CN106374107A - Preparation method of graphene/metal carbide porous micro-sphere electrode - Google Patents
Preparation method of graphene/metal carbide porous micro-sphere electrode Download PDFInfo
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- CN106374107A CN106374107A CN201611096984.3A CN201611096984A CN106374107A CN 106374107 A CN106374107 A CN 106374107A CN 201611096984 A CN201611096984 A CN 201611096984A CN 106374107 A CN106374107 A CN 106374107A
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- 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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a graphene/metal carbide porous micro-sphere electrode, and relates to a preparation method of a hierarchically structured three-dimensional composite material. The invention aims to solve the problems of battery performance degradation and cycling stability influence caused by volume expansion of an existing anode material. The method comprises the following steps: firstly, preparation of oxidized graphene; secondly, preparation of a mixed solution; thirdly, drying; fourthly, annealing treatment to obtain the graphene/metal carbide porous micro-sphere electrode. The graphene/metal carbide porous micro-sphere electrode prepared in the invention as a lithium ion battery anode material has good electrochemical lithium storage performance, the capacity of a battery prepared by using the graphene/metal carbide porous micro-sphere electrode as the battery anode material under the current density of 0.1 A/g is greater than 500 mAh/g, the capacity of the battery under the current density of 3 A/g is greater than 300 mAh/g, and the capacity is hardly attenuated after 500 times of circulation. The preparation method is suitable for preparing the graphene/metal carbide porous micro-sphere electrode.
Description
Technical field
The present invention relates to a kind of three-dimensional composite material preparation method of hierarchy.
Background technology
Rapid economic development, human future faces the threat of lack of energy, and problem of environmental pollution highlights simultaneously, and exploitation is new
The new forms of energy of cleaning green are extremely urgent.Various energy-storage batteries start greatly to be paid close attention to.The electrode material performance of battery is to determine
The key factor of electrochmical power source performance.Lithium ion battery has the superiority such as specific energy is high, memory effect is little, low in the pollution of the environment
Can, have become as widely used secondary cell in the electronic products such as current mobile phone, notebook computer, and lithium ion battery
As electrokinetic cell, huge application prospect is also had on electric motor car.Negative material is the important composition portion of lithium ion battery
Point, electrode material mainly adopts material with carbon element, but its capacity is relatively low, and the theoretical capacity of graphite is 372mah/g, greatly limit
The performance of lithium ion battery is it is impossible to meet the demand to high-capacity battery for the people.Current research considers the higher metal of capacity
Material or the theoretical specific capacity improving negative material by the mode such as compound.No matter by which kind of mode, circulating battery process
In embedding and removing reaction, all can lead to the either large or small expansion of the volume of negative material, thus it is former to destroy negative material
There is pattern, and lead to cell performance decay, affect cyclical stability.In order to solve this difficult problem, current research mainly considers
By three-dimensional graded porous structure, carry out the volumetric expansion of buffer electrode material.
It is combined with Graphene using the high metal carbides of theoretical specific capacity, the theoretical specific volume of battery can be greatly improved
Amount, existing much preparation researches about graphene composite material both at home and abroad, but homogeneous three dimensional structure pattern is difficult to obtain
's.It is combined, by Graphene and metal carbides, the microsphere electrode material that preparation has loose structure, active substance can be increased
With the contact area of electrolyte, and increased voidage, reduce the impact that volumetric expansion brings, the circulation of battery can be improved
Stability, thus improve the performance of lithium ion battery.
Content of the invention
The invention aims to solving the volumetric expansion of existing negative material, lead to cell performance decay, impact circulation
The problem of stability, and a kind of preparation method of Graphene/metal carbides porous microsphere electrode is provided.
