CN107845795A - A kind of CNT/micro- swollen graphite combination electrode material and preparation method thereof - Google Patents
A kind of CNT/micro- swollen graphite combination electrode material and preparation method thereof Download PDFInfo
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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Abstract
The invention discloses a kind of preparation method of CNT/micro- swollen graphite combination electrode material; by micro- swollen graphite impregnation in iron nitrate aqueous solution; ultrasonic vibration filters after certain time; vacuum drying, dried material is placed in stove, 650 ~ 700 DEG C are warming up under protective gas atmosphere; then pass to C2H2 gases; 40 ~ 50min is incubated, room temperature is cooled under protective gas atmosphere, obtains CNT/micro- swollen graphite combination electrode material；The present invention is after micro- swollen graphite is prepared, using CVD deposition method deposition of carbon nanotubes in the surface of micro- swollen graphite and pore space structure, the CNT being prepared/micro- swollen graphite combination electrode material specific capacity is high, good cycling stability, lithium ion diffusion velocity are fast so that the high magnification chemical property of combination electrode material of the present invention is superior.
Description
Technical field
The invention belongs to technical field of material, more particularly to a kind of CNT/micro- swollen graphite combination electrode
Material and preparation method thereof.
Background technology
One of an important factor for negative material of lithium ion battery is influence battery performance, current commercial negative material master
If carbons negative material, it is divided into several forms such as graphitized carbon, hard carbon (difficult graphitized carbon) and nano-carbon material, wherein with stone
Ink application is most.In recent years, application of the lithium ion battery in the Large Electric equipment such as electric car increasingly causes the concern of people,
This requires lithium ion battery to possess higher reversible capacity, high charge-discharge efficiencies and good cyclical stability.Natural stone
Ink is cheap, security performance protrudes, and is still the preferred material of negative electrode of power lithium-ion battery.
The theoretical embedding lithium capacity of graphite is 372m Ah/g, and it crystallizes complete and has a high orientation, Lithium-ion embeding with
During abjection, 10% or so expansion and contraction can be produced in d002 directions, its layer structure is easily broken in cyclic process
It is bad.Have electrolyte solvent unavoidably in cyclic process in addition and be embedded in graphite layers altogether, due to the reduction of organic solvent, in big electricity
Gas expansion can be produced by flowing down, and cause graphite flake layer to peel off, and cause active material irreversible loss and solid electrolyte interface
The continuous destruction of film (SEI films) and live again, so as to cause cycle life not good enough, meanwhile, graphite is relatively low, first there is also specific capacity
The problems such as secondary efficiency for charge-discharge is relatively low, diffusion velocity of the lithium ion in graphite is slower, for problem above, researcher passes through heat
Solution charcoal bag covers, is modified stone with the means such as the mechanical compound, surface oxidation treatment of nano-carbon material (Carbon fibe or CNT etc.)
Ink, it is effectively improved the chemical property of native graphite, but its reversible specific capacity and following under high magnification first
Ring stability etc. still has much room for improvement.
The microdilatancy graphite compound between graphite layers extremely cheap as a kind of cost（GIC）, due to abundant more
Pore dimension structure, larger specific surface area, excellent thermoelectricity conductive performance, the advantages that good chemical stability, and recognized
For be a kind of great potential can large-scale application in lithium ion battery negative material.
In order to improve the reversible capacity of native graphite and cyclical stability, microdilatancy processing can be carried out, expands interlayer
Away from then compound using chemical vapour deposition technique growth CNT, obtained CNT/micro- swollen graphite in larger hole
Negative material.
The content of the invention
The purpose of the present invention is the problem of presence for prior art, there is provided a kind of CNT/micro- swollen graphite compound electric
The preparation method of pole material.
Another object of the present invention is to provide a kind of CNT/micro- swollen graphite combination electrode material.
