CN107381570A - The method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material - Google Patents
The method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material Download PDFInfo
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- CN107381570A CN107381570A CN201710697858.1A CN201710697858A CN107381570A CN 107381570 A CN107381570 A CN 107381570A CN 201710697858 A CN201710697858 A CN 201710697858A CN 107381570 A CN107381570 A CN 107381570A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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 kind of method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material, including：After bamboo is cleaned, drying；Bamboo after drying is placed in porcelain boat, and is placed in high temperature furnace, under argon gas protection, high temperature carbonization, obtains bamboo carbon；By bamboo carbon grind into powder, sieving, evengranular bamboo carbon powder end is obtained；Bamboo carbon powder is passed through carbon dioxide high-temperature activation, natural cooling, the bamboo charcoal material after being activated；Bamboo charcoal material is soaked by deionized water and ethanol respectively, obtains bamboo charcoal base lithium ion battery electrode material.The preparation method of the present invention has the characteristics of operation is simple, and repeatability is strong, and cost is low, environmentally safe.It can effectively increase material specific surface area by the use of bamboo charcoal material prepared by this method as lithium ion battery electrode material, this charing and the physically activated preparation method cleaned, so as to further improve battery capacity, strengthen its cycle performance.
Description
Technical field
The invention belongs to lithium ion battery electrode material preparation field, relate to a kind of bamboo charcoal material, and in particular to a kind of
Bamboo charcoal electrode material applied to lithium ion battery is prepared by charing and physically activated method using bamboo wood.
Background technology
Lithium ion battery is a kind of very promising energy, can be applied to all kinds of because its small volume, energy density are high
In electrical equipment.The electrode material for developing new lithium ion battery is the key for improving its performance.At present, activity cheap and easy to get
Carbon Materials are to apply wide lithium ion battery electrode material, and its theoretical capacity is 372mAh/g.
Bamboo charcoal is a kind of cheap, renewable and environment-friendly porous carbon materials, is now widely used for harmful substance
In absorption.Bamboo and its waste material can prepare bamboo charcoal by high temperature carbonization under nitrogen protection.Bamboo charcoal can keep the bionetwork of bamboo, energy
The migration of lithium ion is enough provided.Therefore, bamboo charcoal is a kind of very potential anode material for lithium-ion batteries.Only pass through letter at present
Bamboo charcoal specific capacitance prepared by single charing is relatively low, and its cycle performance is poor.Meanwhile suitable pore structure be very beneficial for lithium from
Insertion/disengaging of son, so as to have preferable performance.Therefore, the further activation pore-creating to bamboo charcoal is very crucial.Activation at present
Method mainly has Physical and chemical method, and Physical activates in the presence of carbon dioxide or vapor to bamboo charcoal,
The cleaner environmental protection of the method；And chemical activation needs to use substantial amounts of KOH, NaOH, H3PO4、ZnCl2Deng, the method cost compared with
Height, and certain problem of environmental pollution be present.
In this invention, using the bamboo charcoal biomass raw material of abundance as presoma, by simply carbonizing and cleaning
Physically activated pore forming method, prepare the lithium ion battery electrode material with high specific capacitance, and obtain high specific capacitance first
The bamboo charcoal material of (300.9mAh/g), and there is certain service life cycle and stability, circulate and fill under conditions of 0.1C
After electric discharge 500 times, its specific capacitance stills remain in 52% or so, fully proves that the bamboo charcoal material of the inventive method preparation can be into
Work(is applied in li-ion electrode materials.
The content of the invention
In order to overcome current battery poor circulation, and the more expensive shortcoming of the prices of raw materials, it is an object of the invention to carry
For preparation method of the bamboo charcoal as li-ion electrode materials.Using high temperature carbonization and the activation method of cleaning-physically activated
Mode, prepare excellent performance and the lithium ion battery electrode material of long lifespan can be recycled.The inventive method has technique
The features such as simple to operate, repeated high, cost is cheap, raw material sources are extensive.
It is an object of the invention to solve at least the above and/or defect, and provide at least will be described later it is excellent
Point.
