CN107140633A - A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived - Google Patents
A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived Download PDFInfo
- Publication number
- CN107140633A CN107140633A CN201710555280.6A CN201710555280A CN107140633A CN 107140633 A CN107140633 A CN 107140633A CN 201710555280 A CN201710555280 A CN 201710555280A CN 107140633 A CN107140633 A CN 107140633A
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- sulphur
- surface area
- specific surface
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/362—Composites
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
-
- 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
- C01P2006/14—Pore volume
-
- 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
-
- 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
A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived, belong to preparation and the lithium-sulfur cell technical field of carbon material.Present invention utilizes biomass castoff --- and palm shell passes through charing, activation, rinsing and dry easy steps, you can obtain the activated carbon with high specific surface area of biomass derived as carbon source.Activated carbon and sulphur are mixed and carry out attached reaction of Salmon-Saxl, the composite of palm shell activated carbon and sulphur is obtained；Again by the composite of palm shell activated carbon and sulphur and conductive carbon black, Kynoar mixed dissolution in N-methyl pyrrolidones, mixed slurry is formed；Then mixed slurry is coated on aluminium foil, through drying, the positive electrode of lithium-sulfur cell is made.Obtained activated carbon has high-specific surface area, pore-size distribution concentration, high absorption property and high electrochemical performance.
Description
Technical field
The invention belongs to the preparing technical field of carbon material, lithium-sulfur cell technical field is directed to.
Background technology
Non-renewable by tradition, the energy resource consumption or production of limited combustion of fossil fuel are not only World Economics fast
The necessary condition of speed development, and also result in that environmental pollution is increasingly serious, the aggravation of global warming and energy crisis, because
This, environmental pollution and energy supply turn into two most important subjects under discussion.From social sustainability and the viewpoint of environment friendly
From the point of view of, porous carbon materials use of electrode material in lithium-sulfur cell increasingly attracts attention.
Lithium-sulfur cell is very high due to its electric energy density, causes the concern in the fields such as electric automobile application.However, simple substance
The electrons/ions electrical conductivity of sulphur is poor, seriously limits its practical application in the electrodes.Another problem of lithium-sulfur cell is S
Reduction produce various soluble long-chain polysulphides（Li2Sn, 4≤n≤8）, it further combines to form insoluble and insulation with Li
Li2S2/Li2S is precipitated.This bad phenomenon not only results in the loss of low coulombic efficiency and active material, but also can hinder
The accessibility of ion.The improvement of the electrical conductivity of sulfur electrode and suppression ion spread in organic bath will turn into lithium-sulfur cell
The emphasis of research.
With high-specific surface area, the nanostructured carbon material of macropore volume and loose structure, such as mesoporous carbon, CNT,
Porous graphene, hollow carbon balls and activated carbon, all apply to the matrix of elemental sulfur.Carbon framework provides for the insertion and abjection of sulphur
Good conductive network, in addition, nano-porous structure can cause the diffusion of polymer.Therefore, various activation sides are passed through
Method（Physics and chemical activation）, can be used to synthesize and prepare the micro-structural of porous carbon materials.Especially, it is used as activation using KOH
The chemical activation of the various carbon sources of agent is very promising, because its relatively low activation temperature and higher yield, Yi Jiliang
The pore size distribution limited well and up to 3000 m2g-1The superhigh specific surface area porous carbon of left and right.
Carbon source based on fossil is limited and non-renewable, therefore various renewable in the urgent need to developing, abundant
Natural biomass and derivative and waste are used as the economy for preparing activated carbon, environmentally friendly carbon source.
Palm shell is a large amount of solid waste of palm oil factory discharge, originates in Africa, now plants extensively in the torrid zone
Various regions, it is especially most with Malay Peninsula cultivation.If these discarded objects are arbitrarily abandoned in process, not only waste of resource, and
Environmental pollution can be caused.
The content of the invention
Present invention aims at propose a kind of activated carbon with high specific surface area of utilization palm shell preparation biomass derived
Method.
The present invention comprises the following steps：
1）It will be crushed after palm shell in a nitrogen environment charing process, obtain the palm shell powder of charing；
2）After the palm shell powder of charing is mixed with activator, then dry, palm fibre of the acquirement containing activator is placed at 100 ± 10 DEG C
Palmitic acid shell powder；
3）Palm shell powder containing activator is placed in nitrogen atmosphere, activated under 800~1000 DEG C of temperature conditionss, through cold
But, the palm material of activation is obtained；
4）The palm material of activation is rinsed to neutrality with aqueous hydrochloric acid solution and deionized water, then through drying, obtains black powder
The activated carbon with high specific surface area of solid particle, i.e. biomass derived.