A kind of preparation method of Graphene/metal carbides porous microsphere electrode, is specifically realized by the following steps:
First, prepare graphene oxide:
1., native graphite and potassium permanganate are added in the sulphuric acid that mass fraction is 98%, then in ice bath and stirring speed
Spend for stirring 1h～2h under 300r/min～400r/min, obtain mixture a；
Step one 1. described in native graphite and potassium permanganate mass ratio be 1:5；
Step one 1. described in the quality of native graphite and mass fraction be 98% volume ratio of sulphuric acid be 1g:60ml
～100ml；
2., mixture a is heated to 35 DEG C, then is incubated 1h at temperature is 35 DEG C, then add deionization in mixture a
Water, then by add deionized water mixture be warming up to 90 DEG C～95 DEG C, then temperature be 90 DEG C～95 DEG C at insulation 30min～
35min, obtains mixture b；
Step one 2. described in the volume ratio of mixture a and deionized water be 1:1；
3., mixture b is naturally cooled to room temperature, then the h that mass fraction is 35%2o2Solution is added to mixture b
In, under room temperature, low whipping speed is to react 10min under 100r/min～300r/min, obtains graphene oxide water solution；By oxygen
Graphite aqueous solution is centrifuged under the centrifugal speed of 3000r/min～3500r/min, takes the upper strata after centrifugation clear
Liquid；Again the supernatant obtaining after centrifugation is centrifuged under the centrifugal speed of 8000r/min～8500r/min again
Separate, take the deposit after centrifugation, then be dried 1h～3h at temperature is 60 DEG C～80 DEG C, obtain graphite oxide
Alkene；
Step one 1. described in the quality of native graphite and step one 3. described in mass fraction be 35% h2o2Molten
The volume ratio of liquid is 1g:(5ml～6ml)；
2nd, prepare mixed solution:
1., the graphene oxide that 3. step one obtains is dissolved in water, obtains graphene oxide solution；
Step 2 1. described in graphene oxide solution concentration be 5g/l～15g/l；
2., polystyrene microsphere is dissolved in water, obtains the polystyrene microsphere that mass fraction is 8%～15% molten
Liquid；
3., in graphene oxide solution, add metal chloride, then low whipping speed is 500r/min～1000r/min
Lower stirring reaction 1h～2h, then carry out ultrasonic disperse 1h～2h, obtain dark mixed solution；
Step 2 3. described in the volume ratio of the quality of metal chloride and graphene oxide solution be (0.4g～1g):
30ml；
4., add the polystyrene microsphere solution that mass fraction is 8%～15% in dark mixed solution, then in stirring
Speed is stirring reaction 1h～2h under 500r/min～1000r/min, then carries out ultrasonic disperse 1h～2h, obtains mixed solution；
Step 2 4. described in mass fraction be 8%～15% polystyrene microsphere solution and dark mixed solution
Volume ratio is 50:(20～40)；
3rd, it is dried:
The mixed solution that 4. step 2 is obtained is spray-dried at being 130 DEG C～180 DEG C with temperature under agitation, obtains
To light yellow fluffy powder；
4th, make annealing treatment:
The light yellow fluffy powder that step 3 is obtained is put in tube furnace, then under inert gas shielding by tube furnace with
The heating rate of 3 DEG C/min～5 DEG C/min rises to 180 DEG C～240 DEG C from room temperature, is incubated 50min～80min, then with 3 DEG C/min
The heating rate of～5 DEG C/min rises to 750 DEG C～850 DEG C from 180 DEG C～240 DEG C, is incubated 120min～150min, finally with 5
DEG C/rate of temperature fall of min～8 DEG C/min is down to 180 DEG C～240 DEG C from 750 DEG C～850 DEG C, program stopped, is naturally cooling to room
Temperature, annealing terminates, and obtains Graphene/metal carbides porous microsphere electrode.
Compared with prior art, the invention has the advantages that
First, a kind of preparation method of metal chloride porous microsphere electrode that the present invention provides not only makes Graphene and gold
Belong to carbide and carry out good being combined, obtain the porous three-dimensional electrode material with hierarchy；
2nd, the composition of the Graphene/metal carbides porous microsphere electrode of present invention preparation is carbon and metal chloride, main
Want composition to be carbon, through annealing, three-dimensional porous structure firm it is not easy to destroyed during embedding and removing；Product
In contain a certain amount of metal carbides, greatly improve the theoretical specific capacity of composite；
3rd, the present invention builds nanoscale three-dimensional structure in micrometer level porous structure, and specific surface area and voidage are bigger, can
To be effectively increased the contact area of active substance and electrolyte, considerably increase lithium ion transport passage and volumetric expansion buffering
Space, effectively reduces the impact that volumetric expansion is brought, and is more favorable for the embedding and removing reaction in battery, greatly improves
The performance of battery；
4th, preparation process is simple of the present invention, preparation condition gentle, cheap, can be with large-scale production；Most metal chlorine
Compound can be combined with Graphene using the method, it is desirable to relatively low when from metal-containing compound, is not limited to gold
Belong to chloride use, metal sulfide equally can be prepared the Graphene possessing hierarchy and metal carbides are combined three
Dimension electrode material；
5th, the Graphene/metal carbides porous microsphere electrode of present invention preparation is as lithium ion battery negative material exhibition
Reveal good electrochemical lithium storage performance, using the present invention preparation Graphene/metal carbides porous microsphere electrode as lithium from
The button cell of sub- cell negative electrode material capacity under the electric current density of 0.1a/g is more than 500ma h/g, close in the electric current of 3a/g
The lower capacity of degree is more than 300ma h/g, and after 500 circulations of circulation, capacity is not almost decayed, and illustrates good stable circulation
Property.
The present invention is applied to and prepares Graphene/metal carbides porous microsphere electrode.
