CN106532002B - A kind of preparation method of graphene coated nano-graphite electrode material - Google Patents
A kind of preparation method of graphene coated nano-graphite electrode material Download PDFInfo
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Abstract
A kind of preparation method of graphene coated nano-graphite electrode material, it is related to a kind of preparation method of electrode material.The purpose of the present invention is to solve the existing graphite cathode material less than 1 micron since compacted density is low, coulombic efficiency is low for the first time, is difficult the problem of applying as lithium ion battery negative material.Method: one, large scale graphene oxide is prepared；Two, the mixed solution of big size graphene, polyimides and nano graphite powder is prepared；Three, dry；Four, it makes annealing treatment, obtains graphene coated nano-graphite electrode material.Capacity of the button cell at 0.1C using graphene coated nano-graphite electrode material prepared by the present invention as lithium ion battery negative material is greater than 362mAh/g, and coulombic efficiency is greater than 89%, and capacity remains larger than 92% after 500 circulations.The present invention can get a kind of graphene coated nano-graphite electrode material.
Description
Technical field
The present invention relates to a kind of preparation methods of electrode material.
Background technique
Because lithium ion battery itself has big energy density, small in size, light weight, of low pollution, has extended cycle life etc.
Excellent properties, it has closely obtained wide hair in mobile device, digital equipment, portable electronic device, electric car etc. at present
Using.As various electronic equipments are to small-size light-weight and enhancing multi-functional, that drivingization requires for a long time, the energy of lithium ion battery
Improving for metric density and power density will be dependent on the development of its electrode material and perfect.Therefore for a long time, improve lithium from
The specific capacity of sub- cell negative electrode material reduces irreversible capacity for the first time, improves cyclical stability, improves fast charging and discharging performance one
It is directly the emphasis of research and development.
Graphite has become lithium ion battery negative material mainstay material at present, wherein its good conductivity of natural graphite, knot
Brilliant degree is high, charge/discharge capacity is high, efficiency for charge-discharge is high, and irreversible capacity is low, low charge and discharge potential platform, has layer structure
Have become the negative electrode material being most widely used in lithium ion battery.It need to but most before natural graphite negative electrode material application
The pretreatments such as coat to improve compacted density, coulombic efficiency etc., requires particle as lithium ion battery negative material for the first time
Having a size of micron order, if the graphite particle in natural graphite mine less than 1 micron is as negative electrode material, compacted density is low, first
Secondary coulombic efficiency is low etc., is just difficult to obtain commercial applications in lithium ion battery negative material, most enterprises are this part
Material is wasted as waste material, how to be improved the compacted density and its electrochemical lithium storage performance of the graphite cathode of nanoscale, is become
One technical problem.
Summary of the invention
The purpose of the present invention is to solve the existing graphite cathode material less than 1 micron since compacted density is low, for the first time
Coulombic efficiency is low, is difficult the problem of applying as lithium ion battery negative material, and provides a kind of graphene coated nano-graphite
The preparation method of electrode material.
