synthesis has Na5V12O32Crystal structure, lattice parameter is：β=106.56 °, wherein containing about 5% NaV3O8Phase, main phase
Characteristic diffraction peak and XRD standard card PDF#24-1156 it is almost the same, belong to P121/m1 space group, crystallization with higher
Degree.
In order to further prove effect of the present invention, for pure Na5V12O32Electrode film, Na5V12O32/ 4%RGO combination electrode
Film and Na5V12O32Three kinds of/9%RGO combination electrode film compares, as shown in Fig. 2, Fig. 2 is pure Na5V12O32Electrode film,
Na5V12O32/ 4%RGO combination electrode film and Na5V12O32The XRD spectra of/9%RGO combination electrode film.As shown in Figure 2,
Na5V12O32/ RGO combination electrode film has and pure Na5V12O32Electrode film similar XRD characteristic diffraction peak position, due to RGO's
Package, belongs to Na5V12O32Each characteristic peak intensity it is in a slight decrease.Since RGO is calcined at a lower temperature, it is difficult to height stone
Mo Hua, essentially amorphous carbon, and its content in electrode film is low, therefore does not occur feature belonging to RGO on XRD spectra
Diffraction maximum.
Fig. 3 is the SEM photograph of electrode film prepared by the present invention.
Wherein, the a&c in Fig. 3 is pure Na prepared by the present invention5V12O32The SEM photograph of electrode film.As seen from the figure,
Na5V12O32Material has 1-dimention nano band pattern, and length is 100-300 μm, and width is 0.1-1 μm, and nanobelt is interleaved with each other into
For electrode film, there is apparent porous structure between nanobelt.
B&d in Fig. 3 is Na prepared by the present invention5V12O32The SEM picture of/9%RGO combination electrode film.As seen from the figure,
Na5V12O32Nanobelt is wrapped in RGO nanometer sheet, and pattern keeps complete.
Fig. 4 is Na5V12O32The TEM photo of/9%RGO combination electrode film, as shown in Figure 4, Na5V12O32Nanobelt uniformly divides
Be dispersed in RGO matrix, nanobelt with a thickness of 8-27nm.
Fig. 5 is pure Na prepared by the present invention5V12O32Electrode film, Na5V12O32/ 4%RGO combination electrode film and Na5V12O32/
First charge-discharge curve of the 9%RGO combination electrode film under 35mA/g current density.As seen from the figure, the initial charge/discharge of three
Capacity is respectively 295/300,305/311 and 326/331mAh/g, and discharge capacity is slightly larger than charging capacity for the first time, shows to discharge
The lithium ion for being embedded in crystal in journey has minute quantity not deviate from, is trapped in lattice, this is conducive to the stabilization of crystal structure, to change
The cycle performance of kind electrode.
Fig. 6 is Na5V12O32Charging and discharging curve of/9%RGO combination electrode the film under different discharge-rates.It will be appreciated from fig. 6 that
Its in 0.1C (35mA/g), 0.2C, 0.5C, 1C, 2C, 5C and 10C, discharge capacity is respectively 331,308,270,233,197,
158 and 121mAh/g is respectively relative to 52.7,49.0,43.1,37.1,31.3,25.2 and 19.3mAh/cm3Volume specific volume
Amount has excellent high rate performance.
Fig. 7 is Na prepared by the present invention5V12O32The cycle performance curve of/9%RGO combination electrode film under 5C multiplying power.By
Fig. 7 is it is found that after circulation 500 times, and capacity retention ratio 93.7%, cycle performance is good.
Embodiment 3
Weigh 1g vanadic anhydride (V2O5) powder is in beaker, addition 0.02M oxalic acid (H2C2O4) solution 100mL, stirring
1h obtains the solution of blue, 1.06gNaNO is then added3, continue to stir 30min, mixed solution is transferred to 200mL liner poly- four
In the hydrothermal reaction kettle of vinyl fluoride, in 200 DEG C of reaction 12h, the sodium vanadate Na of nano strip is obtained after cooling5V12O32Material.
Precipitating is washed with distilled water, and is then filtered, then obtains suspension with distillation water dispersion, and the solid-to-liquid ratio of suspension is 17mg/mL.?
In resulting suspension, after addition 4mL aminopropyl triethoxysilane KH550, ultrasonic 30min, sodium vanadate suspension is obtained.Subtract
Pressure filters, and extracts the filter cake on filter paper, 50 DEG C of vacuum drying 12h.Dry filter cake is placed in tube-type atmosphere furnace, prior to air
280 DEG C are warming up to 0.2 DEG C/min rate in atmosphere, keeps the temperature 3h；Then it is warming up in nitrogen atmosphere with 0.2 DEG C/min rate
400 DEG C of sintering 3h, then cooled down at a slow speed with furnace, obtain nano strip Na5V12O32Woven electrode film.