Brief description
Fig. 1 is the sem figure of Graphene/5000 times of metal carbides porous microsphere electrode amplification of embodiment one preparation；
Fig. 2 is the sem figure of Graphene/20000 times of metal carbides porous microsphere electrode amplification of embodiment one preparation；
Fig. 3 is xrd spectrogram, and in Fig. 3,1 is the xrd of the Graphene/metal carbides porous microsphere electrode of embodiment one preparation
Curve, 2 is the xrd standard curve of cementite；
Fig. 4 is the sem figure of Graphene/4000 times of metal carbides porous microsphere electrode amplification of embodiment two preparation；
Fig. 5 is the sem figure of Graphene/15000 times of metal carbides porous microsphere electrode amplification of embodiment two preparation；
Fig. 6 is using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery negative
The button cell of material is in the cycle performance figure that discharge and recharge density is under 0.1a/g；
Fig. 7 is using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery negative
The button cell of material is in the coulombic efficiency figure that discharge and recharge density is under 0.1a/g；
Fig. 8 is using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery negative
The high rate performance figure of the button cell of material, in Fig. 8, " " is discharge curve, and "●" is charging curve, and a is that charging and discharging currents are close
Spend for 0.1a/g, b is 0.3a/g for charging and discharging currents density, c is charging and discharging currents density is 0.5a/g, d is charging and discharging currents
Density is 1a/g, and e is 3a/g for charging and discharging currents density, and f is 0.1a/g for charging and discharging currents density.
Specific embodiment:
Below the implementation example of the present invention is elaborated: the present embodiment is entered under premised on technical solution of the present invention
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Specific embodiment one: present embodiment is a kind of preparation side of Graphene/metal carbides porous microsphere electrode
Method, completes according to the following steps:
First, prepare graphene oxide:
1., native graphite and potassium permanganate are added in the sulphuric acid that mass fraction is 98%, then in ice bath and stirring speed
Spend for stirring 1h～2h under 300r/min～400r/min, obtain mixture a；
Step one 1. described in native graphite and potassium permanganate mass ratio be 1:5；
Step one 1. described in the quality of native graphite and mass fraction be 98% volume ratio of sulphuric acid be 1g:60ml
～100ml；
2., mixture a is heated to 35 DEG C, then is incubated 1h at temperature is 35 DEG C, then add deionization in mixture a
Water, then by add deionized water mixture be warming up to 90 DEG C～95 DEG C, then temperature be 90 DEG C～95 DEG C at insulation 30min～
35min, obtains mixture b；
Step one 2. described in the volume ratio of mixture a and deionized water be 1:1；
3., mixture b is naturally cooled to room temperature, then the h that mass fraction is 35%2o2Solution is added to mixture b
In, under room temperature, low whipping speed is to react 10min under 100r/min～300r/min, obtains graphene oxide water solution；By oxygen
Graphite aqueous solution is centrifuged under the centrifugal speed of 3000r/min～3500r/min, takes the upper strata after centrifugation clear
Liquid；Again the supernatant obtaining after centrifugation is centrifuged under the centrifugal speed of 8000r/min～8500r/min again
Separate, take the deposit after centrifugation, then be dried 1h～3h at temperature is 60 DEG C～80 DEG C, obtain graphite oxide
Alkene；
Step one 1. described in the quality of native graphite and step one 3. described in mass fraction be 35% h2o2Molten
The volume ratio of liquid is 1g:(5ml～6ml)；
2nd, prepare mixed solution:
1., the graphene oxide that 3. step one obtains is dissolved in water, obtains graphene oxide solution；
Step 2 1. described in graphene oxide solution concentration be 5g/l～15g/l；
2., polystyrene microsphere is dissolved in water, obtains the polystyrene microsphere that mass fraction is 8%～15% molten
Liquid；
3., in graphene oxide solution, add metal chloride, then low whipping speed is 500r/min～1000r/min
Lower stirring reaction 1h～2h, then carry out ultrasonic disperse 1h～2h, obtain dark mixed solution；
Step 2 3. described in the volume ratio of the quality of metal chloride and graphene oxide solution be (0.4g～1g):
30ml；
4., add the polystyrene microsphere solution that mass fraction is 8%～15% in dark mixed solution, then in stirring
Speed is stirring reaction 1h～2h under 500r/min～1000r/min, then carries out ultrasonic disperse 1h～2h, obtains mixed solution；
Step 2 4. described in mass fraction be 8%～15% polystyrene microsphere solution and dark mixed solution
Volume ratio is 50:(20～40)；
3rd, it is dried:
The mixed solution that 4. step 2 is obtained is spray-dried at being 130 DEG C～180 DEG C with temperature under agitation, obtains
To light yellow fluffy powder；
4th, make annealing treatment:
The light yellow fluffy powder that step 3 is obtained is put in tube furnace, then under inert gas shielding by tube furnace with
The heating rate of 3 DEG C/min～5 DEG C/min rises to 180 DEG C～240 DEG C from room temperature, is incubated 50min～80min, then with 3 DEG C/min
The heating rate of～5 DEG C/min rises to 750 DEG C～850 DEG C from 180 DEG C～240 DEG C, is incubated 120min～150min, finally with 5
DEG C/rate of temperature fall of min～8 DEG C/min is down to 180 DEG C～240 DEG C from 750 DEG C～850 DEG C, program stopped, is naturally cooling to room
Temperature, annealing terminates, and obtains Graphene/metal carbides porous microsphere electrode.