A kind of preparation method of graphene coated nano-graphite electrode material, is specifically realized by the following steps:
One, large scale graphene oxide is prepared:
1., by partial size be that 300 μm~500 μm of crystalline flake graphite is added in the mixed acid of sulfuric acid and nitric acid, then is being stirred
Speed is stirred to react for 24 hours~48h under conditions of being 300r/min~500r/min, then is filtered, and obtains black powder；Make again
Cleaning 3 times~5 times is carried out to black powder with distilled water, then dry 12h at being 60 DEG C~80 DEG C in temperature~for 24 hours, it is done
Black powder after dry；Black powder after drying is put into 60s~180s in the micro-wave oven that power is 500W~1000W, is obtained
To quasiflake graphite；
Step 1 1. described in partial size be 300 μm~500 μm crystalline flake graphite quality and sulfuric acid and nitric acid mixing
The volume ratio of acid is 3g:(400mL~450mL)；
Step 1 1. described in sulfuric acid and nitric acid mixed acid in the volume ratio of sulfuric acid and nitric acid be 3:1；
2., quasiflake graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in the condition of ice bath
Lower reaction 1h~2h, obtains mixed liquor A, by mixed liquor A temperature be 30 DEG C~40 DEG C at keep the temperature 1h~3h, then be added go from
Sub- water, then 30min~50min is kept the temperature at being 90 DEG C~95 DEG C in temperature, cooled to room temperature obtains mixed liquid B；
Step 1 2. described in quasiflake graphite and potassium permanganate mass ratio be 1:5；
Step 1 2. described in quasiflake graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:
200mL；
Step 1 2. described in quasiflake graphite quality and deionized water volume ratio be 1g:(130mL~
140mL)；
3., into mixed liquid B be added mass fraction be 35% H2O2Solution, and stir evenly, then react at room temperature
10min~30min obtains graphene oxide water solution；By graphene oxide water solution low whipping speed be 6000r/min~
Be centrifuged under conditions of 10000r/min, take centrifuge separation after deposit, then by deposit temperature be 60 DEG C~
Dry 12h~48h, obtains large scale graphene oxide at 80 DEG C；
Step 1 3. described in mixed liquid B and mass fraction be 35% H2O2The volume ratio of solution is 50:(1~2)；
Two, the mixed solution of big size graphene, polyimides and nano graphite powder is prepared:
1., 3. large scale graphene oxide that step 1 obtains is dissolved into water, it is molten to obtain large scale graphene oxide
Liquid；
Step 2 1. described in large scale graphene oxide solution concentration be 5g/L~15g/L；
2., nano graphite powder and polyimides aqueous acid be added in distilled water, be 300r/ being stirred for speed
It is stirred to react 20min~40min under min~500r/min, obtains the mixed solution of nano graphite powder and polyimide acid；
Step 2 2. described in nano graphite powder quality and distilled water volume ratio be (3g~10g): 400mL；
Step 2 2. described in polyimides aqueous acid and distilled water volume ratio be (0.5~2): 400；
3., large scale graphene oxide solution and nano graphite powder and the mixed solution of polyimide acid mixed, then
Mixing speed is to be stirred to react 0.5h~2h under 300r/min~500r/min, then the ultrasound in the case where ultrasonic power is 100W~150W
Disperse 0.5h~2h, obtains dark mixed solution；
Three, dry:
It is under stiring to be done by spraying at 140 DEG C~170 DEG C with temperature by 3. dark mixed solution that step 2 obtains
It is dry, obtain fluffy powder；
Four, it makes annealing treatment:
The fluffy powder that step 3 is obtained is put into tube furnace, then under inert gas protection by tube furnace with 3 DEG C/
Min~5 DEG C/min heating rate rises to 180 DEG C~240 DEG C from room temperature, keeps the temperature 50min~80min, then with 3 DEG C/min~5
DEG C/heating rate of min rises to 900 DEG C~1100 DEG C from 180 DEG C~240 DEG C, keep the temperature 120min~150min, finally with 5 DEG C/
Min~8 DEG C/min rate of temperature fall is down to 180 DEG C~240 DEG C from 900 DEG C~1100 DEG C, and program stopped is naturally cooling to room
Temperature, annealing terminate, and obtain graphene coated nano-graphite electrode material.
Step 2 of the present invention 2. described in the purchase of polyimides aqueous acid from Shanghai Ye He Trade Co., Ltd..
Compared with prior art, the present invention has the following advantages:
One, the present invention is in order to solve the existing graphite cathode material less than 1 micron since compacted density is low, and coulomb is imitated for the first time
Rate is low, is difficult the problem of applying as lithium ion battery negative material, proposes to utilize large scale, high-quality graphene is as " viscous
Knot agent " is re-prepared as the graphite coat of nano-scale the new electrode materials of micron-scale, and nano-graphite greatly improved
Compacted density, coulombic efficiency for the first time, the comprehensive performances such as specific capacity；
Two, using graphene coated nano-graphite electrode material prepared by the present invention as the button of lithium ion battery negative material
Capacity of the formula battery at 0.1C is greater than 362mAh/g, and compacted density is greater than 2.1g/cm3, greater than 89%, 500 follow coulombic efficiency
Capacity remains larger than 92% after ring.