In order to realize according to object of the present invention and further advantage, there is provided a kind of physical activation method prepares bamboo charcoal base
The method of lithium ion battery electrode material, comprises the following steps：
Step 1: after bamboo is cleaned with ethanol and deionized water respectively, drying 12~48 is small at 60~120 DEG C of temperature
When；
Step 2: the bamboo after drying is placed in porcelain boat, and it is placed in high temperature furnace, under argon gas protection, with 10-30
DEG C/min programming rate be warming up to 500-1000 DEG C, carbonize 1-12 hours, obtain bamboo carbon；
Step 3: by bamboo carbon grind into powder, with the sieve of 10~300 mesh, evengranular bamboo carbon powder end is obtained；
Step 4: bamboo carbon powder is warming up to 500-1000 DEG C with 10-30 DEG C/min of programming rate, while with 10-
500sccm speed is passed through physically activated dose of CO2, activate 1-12 hours, natural cooling, the bamboo charcoal material after being activated；
Step 5: bamboo charcoal material is soaked by deionized water and ethanol respectively, bamboo charcoal base lithium ion battery electrode is obtained
Material.
Preferably, in the step 4, the temperature-rise period of activation is：250 are warming up to 2~5 DEG C/min speed~
300 DEG C, 90~120min is incubated, is then warming up to 500~700 DEG C with 0.5~1.5 DEG C/min speed, is incubated 3~5h, so
800~1000 DEG C are warming up to 5~10 DEG C/min speed afterwards, is incubated 5~8h, completes activation.
Preferably, the activation is carried out in High Temperature Rotating activation furnace, the rotary speed of the High Temperature Rotating activation furnace
For 15~20r/min.
Preferably, procedure below is also included between the step 1 and step 2：Bamboo after drying is crushed, is used in combination
The sieve of 50~100 mesh, by weight, take 20~30 parts of bamboo powder, 5~10 parts of modifying agent, pore former 3 after sieving
~5 parts, 3~5 parts of hydrochloric acid, 30~50 parts of hot water add in stainless steel spherical containers, spherical container is placed on four axle bevellers,
Four axle bevellers are opened, drive stainless steel spherical container randomly to rotate, 30~60min are reacted, directly by reacted mixed liquor
Drying, obtains being modified bamboo；The charging aperture of the stainless steel spherical container is sealed by threaded cap, threaded cap be tightly connected after with
The surface of stainless steel spherical container flushes.
Preferably, the modifying agent be triblock copolymer F127, PCE, polyoxyethylene-poly-
One or more combinations in styrene block copolymer or Polystyrene-Polyethylene pyridine block copolymer.
Preferably, the modifying agent is that weight ratio is 1:2 triblock copolymer F127 and polyoxyethylene-polystyrene
Block copolymer；The pore former is appointing in ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium acid carbonate, potassium carbonate, saleratus
Meaning is a kind of；The concentration of the hydrochloric acid is 1~2mol/L；The temperature of the hot water is 100 DEG C.
Preferably, it is described directly also to include after the drying of reacted mixed liquor：It is added to after modified bamboo is ground well
In reactor, reactor is placed in Muffle furnace, with 1~5 DEG C/min of temperature programming to 200~300 DEG C, is incubated 1~3 hour.
Preferably, the active rotating speed of the four axles beveller is 100~150rpm, stochastic transition frequency is 30~
60s。
Preferably, the process of the step 5 replaces with：Bamboo charcoal material is added in stainless steel spherical container, added simultaneously
Enter deionized water, sealed spherical container by threaded cap, be placed on four axle bevellers, open four axle bevellers, drive not
Become rusty steel ball shape container randomly 30~60min of rotation, filters, dries；Then method same as described above is used, using ethanol and baking
Dry bamboo charcoal material adds stainless steel spherical container, and 30~60min of random rotation is carried out on four axle bevellers；Dry, obtain
Bamboo charcoal base lithium ion battery electrode material；The active rotating speed of the four axles beveller is 30~60rpm, and stochastic transition frequency is
10~30s.