The purpose of the present invention is achieved by the following technical programs：
The preparation method of a kind of CNT/micro- swollen graphite combination electrode material, by micro- swollen graphite impregnation in iron nitrate aqueous solution
In, ultrasonic vibration filters after certain time, vacuum drying, dried material is placed in stove, risen under protective gas atmosphere
Temperature then passes to C2H2 gases to 650 ~ 700 DEG C, is incubated 40 ~ 50min, is then cooled to room temperature under protective gas atmosphere, obtains
CNT/micro- swollen graphite combination electrode material；
Wherein, micro- swollen graphite preparation process includes：
S1. it is 2 ~ 3 to take crystalline flake graphite and micro crystal graphite mass ratio:1 carries out ball milling, is compound to the mesh of granularity 200 ~ 300；
S2. compound obtained by S1 is placed in Muffle furnace, 350 DEG C ~ 400 DEG C is to slowly warm up under protective gas atmosphere, insulation
10 ~ 30min, it is stand-by to be air-cooled to room temperature；
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite；
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 400 ~ 500 DEG C, obtain micro- swollen graphite.
In the preparation process of the micro- swollen graphite of the present invention, when mechanical milling process, the crystalline flake graphite of appropriate mass ratio and micro-
Spar ink is sufficiently mixed, and in mechanical milling process, part micro crystal graphite particle can enter crystalline flake graphite piece interlayer, be sufficiently mixed, and is mixed
It is heat-treated after closing, heat treatment can activate ball milling mixing material, while can also handle sublimable impurity in raw material,
Chemical graft processing is carried out after heat treatment immediately, intercalation efficiency can be improved, the expansion procedure after being more favorable to,
Ball milling mixing material is in expansion procedure, and crystalline flake graphite is different with the structure of micro crystal graphite, the change that its expansion process occurs
Also different, crystalline flake graphite expansion process expands its piece interlamellar spacing, and micro crystal graphite then it is expanded formed it is cotton-shaped, crystalline flake graphite it
Between cotton-shaped expansion micro crystal graphite be connected between crystalline flake graphite lamella, be mingled with cotton-shaped crystallite between this crystalline flake graphite lamella
The structure of graphite is more beneficial for interelectric conduction, is also more suitable for li-ion electrode materials, is formed after raising expansion micro-
The charge/discharge capacity of swollen graphite material, improve its cycle performance and multiplying power discharging property.
After the present invention prepares micro- swollen graphite, using CVD deposition method deposition of carbon nanotubes in the surface and hole of micro- swollen graphite
In the structure of hole, the CNT/micro- swollen graphite combination electrode material specific capacity being prepared is high, good cycling stability, because lithium
Ion diffusion velocity is fast so that the high magnification chemical property of combination electrode material of the present invention is superior.
Preferably, the concentration of iron nitrate aqueous solution is 0.1 ~ 0.2mol/L.
Preferably, the ultrasonic vibration time is 0.5 ~ 3h, and vacuum drying temperature is 90 DEG C, and vacuum drying time is 8 ~ 12h.
Preferably, crystalline flake graphite phosphorus content described in step S1 is not less than 85%, and the micro crystal graphite is Chenzhou City Shandong pool graphite
Powder, its carbon content are 70 ~ 80%,
Preferably, step S1 mechanical milling processes ratio of grinding media to material is 3 ~ 5:1, Ball-milling Time is 6 ~ 8h, and rotating speed is 200 ~ 300r/min
Preferably, protective atmosphere is one kind in nitrogen, argon gas.
Preferably, compound described in step S2 heats in Muffle furnace, and the heating rate is 5 ~ 20 DEG C/min.
Preferably, chemical graft processing step includes described in step S3：
S31. it is 10~30 by liquid-solid ratio by mixed powder obtained by perchloric acid and step S2：1L/Kg is mixed evenly；
S32. it is 1 by the mass ratio of the mixed powder and potassium permanganate：2~8 add potassium permanganate, are stirred at room temperature uniformly
Afterwards, 30~60 DEG C are warming up to and continues 1~3.0h of stirring reaction；
S33. add deionized water the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h；
S34. filter, then filtrate is washed, dried, obtains inflatable admixed graphite.
Preferably, step S4 carries out high-temperature expansion in graphite expansion stove and comprised the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；
S42. expand：The expansion temperature of burner hearth is 400 ~ 500 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain micro- swollen graphite material in discharge outlet
Material.
Present invention additionally comprises the carbon nanometer that the preparation method of CNT/micro- swollen graphite combination electrode material is prepared
Pipe/micro- swollen graphite combination electrode material.