Present invention utilizes biomass castoff --- and palm shell is used as carbon source.Because palm shell material is hard, containing a small amount of
Ash content, lignin and cellulose etc., can be also a kind of activity of high-quality as inexpensive carbon source as abandoned biomass
Carbon precursor raw material.The present invention is by charing, activation, rinsing and dries easy steps, you can obtain the superelevation of biomass derived
Specific surface area active carbon.Obtained activated carbon has high-specific surface area, pore-size distribution concentration, high absorption property and high electrochemical
Energy.
Compared with prior art, the advantage of present invention process is：
1st, palm shell abundant raw materials, cost are low.Biomass castoff palm shell is used to prepare high performance active carbon for raw material, no
Only fully utilize biomass and be recycled raw material, and be conducive to atmosphere pollution and water pollution control.In the present of energy scarcity
My god, meet people to green, saving, environmentally friendly pursuit direction.
2nd, by activating the biomass porous activated carbon prepared, preparation technology is simple, can be effectively improved carbon-sulphur and be combined
The performance of electrode.The porous hole of gained activated carbon can not only fully be contacted with insulating materials sulphur, improve carbon-sulphur composite
High conductivity, and can be adsorbed in discharge process and store polysulfide, so as to prevent polysulfide to be dissolved in electrolysis
In liquid.In addition, suitable mesopore macropore is conducive to quickly transmitting during electrochemistry is circulated and diffusion ion is to micropore, and show
Land and prevent the aggregation of sulphur.Therefore, the compound porous carbon in lithium-sulfur cell shows that their capacitive property is better than common porous carbon.
Further, step 1 of the present invention）The temperature environment of middle charing process is 500 ± 20 DEG C.Carrying out pre- charing is
By the way that carbon source presoma is directly carried out into high temperature pyrolysis under inert gas conditions, so that basic body transforms are into specific structure
Can controlled porous carbon solid material.In carbonization process, the density of carbon material gradually increases.Pre- charing initial stage, due to small
The effusion of molecule can generate certain hole, and the quantity of hole starts to be continuously increased.If carbonization temperature is too high, it can destroy
The pore structure of carbonized material, can cause structure collapses to a certain extent so that activator cannot be introduced into hole depths and be activated,
So as to cause the performance of prepared activated carbon to reduce；If carbonization temperature is too low, charcoal not exclusively can be caused because of pre- charing
The hole of material does not have complete opening, and the activation for also resulting in activator is uneven so that the property of prepared activated carbon
Can reduction.Therefore, the temperature environment of selection charing process is relatively reasonable for 500 ± 20 DEG C.
The step 2）Described in activator be KOH.The use of most activator is at present KOH solution.It is not activated
Carbonized material there is a small amount of macropore, and surface porosity.Pore structure is conducive to activator（KOH）Progress activation is rapidly entered to make
Hole, therefore, is conducive to obtaining superhigh specific surface area and pore volume.Wherein, when less than 500 DEG C, predominantly carbon material is de-
Water process；When temperature is less than 762 DEG C (boiling point of potassium), it is mainly anti-with amorphous carbon with KOH conducted in activation
Potassium carbonate should be generated, to consume substantial amounts of carbon particle, so as to form substantial amounts of duct gap structure in carbon base body；When temperature after
Continuous when increasing to over the boiling point of potassium, potassium can turn into potassium steam at high temperature, and quarter candle, activation effect raising are carried out to carbon material.
The step 2）Described in the palm shell powder that carbonizes and KOH mixing quality ratio be 3~5: 1.In general, such as charcoal
The palm shell powder consumption of change is excessive, then activated carbon can be because activator is excessive and make it that the reaction between carbon and activator is excessively acute
Strong, mesoporous be counter-bored in part causes meso-hole structure to reduce for macropore, causes performance to reduce；And the palm shell powder consumption such as carbonized
It is too small, then can be very few because of activator, activator is difficult to fully react with carbonized material and carry out sufficient reaming, and causes charing
Material can not be activated fully, and hole is less and then performance is reduced；Alkali charcoal is more lucky than the effect of mixing, then in activation process,
Activator has given full play to the effect of pore-creating, reaming, accelerates the priming reaction of carbonized material so that activated carbon specific surface area is rapidly
Increase, pore volume also further increases.The usage amount of raw material can be reduced to a certain extent simultaneously and the cost of activated carbon is prepared,
Activation temperature, soak time and alkali carbon ratio are reduced, the energy consumption of whole technical process is reduced.