Preferably, the drying is dried using microwave radiation, and its process is：Bamboo charcoal material after filtering is put into quartz
In drier, it is subsequently placed in microwave radiation reacting furnace；Nitrogen is passed through with 50~100mL/min speed, precipitation carried out micro-
Wave radiation drying process；The condition of the microwave radiation drying process is：Microwave radiation frequencies are 2450 ± 50MHz, microwave spoke
It is 0.10~1.00w/g to penetrate unit power, and microwave irradiation time is 30~60min, and microwave radiation temperature is 50~70 DEG C.
The present invention comprises at least following beneficial effect：The present invention preparation method have operation is simple, repeatability
By force, cost is low, it is environmentally safe the characteristics of.The bamboo charcoal material prepared by the use of this method as lithium ion battery electrode material,
The physically activated preparation method of this charing and cleaning can effectively increase material specific surface area, hold so as to further improve battery
Amount, strengthens its cycle performance.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings：
Fig. 1 is that Fig. 1 of the present invention is the bamboo charcoal XRD prepared in embodiment 1.
Fig. 2 is the bamboo charcoal SEM figures prepared in the embodiment of the present invention 1.
Fig. 3 is discharge and recharge ratio electricity of the bamboo charcoal material prepared in the embodiment of the present invention 1 as lithium ion battery electrode material
Rong Tu.
Embodiment：
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of individual other elements or its combination.
Embodiment 1：
A kind of method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material, comprises the following steps：
Step 1: after bamboo is cleaned with ethanol and deionized water respectively, dried 24 hours at 80 DEG C of temperature；
Step 2: the bamboo after drying is placed in porcelain boat, and it is placed in high temperature process furnances, under argon gas protection, with
30 DEG C/min of programming rate is warming up to 800 DEG C, carbonizes 2 hours, obtains bamboo carbon；
Step 3: by bamboo carbon grind into powder, with the sieve of 100 mesh, evengranular bamboo carbon powder end is obtained；
Step 4: bamboo carbon powder is warming up to 800 DEG C with 30 DEG C/min of programming rate, while with 20sccm speed
It is passed through physically activated dose of CO2, activate 2 hours, natural cooling, the bamboo charcoal material after being activated；
Step 5: bamboo charcoal material is soaked by deionized water and ethanol respectively, bamboo charcoal base lithium ion battery electrode is obtained
Material.Fig. 1 is the bamboo charcoal XRD prepared in embodiment 1.Wherein abscissa is angle, and ordinate is relative intensity.Can by Fig. 1
Find out that being 23.5 ° and 43.5 ° in 2 θ nearby has wider hunchbacked shape diffraction maximum, the bamboo charcoal for illustrating to obtain is amorphous graphite carbon knot
Structure.Fig. 2 is the bamboo charcoal SEM figures prepared in the embodiment of the present invention 1.Bamboo charcoal has the lamellar structure of class graphene as seen from Figure 2,
I.e. by simply carbonizing and physically activated method prepares natural class graphene layer structure, and bamboo charcoal surface have it is porous
Structure.Fig. 3 is discharge and recharge specific capacitance of the bamboo charcoal material prepared in the embodiment of the present invention 1 as lithium ion battery electrode material
Figure.Bamboo charcoal material first discharge specific capacity is 300.9mAh/g as seen from Figure 3, and the cycle charge-discharge under conditions of 0.1C
After 500 times, its specific capacitance stills remain in 52% or so.Illustrate, by charing and physically activated mode, to carry out bamboo charcoal
Controllable adjustment, so as to have successfully been obtained a kind of lithium ion battery electrode material long, environment-friendly with service life.
Embodiment 2：
A kind of method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material, comprises the following steps：
Step 1: after bamboo is cleaned with ethanol and deionized water respectively, dried 24 hours at 100 DEG C of temperature；
Step 2: the bamboo after drying is placed in porcelain boat, and it is placed in high temperature process furnances, under argon gas protection, with
15 DEG C/min of programming rate is warming up to 900 DEG C, carbonizes 2 hours, obtains bamboo carbon；
Step 3: by bamboo carbon grind into powder, with the sieve of 100 mesh, evengranular bamboo carbon powder end is obtained；
Step 4: bamboo carbon powder is warming up to 900 DEG C with 15 DEG C/min of programming rate, while with 20sccm speed
It is passed through physically activated dose of CO2, activate 4 hours, natural cooling, the bamboo charcoal material after being activated；
Step 5: bamboo charcoal material is soaked by deionized water and ethanol respectively, bamboo charcoal base lithium ion battery electrode is obtained
Material.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 301.2mAh/g, and is followed under conditions of 0.1C
After ring discharge and recharge 500 times, its specific capacitance stills remain in 53% or so.