Compared with the prior art, the beneficial effects of the present invention are：
The present invention is mixed with micro- swollen graphite material, Chinese micro crystal graphite reserves using micro crystal graphite and crystalline flake graphite first
Greatly, it is cheap, it is mostly low value-added utilization, the present invention provides a kind of high value added utilization approach for micro crystal graphite.So
Afterwards after micro- swollen graphite is prepared, using CVD deposition method deposition of carbon nanotubes in the surface of micro- swollen graphite and pore space structure, system
Standby obtained CNT/micro- swollen graphite combination electrode material specific capacity is high, good cycling stability, lithium ion diffusion velocity soon from
And make the high magnification chemical property of combination electrode material of the present invention superior.
Brief description of the drawings
Fig. 1 is that embodiment 1 obtains micro- swollen graphite material scanning electron microscope (SEM) photograph.
Fig. 2 is the high temperature graphite expansion furnace structure figure of embodiment 1 ~ 4.
Fig. 3 is CNT/micro- swollen graphite combination electrode material scanning electron microscope (SEM) photograph that embodiment 6 obtains.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
The present invention is mixed with micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 70% and the crystalline flake graphite raw material of phosphorus content 85%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 2:1, crushing and grinding, to the mixing graphite powder that granularity is 300 mesh.
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 350 DEG C in a nitrogen atmosphere, be incubated 30min,
It is stand-by to be air-cooled to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry
Intercalation processing comprises the following steps that：
S31. it is 10 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and strong oxidizer is 2：1 adds strong oxidizer, after being stirred at room temperature uniformly, is warming up to 30 DEG C and continues stirring instead
Answer 3h；S33. adding deionized water makes the temperature in reaction unit be increased to 60 DEG C, is further continued for stirring reaction 3h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 400 DEG C, obtain micro- swollen graphite material
Material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 400 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Micro- swollen graphite material.
The scanning electron microscope (SEM) photograph of the micro- swollen graphite material obtained in the present embodiment is as shown in figure 1, obtained micro- swollen graphite material
Pore size distribution range is 1~100nm, and specific surface area is 350 m2/ g, expansion multiple are 21 times, resistivity 1.32*10-3Ω
.m。
Embodiment 2
The present invention is mixed with micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 75% and the crystalline flake graphite raw material of phosphorus content 90%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 2:1, crushing and grinding, to the mixing graphite powder that granularity is 200 mesh；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 400 DEG C in a nitrogen atmosphere, be incubated 10min, air cooling
It is stand-by to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry
Intercalation processing comprises the following steps that：
S31. it is 15 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and potassium permanganate is 4：1 adds potassium permanganate, after being stirred at room temperature uniformly, is warming up to 40 DEG C and continues stirring instead
Answer 2h；S33. adding deionized water makes the temperature in reaction unit be increased to 70 DEG C, is further continued for stirring reaction 2h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 500 DEG C, obtain micro- swollen graphite material
Material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 500 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Micro- swollen graphite material.
The result that morphological feature, structural analysis and the embodiment 1 of the micro- swollen graphite material obtained in the present embodiment are obtained
Essentially identical, obtained micro- swollen graphite material pore size distribution range is 1~100nm, specific surface area 606m2/ g, expansion multiple
For 23 times, resistivity 4.32*10-3Ω.m。
Embodiment 3
The present invention is mixed with micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 75% and the crystalline flake graphite raw material of phosphorus content 85%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 2.5:1, crushing and grinding, to the mixing graphite powder that granularity is 200 mesh；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 400 DEG C in a nitrogen atmosphere, be incubated 10min, air cooling
It is stand-by to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry
Intercalation processing comprises the following steps that：
S31. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and potassium permanganate is 6：1 adds potassium permanganate, after being stirred at room temperature uniformly, is warming up to 50 DEG C and continues stirring instead
Answer 2h；S33. adding deionized water makes the temperature in reaction unit be increased to 80 DEG C, is further continued for stirring reaction 2h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 450 DEG C, obtain micro- swollen graphite material
Material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 450 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Micro- swollen graphite material.