The present invention can get a kind of graphene coated nano-graphite electrode material.
Detailed description of the invention
Fig. 1 is the microscope photo of 3. large scale graphene oxide that one step 1 of embodiment obtains；
Fig. 2 is the Atomic Mechanics microscope photo of 3. large scale graphene oxide that one step 1 of embodiment obtains；
Fig. 3 is the stereoscan photograph for the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains；
Fig. 4 is Raman map, in Fig. 41 be nano-graphite Raman curve, 2 graphite obtained for one step 4 of embodiment
The Raman map of alkene cladding nano-graphite electrode material；
Fig. 5 is the stereoscan photograph for the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains；
Fig. 6 is XRD spectrum, and 1 is the XRD curve of nano-graphite, and 2 graphene coateds obtained for one step 4 of embodiment are received
The XRD curve of rice graphite electrode material；
Fig. 7 is charging and discharging curve, and 1 is the button cell using nano-graphite as lithium ion battery negative material at 0.1C times
Charging and discharging curve under rate, 2 is using the graphene coated nano-graphite electrode materials that one step 4 of embodiment obtains as lithium ion
The button cell of cell negative electrode material charging and discharging curve under 0.1C multiplying power.
Specific embodiment:
Specific embodiment 1: present embodiment is a kind of preparation method of graphene coated nano-graphite electrode material,
It is specifically realized by the following steps:
One, large scale graphene oxide is prepared:
1., by partial size be that 300 μm~500 μm of crystalline flake graphite is added in the mixed acid of sulfuric acid and nitric acid, then is being stirred
Speed is stirred to react for 24 hours~48h under conditions of being 300r/min~500r/min, then is filtered, and obtains black powder；Make again
Cleaning 3 times~5 times is carried out to black powder with distilled water, then dry 12h at being 60 DEG C~80 DEG C in temperature~for 24 hours, it is done
Black powder after dry；Black powder after drying is put into 60s~180s in the micro-wave oven that power is 500W~1000W, is obtained
To quasiflake graphite；
Step 1 1. described in partial size be 300 μm~500 μm crystalline flake graphite quality and sulfuric acid and nitric acid mixing
The volume ratio of acid is 3g:(400mL~450mL)；
Step 1 1. described in sulfuric acid and nitric acid mixed acid in the volume ratio of sulfuric acid and nitric acid be 3:1；
2., quasiflake graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in the condition of ice bath
Lower reaction 1h~2h, obtains mixed liquor A, by mixed liquor A temperature be 30 DEG C~40 DEG C at keep the temperature 1h~3h, then be added go from
Sub- water, then 30min~50min is kept the temperature at being 90 DEG C~95 DEG C in temperature, cooled to room temperature obtains mixed liquid B；
Step 1 2. described in quasiflake graphite and potassium permanganate mass ratio be 1:5；
Step 1 2. described in quasiflake graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:
200mL；
Step 1 2. described in quasiflake graphite quality and deionized water volume ratio be 1g:(130mL~
140mL)；
3., into mixed liquid B be added mass fraction be 35% H2O2Solution, and stir evenly, then react at room temperature
10min~30min obtains graphene oxide water solution；By graphene oxide water solution low whipping speed be 6000r/min~
Be centrifuged under conditions of 10000r/min, take centrifuge separation after deposit, then by deposit temperature be 60 DEG C~
Dry 12h~48h, obtains large scale graphene oxide at 80 DEG C；
Step 1 3. described in mixed liquid B and mass fraction be 35% H2O2The volume ratio of solution is 50:(1~2)；