Compared with prior art, the invention has the advantages that
First, a kind of preparation method of metal chloride porous microsphere electrode that present embodiment provides not only makes Graphene
Carry out good being combined with metal carbides, obtain the porous three-dimensional electrode material with hierarchy；
2nd, the composition of the Graphene/metal carbides porous microsphere electrode of present embodiment preparation is carbon and metal chlorination
Thing, main component is carbon, through annealing, three-dimensional porous structure firm it is not easy to destroyed during embedding and removing；
Contain a certain amount of metal carbides in product, greatly improve the theoretical specific capacity of composite；
3rd, present embodiment builds nanoscale three-dimensional structure in micrometer level porous structure, and specific surface area and voidage are more
Greatly, the contact area of active substance and electrolyte can be effectively increased, considerably increase lithium ion transport passage and volume is swollen
Swollen cushion space, effectively reduces the impact that volumetric expansion is brought, and is more favorable for the embedding and removing reaction in battery, greatly
Improve the performance of battery；
4th, present embodiment preparation process is simple, preparation condition gentle, cheap, can be with large-scale production；Most gold
Belong to chloride to be combined with Graphene using the method, it is desirable to relatively low when from metal-containing compound, do not limit to
In metal chloride use, metal sulfide equally can be prepared the Graphene possessing hierarchy and metal carbides are answered
Close three-diemsnional electrode material；
5th, the Graphene/metal carbides porous microsphere electrode of present embodiment preparation is as lithium ion battery negative material
Material shows good electrochemical lithium storage performance, with the Graphene/metal carbides porous microsphere electrode of present embodiment preparation
As lithium ion battery negative material button cell under the electric current density of 0.1a/g capacity be more than 500ma h/g, in 3a/g
Electric current density under capacity be more than 300ma h/g, circulation 500 circulation after capacity almost do not decay, illustrate good
Cyclical stability.
Present embodiment is applied to prepares Graphene/metal carbides porous microsphere electrode.
Specific embodiment two: the difference from specific embodiment one for the present embodiment is: step 2 3. described in
The power of ultrasonic disperse is 100w～150w.Other are identical with specific embodiment one.
Specific embodiment three: the difference from specific embodiment one or two for the present embodiment is: step 2 4. middle institute
The power of the ultrasonic disperse stated is 100w～150w.Other are identical with specific embodiment one or two.
Specific embodiment four: the difference from one of specific embodiment one to three for the present embodiment is: step 2 is 3.
Described in metal chloride be fecl3·6h2O or cocl2.Other are identical with specific embodiment one to three.
Specific embodiment five: the difference from one of specific embodiment one to four for the present embodiment is: in step 4
Described noble gases are argon or nitrogen.Other are identical with specific embodiment one to four.
Specific embodiment six: the difference from one of specific embodiment one to five for the present embodiment is: step 2 is 1.
Described in graphene oxide solution concentration be 10g/l～15g/l.Other are identical with specific embodiment one to five.
Specific embodiment seven: the difference from one of specific embodiment one to six for the present embodiment is: step 2 is 2.
Middle polystyrene microsphere is dissolved in water, obtain the polystyrene microsphere solution that mass fraction is 10%～15%.Other with
Specific embodiment one to six is identical.
Specific embodiment eight: the difference from one of specific embodiment one to seven for the present embodiment is: in step 3
The mixed solution that 4. step 2 is obtained is spray-dried at being 130 DEG C～160 DEG C with temperature under agitation, obtains light yellow
Fluffy powder.Other are identical with specific embodiment one to seven.
Specific embodiment nine: the difference from one of specific embodiment one to eight for the present embodiment is: in step 4
The light yellow fluffy powder that step 3 is obtained is put in tube furnace, then under inert gas shielding by tube furnace with 3 DEG C/min
Heating rate rise to 200 DEG C from room temperature, be incubated 60min, then rise to 800 DEG C with the heating rate of 3 DEG C/min from 200 DEG C, protect
Warm 120min, is finally down to 200 DEG C with the rate of temperature fall of 5 DEG C/min from 800 DEG C, and program stopped is naturally cooling to room temperature, annealing
Process terminates, and obtains Graphene/metal carbides porous microsphere electrode.Other are identical with specific embodiment one to eight.