The result that morphological feature, structural analysis and the embodiment 1 of the micro- swollen graphite material obtained in the present embodiment are obtained
Essentially identical, obtained micro- swollen graphite material pore size distribution range is 1~100nm, specific surface area 623m2/ g, expansion multiple
For 18.1 times, resistivity 2.64*10-3Ω.m。
Embodiment 4
The present invention is mixed with micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 75% and the crystalline flake graphite raw material of phosphorus content 90%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 3:1, crushing and grinding, to the mixing graphite powder that granularity is 300 mesh；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 350 DEG C in a nitrogen atmosphere, be incubated 30min, air cooling
It is stand-by to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry is inserted
Layer processing comprises the following steps that：
S31. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and potassium permanganate is 6：1 adds potassium permanganate, after being stirred at room temperature uniformly, is warming up to 50 DEG C and continues stirring instead
Answer 2h；S33. adding deionized water makes the temperature in reaction unit be increased to 80 DEG C, is further continued for stirring reaction 2h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 450 DEG C, obtain micro- swollen graphite material
Material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 450 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Micro- swollen graphite material.
The result that morphological feature, structural analysis and the embodiment 1 of the micro- swollen graphite material obtained in the present embodiment are obtained
Essentially identical, obtained micro- swollen graphite material pore size distribution range is 1~100nm, specific surface area 492m2/ g, expansion multiple
For 18 times, resistivity 9.95*10-4Ω.m。
Embodiment 5
Referring to Fig. 1, the graphite expansion stove used for the high-temperature expansion process of embodiment 1 to 4, graphite expansion stove includes body of heater 1, charging
Then device 2, drawing mechanism 3 and control device, raw material are collected by feeding device 2 to body of heater 1 by drawing mechanism 3；Discharging
Device 3 is located above body of heater, and feeding device 2 is located at below body of heater；Heater 11 is provided with body of heater 1, using Resistant heating,
The inner bottom part of body of heater 1 is additionally provided with air-flow shower nozzle 4, and air-flow shower nozzle 4 also includes source of the gas 41, airflow line 42 and control damper 43, gas
Source 41 is air, and connects airflow line 42, and airflow line 42 connects air-flow shower nozzle 4, and control damper 43 is located at airflow line
In 42, the top of air-flow shower nozzle 4 is provided with feeding device 2, specifically includes processor 5 and control using feed screw, control device
Device, processor 5 are provided with and control panel and be connecteds with controller, and controller includes the first controller 53, second controller 52 and the
Three controllers 51, the first controller 53 are connected with the control damper 43 of air-flow shower nozzle 4, second controller 52 and feeding device 2
Connection, the 3rd controller 51 are connected with heater 11；
Wherein, processor 5 uses microprocessor, and the first controller uses air inlet valve-driving circuit, and second controller is using charging
Valve-driving circuit, the 3rd controller use heat driven circuit.
Cooling device 7 is additionally provided between drawing mechanism 3 and body of heater 1, cooling device 7 includes heat exchanger tube 71 and water cooling tube 72,
One end connection body of heater 1 of heat exchanger tube 71, other end connection drawing mechanism 3, heat exchanger tube 71 and horizontal angle are 45 DEG C~90
DEG C, water cooling tube 72 is arranged on heat exchanger tube 71 in the shape of a spiral；
Drawing mechanism 3 includes multiple reserves storehouses 31 and connecting pipe 32, and the one end of connecting pipe 32 is connected with heat exchanger tube 71, and is provided with
Cyclone separator 33, the other end are connected with exhaust outlet 34, be additionally provided with connecting pipe 32 multiple subtubes 35 respectively with reserves storehouse
31 connections；Connecting pipe and 32 horizontal angles are 45 DEG C~90 DEG C；
Agitator 8 is additionally provided with body of heater 1, agitator 8 is spiral agitator, is coordinated by motor and ball-screw so that stir
Mix device 8 and upper and lower linear motion is done in body of heater 1, so as to drive the airflow reflux in body of heater 1.
Wherein：The temperature of discharging opening is controlled by cooling device, and heater 6 also is provided with to control in charging aperture
The temperature of charging aperture processed, specific the present embodiment can be heated using resistance wire 61 to the discharge pipe in feeding device.
Can control time and the temperature of expansion by control panel, specifically processor by control the first controller and
Second controller controls air velocity and charging rate, so as to control the reaction time that intercalated graphite expands, the 3rd controller
The temperature of heater can be controlled, the intellectuality of graphite expansion is realized, reaches and be precisely controlled.