Embodiment 3：
A kind of method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material, comprises the following steps：
Step 1: after bamboo is cleaned with ethanol and deionized water respectively, dried 24 hours at 120 DEG C of temperature；
Step 2: the bamboo after drying is placed in porcelain boat, and it is placed in high temperature process furnances, under argon gas protection, with
20 DEG C/min of programming rate is warming up to 750 DEG C, carbonizes 2 hours, obtains bamboo carbon；
Step 3: by bamboo carbon grind into powder, with the sieve of 100 mesh, evengranular bamboo carbon powder end is obtained；
Step 4: bamboo carbon powder is warming up to 750 DEG C with 20 DEG C/min of programming rate, while with 100sccm speed
It is passed through physically activated dose of CO2, activate 2 hours, natural cooling, the bamboo charcoal material after being activated；
Step 5: bamboo charcoal material is soaked by deionized water and ethanol respectively, bamboo charcoal base lithium ion battery electrode is obtained
Material.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 301.5mAh/g, and is followed under conditions of 0.1C
After ring discharge and recharge 500 times, its specific capacitance stills remain in 52% or so.
Embodiment 4：
A kind of method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material, comprises the following steps：
Step 1: after bamboo is cleaned with ethanol and deionized water respectively, dried 24 hours at 80 DEG C of temperature；
Step 2: the bamboo after drying is placed in porcelain boat, and it is placed in high temperature process furnances, under argon gas protection, with
25 DEG C/min of programming rate is warming up to 1000 DEG C, carbonizes 2 hours, obtains bamboo carbon；
Step 3: by bamboo carbon grind into powder, with the sieve of 100 mesh, evengranular bamboo carbon powder end is obtained；
Step 4: bamboo carbon powder is warming up to 950 DEG C with 15 DEG C/min of programming rate, while with 50sccm speed
It is passed through physically activated dose of CO2, activate 4 hours, natural cooling, the bamboo charcoal material after being activated；
Step 5: bamboo charcoal material is soaked by deionized water and ethanol respectively, bamboo charcoal base lithium ion battery electrode is obtained
Material.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 302.2mAh/g, and is followed under conditions of 0.1C
After ring discharge and recharge 500 times, its specific capacitance stills remain in 51% or so.
Embodiment 5：
In the step 4, the temperature-rise period of activation replaces with：300 DEG C are warming up to 5 DEG C/min speed, insulation
120min, 600 DEG C then are warming up to 1 DEG C/min speed, are incubated 3h, are then warming up to 800 DEG C with 10 DEG C/min speed,
5h is incubated, completes activation；The activation is carried out in High Temperature Rotating activation furnace, and the rotary speed of the High Temperature Rotating activation furnace is
15r/min.Remaining parameter and technical process with it is identical in embodiment 1.The bamboo charcoal base lithium ion battery electrode material is first
Secondary specific discharge capacity is 310.5mAh/g, and under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in
58% or so.Using the process of gradient increased temperature, further increase the utilization rate of activation evergy, and improve bamboo charcoal base lithium from
The specific capacitance of sub- battery electrode material.
Embodiment 6：
In the step 4, the temperature-rise period of activation replaces with：250 DEG C are warming up to 2 DEG C/min speed, insulation
90min, 700 DEG C then are warming up to 1.5 DEG C/min speed, are incubated 3h, are then warming up to 800 DEG C with 5 DEG C/min speed,
6h is incubated, completes activation；The activation is carried out in High Temperature Rotating activation furnace, and the rotary speed of the High Temperature Rotating activation furnace is
20r/min.Remaining parameter and technical process with it is identical in embodiment 1.In remaining parameter and technical process and embodiment 1
It is identical.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 311.2mAh/g, and in 0.1C bar
Under part after cycle charge-discharge 500 times, its specific capacitance stills remain in 59% or so.