Two, the mixed solution of big size graphene, polyimides and nano graphite powder is prepared:
1., 3. large scale graphene oxide that step 1 obtains is dissolved into water, it is molten to obtain large scale graphene oxide
Liquid；
Step 2 1. described in large scale graphene oxide solution concentration be 5g/L~15g/L；
2., nano graphite powder and polyimides aqueous acid be added in distilled water, be 300r/ being stirred for speed
It is stirred to react 20min~40min under min~500r/min, obtains the mixed solution of nano graphite powder and polyimide acid；
Step 2 2. described in nano graphite powder quality and distilled water volume ratio be (3g~10g): 400mL；
Step 2 2. described in polyimides aqueous acid and distilled water volume ratio be (0.5~2): 400；
3., large scale graphene oxide solution and nano graphite powder and the mixed solution of polyimide acid mixed, then
Mixing speed is to be stirred to react 0.5h~2h under 300r/min~500r/min, then the ultrasound in the case where ultrasonic power is 100W~150W
Disperse 0.5h~2h, obtains dark mixed solution；
Three, dry:
It is under stiring to be done by spraying at 140 DEG C~170 DEG C with temperature by 3. dark mixed solution that step 2 obtains
It is dry, obtain fluffy powder；
Four, it makes annealing treatment:
The fluffy powder that step 3 is obtained is put into tube furnace, then under inert gas protection by tube furnace with 3 DEG C/
Min~5 DEG C/min heating rate rises to 180 DEG C~240 DEG C from room temperature, keeps the temperature 50min~80min, then with 3 DEG C/min~5
DEG C/heating rate of min rises to 900 DEG C~1100 DEG C from 180 DEG C~240 DEG C, keep the temperature 120min~150min, finally with 5 DEG C/
Min~8 DEG C/min rate of temperature fall is down to 180 DEG C~240 DEG C from 900 DEG C~1100 DEG C, and program stopped is naturally cooling to room
Temperature, annealing terminate, and obtain graphene coated nano-graphite electrode material.
Present embodiment step 2 2. described in the purchase of polyimides aqueous acid from Shanghai Ye He Trade Co., Ltd..
One, present embodiment is to solve the existing graphite cathode material less than 1 micron since compacted density is low, for the first time library
Human relations low efficiency is difficult the problem of applying as lithium ion battery negative material, proposes to utilize large scale, high-quality graphene conduct
" binder " is re-prepared as the graphite coat of nano-scale the new electrode materials of micron-scale, and a nanometer stone greatly improved
The compacted density of ink, for the first time coulombic efficiency, the comprehensive performances such as specific capacity；
Two, using graphene coated nano-graphite electrode material prepared by present embodiment as lithium ion battery negative material
Capacity of the button cell at 0.1C be greater than 362mAh/g, compacted density is greater than 2.1g/cm3, coulombic efficiency be greater than 89%,
Capacity remains larger than 92% after 500 circulations.
Present embodiment can get a kind of graphene coated nano-graphite electrode material.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: 3. big ruler that step 1 obtains
The partial size of very little graphene oxide is 10 μm~100 μm.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 4
The inert gas stated is argon gas or nitrogen.Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: step 2 2. in
The mass fraction of the polyimides aqueous acid is 50%.Other steps are identical as specific embodiment one to three.
Present embodiment step 2 2. described in the purchase of polyimides aqueous acid from Shanghai Ye He Trade Co., Ltd..