Specific embodiment ten: the difference from one of specific embodiment one to nine for the present embodiment is: in step 4
The light yellow fluffy powder that step 3 is obtained is put in tube furnace, then under inert gas shielding by tube furnace with 3 DEG C/min
The heating rate of～4 DEG C/min rises to 180 DEG C～200 DEG C from room temperature, be incubated 60min～80min, then with 3 DEG C/min～4 DEG C/
The heating rate of min rises to 750 DEG C～800 DEG C from 180 DEG C～200 DEG C, is incubated 120min～150min, finally with 5 DEG C/min
The rate of temperature fall of～6 DEG C/min is down to 180 DEG C～200 DEG C from 750 DEG C～800 DEG C, and program stopped is naturally cooling to room temperature, moves back
Fiery process terminates, and obtains Graphene/metal carbides porous microsphere electrode.Other are identical with specific embodiment one to nine.
Using following examples checking beneficial effects of the present invention:
Embodiment one: a kind of preparation method of Graphene/metal carbides porous microsphere electrode, is to prepare according to the following steps
:
First, prepare graphene oxide:
1., native graphite and potassium permanganate are added in the sulphuric acid that mass fraction is 98%, then in ice bath and stirring speed
Spend for stirring 1.5h under 300r/min, obtain mixture a；
Step one 1. described in native graphite and potassium permanganate mass ratio be 1:5；
Step one 1. described in the quality of native graphite and mass fraction be 98% volume ratio of sulphuric acid be 1g:
40ml；
2., mixture a is heated to 35 DEG C, then is incubated 1h at temperature is 35 DEG C, then add deionization in mixture a
Water, then the mixture adding deionized water is warming up to 95 DEG C, then it is incubated 30min at temperature is 95 DEG C, obtain mixture b；
Step one 2. described in the volume ratio of mixture a and deionized water be 1:1；
3., mixture b is naturally cooled to room temperature, then the h that mass fraction is 35%2o2Solution is added to mixture b
In, under room temperature, low whipping speed is to react 10min under 200r/min, obtains graphene oxide water solution；By graphene oxide water
Solution is centrifuged under the centrifugal speed of 3000r/min, takes the supernatant after centrifugation；Obtain after centrifugation again
The supernatant be centrifuged again under the centrifugal speed of 8000r/min, take the deposit after centrifugation, then
Temperature is dried 3h at being 70 DEG C, obtains graphene oxide；
Step one 1. described in the quality of native graphite and step one 3. described in mass fraction be 35% h2o2Molten
The volume ratio of liquid is 1g:5ml；
2nd, prepare mixed solution:
1., the graphene oxide that 3. step one obtains is dissolved in water, obtains graphene oxide solution；
Step 2 1. described in graphene oxide solution concentration be 10g/l；
2., polystyrene microsphere is dissolved in water, obtains the polystyrene microsphere solution that mass fraction is 10%；
3., in graphene oxide solution, add metal chloride, then low whipping speed is stirring reaction under 500r/min
1h, then carry out ultrasonic disperse 1h, obtain dark mixed solution；
Step 2 3. described in metal chloride be fecl3·6h2o；
Step 2 3. described in the volume ratio of the quality of metal chloride and graphene oxide solution be 0.65g:30ml；
Step 2 3. described in ultrasonic disperse power be 100w；
4., add the polystyrene microsphere solution that mass fraction is 10% in dark mixed solution, then low whipping speed
For stirring reaction 1h under 500r/min, then carry out ultrasonic disperse 1h, obtain mixed solution；
Step 2 4. described in mass fraction be 10% polystyrene microsphere solution and dark mixed solution volume
Than for 50:30；
Step 2 4. described in ultrasonic disperse power be 100w；
3rd, it is dried:
The mixed solution that 4. step 2 is obtained is spray-dried at being 150 DEG C with temperature under agitation, obtains pale yellow
Color fluffy powder；
4th, make annealing treatment:
The light yellow fluffy powder that step 3 is obtained is put in tube furnace, more under an argon atmosphere by tube furnace with 3 DEG C/
The heating rate of min rises to 200 DEG C from room temperature, is incubated 60min, then rises to 800 DEG C with the heating rate of 3 DEG C/min from 200 DEG C,
Insulation 120min, is finally down to 200 DEG C with the rate of temperature fall of 5 DEG C/minn from 800 DEG C, and program stopped is naturally cooling to room temperature,
Annealing terminates, and obtains Graphene/metal carbides porous microsphere electrode.