Embodiment 7：
Also include procedure below between the step 1 and step 2：Bamboo after drying is crushed, and with the sieve of 100 mesh
Son sieving, by weight, take 25 parts of bamboo powder, 10 parts of modifying agent, 5 parts of pore former, 3 parts of hydrochloric acid, 40 parts of hot water after sieving
Add in stainless steel spherical container, spherical container is placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical
Container randomly rotates, and reacts 30min, directly dries reacted mixed liquor, obtain being modified bamboo；The stainless steel ball describes
The charging aperture of device is sealed by threaded cap, and threaded cap flushes after being tightly connected with the surface of stainless steel spherical container.The modification
Agent is triblock copolymer F127；The pore former is ammonium carbonate；The concentration of the hydrochloric acid is 1mol/L；The temperature of the hot water
For 100 DEG C.Remaining parameter and technical process with it is identical in embodiment 1.The bamboo charcoal base lithium ion battery electrode material is first
Secondary specific discharge capacity is 321.5mAh/g, and under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in
65% or so.The present invention carries spherical container by four axle bevellers, realizes the random rotation solidification in spherical container.Will be close
Envelope spherical container be fixed by four support shafts of four axle bevellers, adjust four axle slewing rates and actively with it is driven
Change-over period between axle, realize the trackless orientation in additional flow field.This method makes bamboo modified-reaction more complete, passes through the mistake
The modification of journey, bamboo is formed more pore structures, and introduce new chemical group, after high temperature cabonization, form high electrification
The group of activity is learned, makes bamboo charcoal that there is excellent electrochemical capacitor characteristic, obtains the bamboo charcoal base lithium ion battery electricity of excellent performance
Pole material.
Embodiment 8：
Also include procedure below between the step 1 and step 2：Bamboo after drying is crushed, and with the sieve of 100 mesh
Son sieving, by weight, 50 parts of 30 parts of bamboo powder, 8 parts of modifying agent, 3 parts of pore former, 5 parts of hydrochloric acid, hot water after sieving is taken to add
Enter in stainless steel spherical container, spherical container is placed on four axle bevellers, open four axle bevellers, drive stainless steel ball to describe
Device randomly rotates, and reacts 60min, directly dries reacted mixed liquor, obtain being modified bamboo；The stainless steel spherical container
Charging aperture sealed by threaded cap, threaded cap be tightly connected after flushed with the surface of stainless steel spherical container.Four axle is ground
The active rotating speed for grinding instrument is 100rpm, and stochastic transition frequency is 30s；The modifying agent is that weight ratio is 1:2 three block is total to
Polymers F127 and polyoxyethylene-polystyrene block copolymer；The pore former is sodium acid carbonate；The concentration of the hydrochloric acid is
2mol/L；The temperature of the hot water is 100 DEG C.Remaining parameter and technical process with it is identical in embodiment 1.The bamboo charcoal base
Lithium ion battery electrode material first discharge specific capacity is 325.3mAh/g, and cycle charge-discharge 500 times under conditions of 0.1C
Afterwards, its specific capacitance stills remain in 67% or so.
Embodiment 9：
It is described directly also to include after the drying of reacted mixed liquor：It is added to after modified bamboo is ground well in reactor,
Reactor is placed in Muffle furnace, with 2 DEG C/min of temperature programmings to 200 DEG C, is incubated 1 hour.Remaining parameter and technical process with
It is identical in embodiment 8.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 328.5mAh/g, and
Under conditions of 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in 70% or so.
Embodiment 10：
The process of the step 5 replaces with：Bamboo charcoal material is added in stainless steel spherical container, while adds deionization
Water, spherical container is sealed by threaded cap, be placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical
Container randomly rotates 30min, filters, and dries；Then method same as described above is used, using ethanol and the bamboo charcoal material of drying
Stainless steel spherical container is added, random rotation 30min is carried out on four axle bevellers；Dry, obtain bamboo charcoal base lithium ion battery
Electrode material；The active rotating speed of the four axles beveller is 30rpm, and stochastic transition frequency is 10s.Remaining parameter and technique mistake
Journey with it is identical in embodiment 1.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 312.5mAh/g,
And under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in 60% or so.