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: step 2 1. in
The concentration of the large scale graphene oxide solution is 5g/L~10g/L.Other steps and one to four phase of specific embodiment
Together.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: step 2 1. in
The concentration of the large scale graphene oxide solution is 10g/L~15g/L.Other steps and one to five phase of specific embodiment
Together.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: step 2 2. in
The quality of the nano graphite powder and the volume ratio of distilled water are 5g:400mL.Other steps and specific embodiment one to six
It is identical.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: step 2 2. in
The volume ratio of the polyimides aqueous acid and distilled water is 1:400.Other steps and one to seven phase of specific embodiment
Together.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: will in step 3
3. dark mixed solution that step 2 obtains is to be spray-dried at 160 DEG C~170 DEG C with temperature under stiring, is obtained fluffy
Powder.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: will in step 4
The fluffy powder that step 3 obtains is put into tube furnace, then under inert gas protection by tube furnace with the heating speed of 3 DEG C/min
Rate rises to 200 DEG C from room temperature, keeps the temperature 60min, then 1000 DEG C are risen to from 200 DEG C with the heating rate of 3 DEG C/min, heat preservation
120min is finally down to 200 DEG C from 1000 DEG C with the rate of temperature fall of 5 DEG C/min, and program stopped is naturally cooling to room temperature, annealing
Processing terminate, obtains graphene coated nano-graphite electrode material.Other steps are identical as specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of graphene coated nano-graphite electrode material is completed by the following steps:
One, large scale graphene oxide is prepared:
1., by partial size be that 300 μm~500 μm of crystalline flake graphite is added in the mixed acid of sulfuric acid and nitric acid, then is being stirred
Speed is stirred to react for 24 hours under conditions of being 300r/min, then is filtered, and black powder is obtained；Distilled water is reused to black
Powder carries out cleaning 5 times, then dries 12h at being 80 DEG C in temperature, the black powder after being dried；By the black powder after drying
End is put into 60s in the micro-wave oven that power is 500W, obtains quasiflake graphite；
Step 1 1. described in partial size be 300 μm~500 μm crystalline flake graphite quality and sulfuric acid and nitric acid mixing
The volume ratio of acid is 3g:400mL；
Step 1 1. described in sulfuric acid and nitric acid mixed acid in the volume ratio of sulfuric acid and nitric acid be 3:1；
2., quasiflake graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then in the condition of ice bath
Lower reaction 2h, obtains mixed liquor A, keeps the temperature 2h at being 35 DEG C in temperature by mixed liquor A, deionized water is then added, then in temperature
It is to keep the temperature 30min at 95 DEG C, cooled to room temperature obtains mixed liquid B；
Step 1 2. described in quasiflake graphite and potassium permanganate mass ratio be 1:5；
Step 1 2. described in quasiflake graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:
200mL；
Step 1 2. described in quasiflake graphite quality and deionized water volume ratio be 1g:140mL；
3., into mixed liquid B be added mass fraction be 35% H2O2Solution, and stir evenly, then react at room temperature
20min obtains graphene oxide water solution；By graphene oxide water solution low whipping speed be 8000r/min under conditions of into
Row centrifugation, the deposit after taking centrifuge separation, then by deposit be 70 DEG C in temperature at dry 12h, obtain large scale oxygen
Graphite alkene；
Step 1 3. described in mixed liquid B and mass fraction be 35% H2O2The volume ratio of solution is 50:1.5；
Two, the mixed solution of big size graphene, polyimides and nano graphite powder is prepared:
1., 3. large scale graphene oxide that step 1 obtains is dissolved into water, it is molten to obtain large scale graphene oxide
Liquid；
Step 2 1. described in large scale graphene oxide solution concentration be 10g/L；
2., nano graphite powder and polyimides aqueous acid be added in distilled water, be 500r/ being stirred for speed
It is stirred to react 30min under min, obtains the mixed solution of nano graphite powder and polyimide acid；
Step 2 2. described in the mass fraction of polyimides aqueous acid be polyimides aqueous acid, purchase is from upper
Hai Yehe Trade Co., Ltd.；
Step 2 2. described in nano graphite powder quality and distilled water volume ratio be 5g:400mL；
Step 2 2. described in polyimides aqueous acid and distilled water volume ratio be 1:400；
3., large scale graphene oxide solution and nano graphite powder and the mixed solution of polyimide acid mixed, then
It is molten to obtain dark mixing to be stirred to react 1h, then the ultrasonic disperse 1h in the case where ultrasonic power is 100W under 500r/min for mixing speed
Liquid；
Three, dry:
Under stiring it is to be spray-dried at 160 DEG C with temperature by 3. dark mixed solution that step 2 obtains, obtains
Fluffy powder；
Four, it makes annealing treatment:
The fluffy powder that step 3 is obtained is put into tube furnace, then under inert gas protection by tube furnace with 3 DEG C/
The heating rate of min rises to 200 DEG C from room temperature, keeps the temperature 60min, then rise to 1000 from 200 DEG C with the heating rate of 3 DEG C/min
DEG C, 120min is kept the temperature, is finally down to 200 DEG C from 1000 DEG C with the rate of temperature fall of 5 DEG C/min, program stopped is naturally cooling to room
Temperature, annealing terminate, and obtain graphene coated nano-graphite electrode material.