Embodiment two: a kind of preparation method of Graphene/metal carbides porous microsphere electrode, is to prepare according to the following steps
:
First, prepare graphene oxide:
1., native graphite and potassium permanganate are added in the sulphuric acid that mass fraction is 98%, then in ice bath and stirring speed
Spend for stirring 1.5h under 300r/min, obtain mixture a；
Step one 1. described in native graphite and potassium permanganate mass ratio be 1:5；
Step one 1. described in the quality of native graphite and mass fraction be 98% volume ratio of sulphuric acid be 1g:
40ml；
2., mixture a is heated to 35 DEG C, then is incubated 1h at temperature is 35 DEG C, then add deionization in mixture a
Water, then the mixture adding deionized water is warming up to 95 DEG C, then it is incubated 30min at temperature is 95 DEG C, obtain mixture b；
Step one 2. described in the volume ratio of mixture a and deionized water be 1:1；
3., mixture b is naturally cooled to room temperature, then the h that mass fraction is 35%2o2Solution is added to mixture b
In, under room temperature, low whipping speed is to react 10min under 200r/min, obtains graphene oxide water solution；By graphene oxide water
Solution is centrifuged under the centrifugal speed of 3000r/min, takes the supernatant after centrifugation；Obtain after centrifugation again
The supernatant be centrifuged again under the centrifugal speed of 8000r/min, take the deposit after centrifugation, then
Temperature is dried 3h at being 70 DEG C, obtains graphene oxide；
Step one 1. described in the quality of native graphite and step one 3. described in mass fraction be 35% h2o2Molten
The volume ratio of liquid is 1g:5ml；
2nd, prepare mixed solution:
1., the graphene oxide that 3. step one obtains is dissolved in water, obtains graphene oxide solution；
Step 2 1. described in graphene oxide solution concentration be 10g/l；
2., polystyrene microsphere is dissolved in water, obtains the polystyrene microsphere solution that mass fraction is 10%；
3., in graphene oxide solution, add metal chloride, then low whipping speed is stirring reaction under 500r/min
1h, then carry out ultrasonic disperse 1h, obtain dark mixed solution；
Step 2 3. described in metal chloride be cocl2；
Step 2 3. described in the volume ratio of the quality of metal chloride and graphene oxide solution be 0.65g:30ml；
Step 2 3. described in ultrasonic disperse power be 120w；
4., add the polystyrene microsphere solution that mass fraction is 10% in dark mixed solution, then low whipping speed
For stirring reaction 1h under 500r/min, then carry out ultrasonic disperse 1h, obtain mixed solution；
Step 2 4. described in mass fraction be 10% polystyrene microsphere solution and dark mixed solution volume
Than for 50:30；
Step 2 4. described in ultrasonic disperse power be 120w；
3rd, it is dried:
The mixed solution that 4. step 2 is obtained is spray-dried at being 160 DEG C with temperature under agitation, obtains pale yellow
Color fluffy powder；
4th, make annealing treatment:
The light yellow fluffy powder that step 3 is obtained is put in tube furnace, more under an argon atmosphere by tube furnace with 3 DEG C/
The heating rate of min rises to 200 DEG C from room temperature, is incubated 60min, then rises to 800 DEG C with the heating rate of 3 DEG C/min from 200 DEG C,
Insulation 120min, is finally down to 200 DEG C with the rate of temperature fall of 5 DEG C/minn from 800 DEG C, and program stopped is naturally cooling to room temperature,
Annealing terminates, and obtains Graphene/metal carbides porous microsphere electrode.
Assembled battery: Graphene prepared by embodiment one/metal carbides porous microsphere electrode is made slurry and is coated on
On Copper Foil, make a diameter of 24 millimeters of electrode slice after being dried；A diameter of 24 millimeters of electrode slice is put into the negative electrode casing of battery,
Deca 50 μ l electrolyte, makes barrier film cover electrode material, then Deca 50 μ l electrolyte, puts into lithium piece, adds anode cover, by battery
Compression, after standing 24h, that is, completes, obtains the Graphene/metal carbides porous microsphere electrode conduct of embodiment one preparation
The button cell of lithium ion battery negative material；Described electrolyte is the lipf that concentration is 1mol/l6Solution；Described barrier film
For polypropylene diaphragm；Described electrolyte is the mixed liquor of ethylene carbonate, diethyl carbonate and fluorinated ethylene carbonate, mixing
In liquid, ethylene carbonate and the volume ratio of diethyl carbonate are 1:1；Ethylene carbonate with the volume ratio of fluorinated ethylene carbonate is
1:0.03.