Embodiment 11：
The drying is dried using microwave radiation, and its process is：Bamboo charcoal material after filtering is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；Nitrogen is passed through with 100mL/min speed, precipitation is carried out at microwave radiation drying
Reason；The condition of the microwave radiation drying process is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
0.5w/g, microwave irradiation time 30min, microwave radiation temperature are 70 DEG C.In remaining parameter and technical process and embodiment 10
It is identical.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 317.5mAh/g, and in 0.1C bar
Under part after cycle charge-discharge 500 times, its specific capacitance stills remain in 65% or so.Dried using microwave radiation, microwave is in quilt
Heating caused by inside thing, thermal source comes from interior of articles, homogeneous heating, is advantageous to improve bamboo charcoal material quality, simultaneously because in
Outer heating simultaneously substantially reduces the heat time, and the efficiency of heating surface is high, is advantageous to improve bamboo charcoal material yield, obtains excellent performance
Bamboo charcoal base lithium ion battery electrode material.
Embodiment 12：
Also include procedure below between the step 1 and step 2：Bamboo after drying is crushed, and with the sieve of 100 mesh
Son sieving, by weight, take 25 parts of bamboo powder, 10 parts of modifying agent, 5 parts of pore former, 3 parts of hydrochloric acid, 40 parts of hot water after sieving
Add in stainless steel spherical container, spherical container is placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical
Container randomly rotates, and reacts 30min, directly dries reacted mixed liquor, obtain being modified bamboo；The stainless steel ball describes
The charging aperture of device is sealed by threaded cap, and threaded cap flushes after being tightly connected with the surface of stainless steel spherical container.The modification
Agent is triblock copolymer F127；The pore former is ammonium carbonate；The concentration of the hydrochloric acid is 1mol/L；The temperature of the hot water
For 100 DEG C.Remaining parameter and technical process with it is identical in embodiment 6.The bamboo charcoal base lithium ion battery electrode material is first
Secondary specific discharge capacity is 331.2mAh/g, and under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in
75% or so.
Embodiment 13：
Also include procedure below between the step 1 and step 2：Bamboo after drying is crushed, and with the sieve of 100 mesh
Son sieving, by weight, take 25 parts of bamboo powder, 10 parts of modifying agent, 5 parts of pore former, 3 parts of hydrochloric acid, 40 parts of hot water after sieving
Add in stainless steel spherical container, spherical container is placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical
Container randomly rotates, and reacts 30min, directly dries reacted mixed liquor, obtain being modified bamboo；The stainless steel ball describes
The charging aperture of device is sealed by threaded cap, and threaded cap flushes after being tightly connected with the surface of stainless steel spherical container.The modification
Agent is triblock copolymer F127；The pore former is ammonium carbonate；The concentration of the hydrochloric acid is 1mol/L；The temperature of the hot water
For 100 DEG C.Remaining parameter and technical process with it is identical in embodiment 10.The bamboo charcoal base lithium ion battery electrode material is first
Secondary specific discharge capacity is 328.2mAh/g, and under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in
73% or so.
Embodiment 14：
Also include procedure below between the step 1 and step 2：Bamboo after drying is crushed, and with the sieve of 100 mesh
Son sieving, by weight, take 25 parts of bamboo powder, 10 parts of modifying agent, 5 parts of pore former, 3 parts of hydrochloric acid, 40 parts of hot water after sieving
Add in stainless steel spherical container, spherical container is placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical
Container randomly rotates, and reacts 30min, directly dries reacted mixed liquor, obtain being modified bamboo；The stainless steel ball describes
The charging aperture of device is sealed by threaded cap, and threaded cap flushes after being tightly connected with the surface of stainless steel spherical container.The modification
Agent is triblock copolymer F127；The pore former is ammonium carbonate；The concentration of the hydrochloric acid is 1mol/L；The temperature of the hot water
For 100 DEG C.Remaining parameter and technical process with it is identical in embodiment 11.The bamboo charcoal base lithium ion battery electrode material is first
Secondary specific discharge capacity is 335.2mAh/g, and under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in
78% or so.