Slurry is made in graphene coated nano-graphite electrode material prepared by embodiment one to be coated on copper foil, after dry
The electrode slice that diameter is 24 millimeters is made；The electrode slice that diameter is 24 millimeters is put into the negative electrode casing of battery, 50 μ L electrolysis is added dropwise
Matter makes diaphragm cover electrode material, then 50 μ L electrolyte is added dropwise, and is put into lithium piece, in addition anode cover, battery is compressed, stands for 24 hours
Afterwards, that is, it completes, obtains the graphene coated nano-graphite electrode material of the preparation of embodiment one as negative electrode of lithium ion battery
The button cell of material；The electrolyte concentration is the LiPF of 1mol/L6Solution；The diaphragm is polypropylene diaphragm；Institute
The electrolyte stated is the mixed liquor of ethylene carbonate, diethyl carbonate and fluorinated ethylene carbonate, ethylene carbonate in mixed liquor
Volume ratio with diethyl carbonate is 1:1；The volume ratio of ethylene carbonate and fluorinated ethylene carbonate is 1:0.03.
Fig. 1 is the microscope photo of 3. large scale graphene oxide that one step 1 of embodiment obtains；
From fig. 1, it can be seen that graphene size is about at 40 μm or more, the thickness of graphene is about 4nm, and the number of plies is being 4 layers.
Fig. 2 is the Atomic Mechanics microscope photo of 3. large scale graphene oxide that one step 1 of embodiment obtains；
As can be seen from Figure 2, the large scale graphene oxide size that 3. one step 1 of embodiment obtains at 10 μm~30 μm or more,
And even size distribution.
Fig. 3 is the stereoscan photograph for the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains；
As can be seen from Figure 3, the particle size for the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains is 2
μm~10 μm, it was demonstrated that big size graphene plays good cementation, and nano particle is bonded to micron particles, this
Also it is to provide the key of compacted density.
Fig. 4 is Raman map, in Fig. 41 be nano-graphite Raman curve, 2 graphite obtained for one step 4 of embodiment
The Raman map of alkene cladding nano-graphite electrode material；
As can be seen from Figure 4, graphene is moving back in the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains
Good reduction is obtained after fire, electric conductivity improves, this is the key that promote composite material chemical property.
Fig. 5 is the stereoscan photograph for the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains；
As can be seen from Figure 5, the particle size for the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains is 2
μm~8 μm, it was demonstrated that nano particle is bonded to micron particles by big size graphene.
Fig. 6 is XRD spectrum, and 1 is the XRD curve of nano-graphite, and 2 graphene coateds obtained for one step 4 of embodiment are received
The XRD curve of rice graphite electrode material；
As can be seen from Figure 6, the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains, which still maintains, to be received
The crystalline properties of meter Shi Mo, this is the key that storage lithium characteristic of the package without influence graphite of graphene.
Fig. 7 is charging and discharging curve, and 1 is the button cell using nano-graphite as lithium ion battery negative material at 0.1C times
Charging and discharging curve under rate, 2 is using the graphene coated nano-graphite electrode materials that one step 4 of embodiment obtains as lithium ion
The button cell of cell negative electrode material charging and discharging curve under 0.1C multiplying power.
As can be seen from Figure 7, using the graphene coated nano-graphite electrode material that one step 4 of embodiment obtains as lithium ion
No matter all more negative than using nano-graphite as lithium ion battery on capacity or coulombic efficiency the button cell of cell negative electrode material is
The button cell of pole material is greatly improved.