Fig. 1 is the sem figure of Graphene/5000 times of metal carbides porous microsphere electrode amplification of embodiment one preparation；
From fig. 1, it can be seen that Graphene/metal carbides porous microsphere the electrode size of embodiment one preparation is evenly distributed, many
Number diameter concentrates on 1 μm～2 μm.
Fig. 2 is the sem figure of Graphene/20000 times of metal carbides porous microsphere electrode amplification of embodiment one preparation；
As can be seen from Figure 2, embodiment one preparation Graphene/metal carbides porous microsphere electrode in be dispersed with 400nm～
The uniform bore of 500nm, hole wall is made up of thin graphene, is also dispersed with carbonization iron nano-particle in hole wall.
Fig. 3 is xrd spectrogram, and in Fig. 3,1 is the xrd of the Graphene/metal carbides porous microsphere electrode of embodiment one preparation
Curve, 2 is the xrd standard curve of cementite；
As can be seen from Figure 3, the Graphene/metal carbides porous microsphere electrode of embodiment one preparation and cementite xrd standard
Curve coincide well it was demonstrated that embodiment one has successfully synthesized Graphene/metal carbides porous microsphere electrode.
Fig. 4 is the sem figure of Graphene/4000 times of metal carbides porous microsphere electrode amplification of embodiment two preparation；
As can be seen from Figure 4, the Graphene of embodiment two preparation/most diameter of metal carbides porous microsphere electrode size distribution
Concentrate on 1 μm～5 μm.
Fig. 5 is the sem figure of Graphene/15000 times of metal carbides porous microsphere electrode amplification of embodiment two preparation；
As can be seen from Figure 5, embodiment two preparation Graphene/metal carbides porous microsphere electrode in be dispersed with 300nm～
The uniform bore of 500nm, hole wall is made up of thin graphene, is also dispersed with carbonization cobalt nano-particle in hole wall.
Fig. 6 is using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery negative
The button cell of material is in the cycle performance figure that discharge and recharge density is under 0.1a/g；
As can be seen from Figure 6, using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery
The button cell of negative material shows good cyclical stability, and after 500 circulations of circulation, capacity is not almost decayed.
Fig. 7 is using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery negative
The button cell of material is in the coulombic efficiency figure that discharge and recharge density is under 0.1a/g；
As can be seen from Figure 7, using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery
The button cell of negative material shows good cyclical stability, and after 500 circulations of circulation, coulombic efficiency almost maintains
Between 99%～100.
Fig. 8 is using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery negative
The high rate performance figure of the button cell of material, in Fig. 8, " " is discharge curve, and "●" is charging curve, and a is that charging and discharging currents are close
Spend for 0.1a/g, b is 0.3a/g for charging and discharging currents density, c is charging and discharging currents density is 0.5a/g, d is charging and discharging currents
Density is 1a/g, and e is 3a/g for charging and discharging currents density, and f is 0.1a/g for charging and discharging currents density.
As it can be observed in the picture that using the Graphene/metal carbides porous microsphere electrode of embodiment one preparation as lithium ion battery
The button cell of negative material shows good multiplying power stability, and, in the case that electric current density is for 3a/g, its capacity is still for it
300mah/g can be more than.
Claims (10)
1. a kind of Graphene/metal carbides porous microsphere electrode preparation method it is characterised in that the method specifically press with
Lower step completes:
First, prepare graphene oxide:
1., native graphite and potassium permanganate are added in the sulphuric acid that mass fraction is 98%, then in ice bath and mixing speed are
Stir 1h～2h under 300r/min～400r/min, obtain mixture a；
Step one 1. described in native graphite and potassium permanganate mass ratio be 1:5；
Step one 1. described in the quality of native graphite and mass fraction be 98% sulphuric acid volume ratio be 1g:60ml～
100ml；
2., mixture a is heated to 35 DEG C, then is incubated 1h at temperature is 35 DEG C, then add deionized water in mixture a,
Again by add deionized water mixture be warming up to 90 DEG C～95 DEG C, then temperature be 90 DEG C～95 DEG C at insulation 30min～
35min, obtains mixture b；
Step one 2. described in the volume ratio of mixture a and deionized water be 1:1；
3., mixture b is naturally cooled to room temperature, then the h that mass fraction is 35%2o2Solution is added in mixture b, room
The lower low whipping speed of temperature is to react 10min under 100r/min～300r/min, obtains graphene oxide water solution；By graphite oxide
Aqueous solution is centrifuged under the centrifugal speed of 3000r/min～3500r/min, takes the supernatant after centrifugation；Again