Na is tested as described in Example 15V12O32The chemical property of electrode film.In 1.5-4.0V voltage range,
With charge and discharge under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C multiplying power, first discharge specific capacity is respectively 300,267,203,
152,115,58 and 20mAh/g is respectively relative to 47.7,42.6,32.3,24.2,18.3,9.2 and 3.2mAh/cm3Volume
Specific capacity.Under 2C multiplying power, after circulation 200 times, specific discharge capacity conservation rate is 76.5%.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of high-performance flexible cathode plate for lithium secondary battery, which is characterized in that the high-performance flexible cathode plate for lithium secondary battery by
Sodium vanadate nanobelt and the compound composition of redox graphene, the sodium vanadate nanobelt is woven into soft with redox graphene
Property electrode film, wherein the molecular formula of sodium vanadate be Na5V12O32,, electroactive substance Na in the flexible electrode film5V12O32's
Mass fraction is 91%-96%.
2. a kind of high-performance flexible cathode plate for lithium secondary battery according to claim 1, which is characterized in that the sodium vanadate is received
The length of rice band is 100-300 μm, and width is 0.1-1 μm, with a thickness of 8-27nm.
3. -2 described in any item a kind of preparation methods of high-performance flexible cathode plate for lithium secondary battery according to claim 1, special
Sign is that specific step is as follows：
Step 1: preparing redox graphene RGO
Graphene oxide GO is added in deionized water, obtains brown suspension after ultrasonic disperse 7-8h；
Sodium hydroxide is added in this suspension, stirs, is then transferred into the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and reacts,
It is cooled to after room temperature and obtains the suspension of black, the mass ratio of the sodium hydroxide and graphene oxide GO are 1:20-30；
It filters, is filtered resulting filter residue and be washed with deionized to neutrality, then with ethanol wash, finally deploy to obtain with ethyl alcohol
The suspension of the graphene oxide RGO tentatively restored in ethanol；
Step 2: preparing sodium vanadate nanobelt
Vanadium pentoxide powder is weighed, it is rear that 0.02M oxalic acid solution is added, 0.5-1h is stirred, blue solution is obtained；Five oxidation
Ratio between two vanadium powders and 0.02M oxalic acid solution is specially 1:0.2-0.3；
Then sodium salt is added to continue to stir, mixed liquor is transferred in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and is reacted, cooling
The sodium vanadate Na of nano strip is obtained afterwards5V12O32Material, precipitating, with distilled water dispensing laundry；
Then it filters, then obtains suspension with distillation water dispersion, be eventually adding propyl-triethoxysilicane APTES ultrasound 30mi n
Afterwards, sodium vanadate suspension is obtained, the ratio of the propyl-triethoxysilicane APTES and 0.02M oxalic acid solution is 16.5-
33.5:1；
Step 3: preparation Na5V12O32/ RGO presoma
By the volume ratio 1 of RGO and sodium vanadate suspension:The ratio of 10-20 measures the above-mentioned RGO being prepared and sodium vanadate is suspended
Liquid is stirred by ultrasonic 20-40mi n, obtains Na after mixing5V12O32The mixed liquor of/RGO, suction filtration obtain membranaceous Na5V12O32/RGO
Composite material；
It is subsequently placed in vacuum oven and dries, obtain membranaceous Na5V12O32/ RGO presoma；
Step 4: the Na of preparation5V12O32/ RGO combination electrode film
By the membranaceous Na of gained in step 35V12O32/ RGO presoma is placed in tube-type atmosphere furnace, after being passed through inert gas, is risen at a slow speed
Warm calcine by steps, and cooled down at a slow speed with furnace, obtain Na flexible5V12O32/ RGO combination electrode film.
4. a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery according to claim 3, which is characterized in that institute
The hydrothermal reaction condition stated in step 1 is：Reaction time is 10-24h, and reaction temperature is 120-200 DEG C.
5. a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery according to claim 3, which is characterized in that institute
Stating the sodium salt in step 2 is one of sodium nitrate, sodium sulphate, sodium chloride or sodium acetate, the aminopropyl-triethoxy silicon
Alkane APTES is coating material, model KH550.
6. a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery according to claim 3, which is characterized in that institute
The hydrothermal reaction condition stated in step 2 is：Reaction time is 8-15h, and reaction temperature is 160-240 DEG C.
7. a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery according to claim 3, which is characterized in that institute
State Na in step 45V12O32The segmentation of/RGO presoma the calcining manners that heat up at a slow speed are：First in air with 0.2 DEG C/mi n speed
Rate is warming up to 280 DEG C, keeps 3h；
400 DEG C of sintering 3h are warming up to 0.2 DEG C/mi n rate in nitrogen again, are cooled to room temperature at a slow speed with furnace.
8. a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery according to claim 3, which is characterized in that institute
The drying temperature for stating flexible compound electrode film in step 4 is 50-80 DEG C.
9. a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery according to claim 3, which is characterized in that institute
The content for stating redox graphene RGO in flexible compound electrode film obtained in step 4 is 0-15%.
10. a kind of preparation method of high-performance flexible cathode plate for lithium secondary battery according to claim 9, which is characterized in that
The content of redox graphene RGO is 9% in the flexible compound electrode film obtained in step 4.
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