The performance for the graphene coated nano-graphite electrode material that nano-graphite and one step 4 of embodiment obtain is listed in table
1；
Table 1
Above embodiments are to graphene provided by the present invention/metal carbides complex three-dimensional nanoscale twins electrode material
Preparation method is described in detail, and principle and implementation of the present invention are described, is only used for helping to understand this hair
Bright method and its core concept；Simultaneously, it is noted that for those skilled in the art, do not departing from this hair
Under the premise of bright design, various modifications and improvements can be made, and these are all within the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of graphene coated nano-graphite electrode material, it is characterised in that this method is specifically to press following step
Suddenly it completes:
One, large scale graphene oxide is prepared:
1., by partial size be that 300 μm~500 μm of crystalline flake graphite is added in the mixed acid of sulfuric acid and nitric acid, then low whipping speed
It to be stirred to react for 24 hours~48h under conditions of 300r/min~500r/min, then is filtered, obtains black powder；Reuse steaming
Distilled water carries out cleaning 3 times~5 times to black powder, then dry 12h at being 60 DEG C~80 DEG C in temperature~for 24 hours, after being dried
Black powder；Black powder after drying is put into 60s~180s in the micro-wave oven that power is 500W~1000W, is obtained compacted
Worm shape graphite；
Step 1 1. described in partial size be 300 μm~500 μm crystalline flake graphite quality and sulfuric acid and nitric acid mixed acid
Volume ratio is 3g:(400mL~450mL)；
Step 1 1. described in sulfuric acid and nitric acid mixed acid in the volume ratio of sulfuric acid and nitric acid be 3:1；
2., quasiflake graphite and potassium permanganate be added in the sulfuric acid that mass fraction is 98%, then under conditions of ice bath it is anti-
1h~2h is answered, mixed liquor A is obtained, 1h~3h is kept the temperature at being 30 DEG C~40 DEG C in temperature by mixed liquor A, deionization is then added
Water, then 30min~50min is kept the temperature at being 90 DEG C~95 DEG C in temperature, cooled to room temperature obtains mixed liquid B；
Step 1 2. described in quasiflake graphite and potassium permanganate mass ratio be 1:5；
Step 1 2. described in quasiflake graphite quality and mass fraction be 98% the volume ratio of sulfuric acid be 1g:200mL；
Step 1 2. described in quasiflake graphite quality and deionized water volume ratio be 1g:(130mL~140mL)；
3., into mixed liquid B be added mass fraction be 35% H2O2Solution, and stir evenly, then react 10min at room temperature
~30min, obtains graphene oxide water solution；It is 6000r/min~10000r/ by graphene oxide water solution low whipping speed
Be centrifuged under conditions of min, take centrifuge separation after deposit, then by deposit temperature be 60 DEG C~80 DEG C at do
Dry 12h~48h obtains large scale graphene oxide；
Step 1 3. described in mixed liquid B and mass fraction be 35% H2O2The volume ratio of solution is 50:(1~2)；
The partial size of 3. large scale graphene oxide that step 1 obtains is 10 μm~100 μm；
Two, the mixed solution of big size graphene, polyimides and nano graphite powder is prepared:
1., 3. large scale graphene oxide that step 1 obtains is dissolved into water, obtain large scale graphene oxide solution；
Step 2 1. described in large scale graphene oxide solution concentration be 5g/L~15g/L；
2., nano graphite powder and polyimides aqueous acid be added in distilled water, be stirred for speed be 300r/min~
It is stirred to react 20min~40min under 500r/min, obtains the mixed solution of nano graphite powder and polyimide acid；
Step 2 2. described in nano graphite powder quality and distilled water volume ratio be (3g~10g): 400mL；
Step 2 2. described in polyimides aqueous acid and distilled water volume ratio be (0.5~2): 400；
3., large scale graphene oxide solution and nano graphite powder and the mixed solution of polyimide acid mixed, then stirring
Speed is to be stirred to react 0.5h~2h under 300r/min~500r/min, then the ultrasonic disperse in the case where ultrasonic power is 100W~150W
0.5h~2h obtains dark mixed solution；
Three, dry:
Under stiring it is to be spray-dried at 140 DEG C~170 DEG C with temperature by 3. dark mixed solution that step 2 obtains, obtains
To fluffy powder；
Four, it makes annealing treatment:
The fluffy powder that step 3 is obtained is put into tube furnace, then under inert gas protection by tube furnace with 3 DEG C/min~5
DEG C/heating rate of min from room temperature rises to 180 DEG C~240 DEG C, 50min~80min is kept the temperature, then with 3 DEG C/min~5 DEG C/min
Heating rate rise to 900 DEG C~1100 DEG C from 180 DEG C~240 DEG C, 120min~150min is kept the temperature, finally with 5 DEG C/min~8
DEG C/rate of temperature fall of min is down to 180 DEG C~240 DEG C from 900 DEG C~1100 DEG C, program stopped is naturally cooling to room temperature, annealing
Processing terminate, obtains graphene coated nano-graphite electrode material；
Inert gas described in step 4 is argon gas or nitrogen.