The supernatant obtaining after centrifugation is centrifuged under the centrifugal speed of 8000r/min～8500r/min again,
Take the deposit after centrifugation, then be dried 1h～3h at temperature is 60 DEG C～80 DEG C, obtain graphene oxide；
Step one 1. described in the quality of native graphite and step one 3. described in mass fraction be 35% h2o2Solution
Volume ratio is 1g:(5ml～6ml)；
2nd, prepare mixed solution:
1., the graphene oxide that 3. step one obtains is dissolved in water, obtains graphene oxide solution；
Step 2 1. described in graphene oxide solution concentration be 5g/l～15g/l；
2., polystyrene microsphere is dissolved in water, obtains the polystyrene microsphere solution that mass fraction is 8%～15%；
3., in graphene oxide solution, add metal chloride, then low whipping speed is to stir under 500r/min～1000r/min
Mix reaction 1h～2h, then carry out ultrasonic disperse 1h～2h, obtain dark mixed solution；
Step 2 3. described in the volume ratio of the quality of metal chloride and graphene oxide solution be (0.4g～1g):
30ml；
4., add the polystyrene microsphere solution that mass fraction is 8%～15% in dark mixed solution, then low whipping speed
For stirring reaction 1h under 500r/min～1000r/min～2h, then carry out ultrasonic disperse 1h～2h, obtain mixed solution；
Step 2 4. described in mass fraction be 8%～15% polystyrene microsphere solution and dark mixed solution volume
Than for 50:(20～40)；
3rd, it is dried:
The mixed solution that 4. step 2 is obtained is spray-dried at being 130 DEG C～180 DEG C with temperature under agitation, obtains shallow
Yellow fluffy powder；
4th, make annealing treatment:
The light yellow fluffy powder that step 3 is obtained is put in tube furnace, then under inert gas shielding by tube furnace with 3 DEG C/
The heating rate of min～5 DEG C/min rises to 180 DEG C～240 DEG C from room temperature, is incubated 50min～80min, then with 3 DEG C/min～5
DEG C/heating rate of min rises to 750 DEG C～850 DEG C from 180 DEG C～240 DEG C, is incubated 120min～150min, finally with 5 DEG C/
The rate of temperature fall of min～8 DEG C/min is down to 180 DEG C～240 DEG C from 750 DEG C～850 DEG C, and program stopped is naturally cooling to room temperature,
Annealing terminates, and obtains Graphene/metal carbides porous microsphere electrode.
2. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
In step 2 3. described in ultrasonic disperse power be 100w～150w.
3. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
In step 2 4. described in ultrasonic disperse power be 100w～150w.
4. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
In step 2 3. described in metal chloride be fecl3·6h2O or cocl2.
5. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
Noble gases described in step 4 are argon or nitrogen.
6. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
In step 2 1. described in graphene oxide solution concentration be 10g/l～15g/l.
7. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
In step 2 2. in polystyrene microsphere is dissolved in water, obtain the polystyrene microsphere that mass fraction is 10%～15% molten
Liquid.
8. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
4. the mixed solution obtaining step 2 in the step 3 is spray-dried at being 130 DEG C～160 DEG C with temperature under agitation,
Obtain light yellow fluffy powder.
9. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature exists
In step 4, the light yellow fluffy powder that step 3 obtains is put in tube furnace, then by tube furnace under inert gas shielding
Rise to 200 DEG C with the heating rate of 3 DEG C/min from room temperature, be incubated 60min, then risen to from 200 DEG C with the heating rate of 3 DEG C/min
800 DEG C, it is incubated 120min, is finally down to 200 DEG C with the rate of temperature fall of 5 DEG C/min from 800 DEG C, program stopped, it is naturally cooling to
Room temperature, annealing terminates, and obtains Graphene/metal carbides porous microsphere electrode.
10. the preparation method of a kind of Graphene according to claim 1/metal carbides porous microsphere electrode, its feature
It is in step 4 to put into the light yellow fluffy powder that step 3 obtains in tube furnace, then by tubular type under inert gas shielding
Stove rises to 180 DEG C～200 DEG C with the heating rate of 3 DEG C/min～4 DEG C/min from room temperature, is incubated 60min～80min, then with 3
DEG C/heating rate of min～4 DEG C/min rises to 750 DEG C～800 DEG C from 180 DEG C～200 DEG C, is incubated 120min～150min,
It is down to 180 DEG C～200 DEG C with the rate of temperature fall of 5 DEG C/min～6 DEG C/min from 750 DEG C～800 DEG C afterwards, program stopped, drops naturally
Warm to room temperature, annealing terminates, obtain Graphene/metal carbides porous microsphere electrode.
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| CN108794942A (en) * | 2018-07-09 | 2018-11-13 | 黑龙江科技大学 | A kind of preparation method of polymer and the compound Meta Materials of three-dimensional porous graphene |
| CN111370699A (en) * | 2020-03-11 | 2020-07-03 | 肇庆市华师大光电产业研究院 | Lithium-sulfur battery positive electrode material and preparation method thereof |
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