Embodiment 15：
The process of the step 5 replaces with：Bamboo charcoal material is added in stainless steel spherical container, while adds deionization
Water, spherical container is sealed by threaded cap, be placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical
Container randomly rotates 30min, filters, and dries；Then method same as described above is used, using ethanol and the bamboo charcoal material of drying
Stainless steel spherical container is added, random rotation 30min is carried out on four axle bevellers；Dry, obtain bamboo charcoal base lithium ion battery
Electrode material；The active rotating speed of the four axles beveller is 30rpm, and stochastic transition frequency is 10s.Remaining parameter and technique mistake
Journey with it is identical in embodiment 6.The bamboo charcoal base lithium ion battery electrode material first discharge specific capacity is 320.2mAh/g,
And under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in 65% or so.The present invention is ground by four axles
Grind instrument and carry spherical container, realize the random rotation solidification in spherical container.Sealing spherical container is passed through into four axle bevellers
Four support shafts be fixed, adjust the change-over period between four axle slewing rates and active and driven shaft, realize additional stream
The trackless orientation of field.Bamboo charcoal is cleaned by this method, under the trackless orientation effect in additional flow field, makes the cleaning performance of bamboo charcoal more
Excellent, impurity can be cleaned completely, bamboo charcoal is had excellent electrochemical capacitor characteristic, obtain the bamboo charcoal base lithium of excellent performance from
Sub- battery electrode material.
Embodiment 16：
In the step 4, the temperature-rise period of activation replaces with：250 DEG C are warming up to 2 DEG C/min speed, insulation
90min, 700 DEG C then are warming up to 1.5 DEG C/min speed, are incubated 3h, are then warming up to 800 DEG C with 5 DEG C/min speed,
6h is incubated, completes activation；The activation is carried out in High Temperature Rotating activation furnace, and the rotary speed of the High Temperature Rotating activation furnace is
20r/min.Remaining parameter and technical process with it is identical in embodiment 11.The bamboo charcoal base lithium ion battery electrode material is first
Secondary specific discharge capacity is 325.2mAh/g, and under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in
70% or so.
Embodiment 17：
Also include procedure below between the step 1 and step 2：Bamboo after drying is crushed, and with the sieve of 100 mesh
Son sieving, by weight, take 25 parts of bamboo powder, 10 parts of modifying agent, 5 parts of pore former, 3 parts of hydrochloric acid, 40 parts of hot water after sieving
Add in stainless steel spherical container, spherical container is placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical
Container randomly rotates, and reacts 30min, directly dries reacted mixed liquor, obtain being modified bamboo；The stainless steel ball describes
The charging aperture of device is sealed by threaded cap, and threaded cap flushes after being tightly connected with the surface of stainless steel spherical container.The modification
Agent is triblock copolymer F127；The pore former is ammonium carbonate；The concentration of the hydrochloric acid is 1mol/L；The temperature of the hot water
For 100 DEG C.Remaining parameter and technical process with it is identical in embodiment 16.The bamboo charcoal base lithium ion battery electrode material is first
Secondary specific discharge capacity is 355.5mAh/g, and under conditions of the 0.1C after cycle charge-discharge 500 times, its specific capacitance stills remain in
85% or so.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited
In specific details and shown here as the legend with description.
Claims (10)
1. a kind of method that physical activation method prepares bamboo charcoal base lithium ion battery electrode material, it is characterised in that including following step
Suddenly：
Step 1: after bamboo is cleaned with ethanol and deionized water respectively, dried 12~48 hours at 60~120 DEG C of temperature；
Step 2: the bamboo after drying is placed in porcelain boat, and be placed in high temperature furnace, argon gas protection under, with 10-30 DEG C/
The programming rate of minute is warming up to 500-1000 DEG C, carbonizes 1-12 hours, obtains bamboo carbon；
Step 3: by bamboo carbon grind into powder, with the sieve of 10~300 mesh, evengranular bamboo carbon powder end is obtained；
Step 4: bamboo carbon powder is warming up to 500-1000 DEG C with 10-30 DEG C/min of programming rate, while with 10-
500sccm speed is passed through physically activated dose of CO2, activate 1-12 hours, natural cooling, the bamboo charcoal material after being activated；
Step 5: bamboo charcoal material is soaked by deionized water and ethanol respectively, bamboo charcoal base lithium ion battery electrode material is obtained.