2. a kind of preparation method of graphene coated nano-graphite electrode material according to claim 1, it is characterised in that
Step 2 2. described in polyimides aqueous acid mass fraction be 50%.
3. a kind of preparation method of graphene coated nano-graphite electrode material according to claim 1, it is characterised in that
Step 2 1. described in large scale graphene oxide solution concentration be 5g/L~10g/L.
4. a kind of preparation method of graphene coated nano-graphite electrode material according to claim 1, it is characterised in that
Step 2 1. described in large scale graphene oxide solution concentration be 10g/L~15g/L.
5. a kind of preparation method of graphene coated nano-graphite electrode material according to claim 1, it is characterised in that
Step 2 2. described in nano graphite powder quality and distilled water volume ratio be 5g:400mL.
6. a kind of preparation method of graphene coated nano-graphite electrode material according to claim 1, it is characterised in that
Step 2 2. described in polyimides aqueous acid and distilled water volume ratio be 1:400.
7. a kind of preparation method of graphene coated nano-graphite electrode material according to claim 1, it is characterised in that
It by 3. dark mixed solution that step 2 obtains under stiring is to be done by spraying at 160 DEG C~170 DEG C with temperature in step 3
It is dry, obtain fluffy powder.
8. a kind of preparation method of graphene coated nano-graphite electrode material according to claim 1, it is characterised in that
The fluffy powder for obtaining step 3 in step 4 is put into tube furnace, then under inert gas protection by tube furnace with 3 DEG C/
The heating rate of min rises to 200 DEG C from room temperature, keeps the temperature 60min, then rise to 1000 from 200 DEG C with the heating rate of 3 DEG C/min
DEG C, 120min is kept the temperature, is finally down to 200 DEG C from 1000 DEG C with the rate of temperature fall of 5 DEG C/min, program stopped is naturally cooling to room
Temperature, annealing terminate, and obtain graphene coated nano-graphite electrode material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102187498A (en) * | 2008-10-10 | 2011-09-14 | 江原大学校产学协力团 | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery comprising the same |
| KR20130016727A (en) * | 2011-08-05 | 2013-02-18 | 강원대학교산학협력단 | Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same |
| KR20130107892A (en) * | 2012-03-23 | 2013-10-02 | 강원대학교산학협력단 | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN104617301A (en) * | 2015-03-11 | 2015-05-13 | 黑龙江科技大学 | Preparation method of large-size graphene/graphite composite negative pole material |
| CN105280891A (en) * | 2014-06-02 | 2016-01-27 | 三星Sdi株式会社 | Negative active material, cathode and rechargeable lithium battery including same |
| CN105633368A (en) * | 2015-12-31 | 2016-06-01 | 深圳市贝特瑞新能源材料股份有限公司 | Negative electrode material of lithium ion battery and preparation method for negative electrode material |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102187498A (en) * | 2008-10-10 | 2011-09-14 | 江原大学校产学协力团 | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery comprising the same |
| KR20130016727A (en) * | 2011-08-05 | 2013-02-18 | 강원대학교산학협력단 | Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same |
| KR20130107892A (en) * | 2012-03-23 | 2013-10-02 | 강원대학교산학협력단 | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN105280891A (en) * | 2014-06-02 | 2016-01-27 | 三星Sdi株式会社 | Negative active material, cathode and rechargeable lithium battery including same |
| CN104617301A (en) * | 2015-03-11 | 2015-05-13 | 黑龙江科技大学 | Preparation method of large-size graphene/graphite composite negative pole material |
| CN105633368A (en) * | 2015-12-31 | 2016-06-01 | 深圳市贝特瑞新能源材料股份有限公司 | Negative electrode material of lithium ion battery and preparation method for negative electrode material |
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