Graphite expansion stove is placed using two floors, and the processing sequence according to raw material is heat exchanger tube and connection from the bottom up
Pipeline and horizontal line have certain angle, by the cooperation of gravity and wind speed, that is, solve expanded graphite and get stuck problem, improve anti-
Yield is answered, while also solves space compared to being disposed vertically.
Graphite expansion stove adds agitator 8 in body of heater 1 so that the air-flow in body of heater 1 forms convection current, ensure that intercalation stone
Ink is heated evenly, so as to which the expanded reaction efficiency of intercalated graphite be significantly increased..
Comparative example 1
Comparative example 1 is with the difference of embodiment 1：Comparative example 1 is not provided with step S2, and other steps are same as Example 1.
Micro- swollen graphite material pore size distribution range that comparative example 1 obtains is 1~150nm, specific surface area 305m2/ g, it is swollen
Swollen multiple is 10 times, resistivity 9.95*10-2Ω.m。
Comparative example 2
Comparative example 2 is with the difference of embodiment 1：The step S4 of comparative example 1 is different, and other steps are same as Example 1, specifically
For：
S4. will obtained by S3 in the inflatable electric furnace of admixed graphite under nitrogen atmosphere 400 DEG C carry out heating roasting 60s, obtain
Micro- swollen graphite material.
Micro- swollen graphite material pore size distribution range that comparative example 2 obtains is 1~150nm, specific surface area 290m2/ g, it is swollen
Swollen multiple is 12.9 times, resistivity 8.13*10-2Ω.m。
Comparative example 3
Comparative example 3 is with the difference of embodiment 1：The micro crystal graphite raw material of all phosphorus content 70% of raw material of comparative example 3 crushes
Grinding, to the graphite powder that granularity is 300 mesh.Other steps are same as Example 1.
Micro- swollen graphite material pore size distribution range that comparative example 3 obtains is 1~80nm, specific surface area 380m2/ g, expansion
Multiple is 2.1 times, resistivity 3.89*10-3Ω.m。
Comparative example 4
Comparative example 4 is with the difference of embodiment 1：The crystalline flake graphite raw material of all phosphorus content 85% of raw material of comparative example 4 crushes
Grinding, to the graphite powder that granularity is 300 mesh.Other steps are same as Example 1.
Micro- swollen graphite material pore size distribution range that comparative example 4 obtains is 1~300nm, specific surface area 169m2/ g, it is swollen
Swollen multiple is 30.5 times, resistivity 8.14*10-3Ω.m。
Embodiment 6
The present embodiment provides a kind of preparation method of CNT/micro- swollen graphite combination electrode material.
Micro- swollen graphite that the present embodiment is prepared using embodiment 1 is raw material, by micro- swollen graphite impregnation in 0.1mol/L nitre
In sour water solution, filtered after ultrasonic vibration 2h, be then dried in vacuo 10h at 90 DEG C, dried material is placed in tubular type
Stove, 700 DEG C are warming up under nitrogen atmosphere, then passes to C2H2Gas, 40min is incubated, is then cooled to room under nitrogen atmosphere
Temperature, obtain CNT/micro- swollen graphite combination electrode material.
CNT/micro- swollen graphite combination electrode material scanning electron microscope (SEM) photograph is as shown in figure 3, gained carbon is received obtained by the present embodiment
Mitron/first charge-discharge capacity of micro- swollen graphite combination electrode material under 50mA/g current density is 526mAh/g, through 50
There is 509mAh/g reversible capacity after secondary circulation.
Embodiment 7
The present embodiment provides a kind of preparation method of CNT/micro- swollen graphite combination electrode material.
Micro- swollen graphite that the present embodiment is prepared using embodiment 1 is raw material, by micro- swollen graphite impregnation in 0.2mol/L nitre
In sour water solution, filtered after ultrasonic vibration 1h, be then dried in vacuo 10h at 90 DEG C, dried material is placed in tubular type
Stove, 650 DEG C are warming up under nitrogen atmosphere, then passes to C2H2Gas, 50min is incubated, is then cooled to room under nitrogen atmosphere
Temperature, obtain CNT/micro- swollen graphite combination electrode material.