2. the method that physical activation method as claimed in claim 1 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In in the step 4, the temperature-rise period of activation is：250~300 DEG C are warming up to 2~5 DEG C/min speed, insulation 90~
120min, 500~700 DEG C then are warming up to 0.5~1.5 DEG C/min speed, 3~5h are incubated, then with 5~10 DEG C/min
Speed be warming up to 800~1000 DEG C, be incubated 5~8h, complete activation.
3. the method that physical activation method as claimed in claim 2 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In the activation is carried out in High Temperature Rotating activation furnace, and the rotary speed of the High Temperature Rotating activation furnace is 15~20r/min.
4. the method that physical activation method as claimed in claim 1 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In also including procedure below between the step 1 and step 2：Bamboo after drying is crushed, and with the sieve of 50~100 mesh
Son sieving, by weight, take sieving after 20~30 parts of bamboo powder, 5~10 parts of modifying agent, 3~5 parts of pore former, hydrochloric acid 3~
5 parts, 30~50 parts of hot water add in stainless steel spherical containers, spherical container is placed on four axle bevellers, opens the grinding of four axles
Instrument, drive stainless steel spherical container randomly to rotate, react 30~60min, directly reacted mixed liquor is dried, is modified
Bamboo；The charging aperture of the stainless steel spherical container is sealed by threaded cap, and threaded cap describes after being tightly connected with stainless steel ball
The surface of device flushes.
5. the method that physical activation method as claimed in claim 4 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In the modifying agent is triblock copolymer F127, PCE, polyoxyethylene-polystyrene block copolymerization
One or more combinations in thing or Polystyrene-Polyethylene pyridine block copolymer.
6. the method that physical activation method as claimed in claim 4 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In the modifying agent is that weight ratio is 1:2 triblock copolymer F127 and polyoxyethylene-polystyrene block copolymer；Institute
Pore former is stated as any one in ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium acid carbonate, potassium carbonate, saleratus；The salt
The concentration of acid is 1~2mol/L；The temperature of the hot water is 100 DEG C.
7. the method that physical activation method as claimed in claim 4 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In described directly also to include after the drying of reacted mixed liquor：It is added in reactor, will reacts after modified bamboo is ground well
Kettle is placed in Muffle furnace, with 1~5 DEG C/min of temperature programming to 200~300 DEG C, is incubated 1~3 hour.
8. the method that physical activation method as claimed in claim 4 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In the active rotating speed of the four axles beveller is 100~150rpm, and stochastic transition frequency is 30~60s.
9. the method that physical activation method as claimed in claim 4 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In the process of the step 5 replaces with：Bamboo charcoal material is added in stainless steel spherical container, while adds deionized water, is led to
Cross threaded cap to seal spherical container, be placed on four axle bevellers, open four axle bevellers, drive stainless steel spherical container without
Rule 30~60min of rotation, filters, dries；Then method same as described above is used, the bamboo charcoal material using ethanol and drying adds
Enter stainless steel spherical container, 30~60min of random rotation is carried out on four axle bevellers；Dry, obtain bamboo charcoal base lithium ion electricity
Pond electrode material；The active rotating speed of the four axles beveller is 30~60rpm, and stochastic transition frequency is 10~30s.
10. the method that physical activation method as claimed in claim 9 prepares bamboo charcoal base lithium ion battery electrode material, its feature exists
In the drying is dried using microwave radiation, and its process is：Bamboo charcoal material after filtering is put into quartzy drier, then
It is placed in microwave radiation reacting furnace；Nitrogen is passed through with 50~100mL/min speed, precipitation is carried out at microwave radiation drying
Reason；The condition of the microwave radiation drying process is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
0.10~1.00w/g, microwave irradiation time are 30~60min, and microwave radiation temperature is 50~70 DEG C.
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