CNT/micro- swollen graphite combination electrode material filling first under 50mA/g current density obtained by the present embodiment
Discharge capacity is 513mAh/g, there is 493mAh/g reversible capacity after 50 circulations.
Comparative example 5 ~ 8
Comparative example 5 ~ 8 provides a kind of preparation method of CNT/micro- swollen graphite combination electrode material.
Micro- swollen graphite that comparative example 5 ~ 8 is prepared using comparative example 1 ~ 4 respectively is raw material, other steps and the phase of embodiment 6
Together.
The gained CNT of comparative example 5/micro- swollen graphite combination electrode material filling first under 50mA/g current density
Discharge capacity is 410mAh/g, there is 351mAh/g reversible capacity after 50 circulations.
The gained CNT of comparative example 6/micro- swollen graphite combination electrode material filling first under 50mA/g current density
Discharge capacity is 392mAh/g, there is 361mAh/g reversible capacity after 50 circulations.
The gained CNT of comparative example 7/micro- swollen graphite combination electrode material filling first under 50mA/g current density
Discharge capacity is 296mAh/g, there is 227mAh/g reversible capacity after 50 circulations.
The gained CNT of comparative example 8/micro- swollen graphite combination electrode material filling first under 50mA/g current density
Discharge capacity is 483mAh/g, there is 459mAh/g reversible capacity after 50 circulations.
Claims (10)
1. the preparation method of a kind of CNT/micro- swollen graphite combination electrode material, it is characterised in that micro- swollen graphite impregnation exists
In iron nitrate aqueous solution, ultrasonic vibration filters after certain time, vacuum drying, dried material is placed in stove, protected
650 ~ 700 DEG C are warming up under atmosphere, then passes to C2H2Gas, 40 ~ 50min is incubated, it is then cold under protective gas atmosphere
But to room temperature, CNT/micro- swollen graphite combination electrode material is obtained；
Wherein, micro- swollen graphite preparation process includes：
S1. it is 2 ~ 3 to take crystalline flake graphite and micro crystal graphite mass ratio:1 carries out ball milling, is compound to the mesh of granularity 200 ~ 300；
S2. compound obtained by S1 is placed in Muffle furnace, 350 DEG C ~ 400 DEG C is to slowly warm up under protective gas atmosphere, insulation
10 ~ 30min, it is stand-by to be air-cooled to room temperature；
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite；
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 400 ~ 500 DEG C, obtain micro- swollen graphite.
2. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, the concentration of iron nitrate aqueous solution is 0.1 ~ 0.2mol/L.
3. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, the ultrasonic vibration time is 0.5 ~ 3h, and vacuum drying temperature is 90 DEG C, and vacuum drying time is 8 ~ 12h.
4. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, crystalline flake graphite phosphorus content described in step S1 is not less than 85%, and the micro crystal graphite is Chenzhou City Shandong pool graphite powder, and its carbon contains
Measure as 70 ~ 80%.
5. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, step S1 mechanical milling processes ratio of grinding media to material is 3 ~ 5:1, Ball-milling Time is 6 ~ 8h, and rotating speed is 200 ~ 300r/min.
6. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, protective atmosphere is one kind in nitrogen, argon gas.
7. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, compound described in step S2 heats in Muffle furnace, and the heating rate is 5 ~ 20 DEG C/min.
8. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is,
Chemical graft processing step includes described in step S3：
S31. it is 10~30 by liquid-solid ratio by mixed powder obtained by perchloric acid and step S2：1L/Kg is mixed evenly；
S32. it is 1 by the mass ratio of the mixed powder and potassium permanganate：2~8 add potassium permanganate, are stirred at room temperature uniformly
Afterwards, 30~60 DEG C are warming up to and continues 1~3.0h of stirring reaction；
S33. add deionized water the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h；
S34. filter, then filtrate is washed, dried, obtains inflatable admixed graphite.
9. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, step S4 carries out high-temperature expansion in graphite expansion stove and comprised the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；
S42. expand：The expansion temperature of burner hearth is 400 ~ 500 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain micro- swollen graphite material in discharge outlet
Material.
10. it is prepared into according to the preparation method of any one of claim 1 ~ 9 CNT/micro- swollen graphite combination electrode material
The CNT arrived/micro- swollen graphite combination electrode material.
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