The step 3）The time of middle activation is 1 h.On the premise of activation temperature and alkali carbon ratio are constant, soak time mistake
It is long, charcoal and the time lengthening of the reaction of oxygen potassium oxide can be caused, more carbonized materials is reacted in activation process so that
Hole in activated carbon is by dilatation, and the micropore quantity for ultimately resulting in activated carbon is reduced；Soak time is too short, then can cause potassium hydroxide
Reaction time with carbon is too short, so as to cause the incomplete of activation process progress, carbonized material is not activated fully so that living
Property charcoal in many pore structures do not open completely, the micropore quantity of activated carbon is reduced.And carbonized material exist macropore with
And loose structure enables activator comparatively fast preferably to perform etching pore-creating reaction with carbon atom, shortens priming reaction
Time.This also show soak time influences relatively small to activated carbon.
The present invention is another object is that propose the application of activated carbon produced above in lithium-sulfur cell.
Attached reaction of Salmon-Saxl is carried out after first mixing the activated carbon and sulphur, the composite of palm shell activated carbon and sulphur is obtained；
Again by the composite of palm shell activated carbon and sulphur and conductive carbon black, Kynoar mixed dissolution in n-methlpyrrolidone
In, form mixed slurry；Then mixed slurry is coated on aluminium foil, through drying, the positive electrode of lithium-sulfur cell is made.
After tested, in electrolyte solution, it is using the positive electrode as working electrode, by negative electrode membrane of metal lithium sheet
The lithium-sulfur cell that Celgard-2250 type polypropylene screens are assembled into has following characteristic：
Experiment shows：Palm shell activated carbon has 2760m2/ g specific surface area and 1.6cm3/ g pore volume, what is prepared is larger
The porous carbon of specific surface area is conducive to positive electrode preferably to permeate in electrolyte.Palm shell activated carbon is not year-on-year with sulphur simple substance
The mixed C/S compounds to different sulfur contents of example.C/S compound of the sulfur content up to 60% is under 200mA/g current densities
Initial reversible capacity is up to 945mAh/g, and shows after superior cycle performance, the circle of circulation 100, and reversible capacity can also be kept
822mAh/g, capacity is high, good cycling stability.During initial cycle, the coulombic efficiency of battery is positively retained at more than 95%.
In addition, the mixing quality ratio of the activated carbon and sulphur is 1: 1.5~4.Due to elemental sulfur electron conduction very
It is low, the positive pole of lithium-sulfur cell can hardly be directly used as, so it must be combined by using the material of high conductivity from
And improve the electronic conductivity of active sulfur material surface.The solution mainly used at present is that appropriate mix is carried out to elemental sulfur
Miscellaneous, by introducing high conductivity matrix in sulphur positive electrode, and it is such as more that fine suction-operated can be played to polysulfide
Hole carbon.The main pore volume according to prepared activated carbon of usual attached sulfur content, which is calculated, to be obtained, and is calculated by the pore volume and density of porous carbon
To porous carbon quality, the quality of elemental sulfur and attached sulphur rate is calculated according to appended by being obtained S/C molal weight fractions, this experimental calculation institute
The attached sulphur rate obtained is 58.2%.It is generally acknowledged that the performance of lithium-sulfur cell could have been carried when sulfur content is not less than 60% in positive electrode
Height, so the mixing quality ratio of currently preferred activated carbon and sulphur is 1: 1.5~4.
The attached reaction of Salmon-Saxl is carried out under the conditions of 155 DEG C.Because composite is in 155 DEG C of heat treatment processes, elemental sulfur
Be melted into molten, mobility it is optimal and to pore space structure to be sufficient filling with effect best, it is possible to increase contact area, be conducive to carrying
High-performance.If temperature is too high, the structure of sulphur starts fracture, and the increasing with the continuation vapor pressure enhancement of temperature causes liquid sulfur
Gradually become sulphur steam to run out of, element sulphur largely runs out of matrix with the form of sulphur steam at 400 DEG C.
In addition, on the positive electrode of lithium-sulfur cell, it is typically high by adding for the non-conductive problem of wherein elemental sulfur
Conduction, the conductive carrier of high-specific surface area is that prepared palm shell porous carbon is combined with elemental sulfur, to increase positive pole material
The electric conductivity of material and the diffusion path for shortening lithium ion and electronics, are conducive to the fast charging and discharging process of battery.Directly by carbon
Source and sulphur are simply mixed, and battery capacity is low, decay is fast, therefore this experiment adds appropriate second in electrode composite material
Acetylene black conductive agent, can promote electro transfer to set up a good conductive network, reaction is had enough reactivities, to carry
Rise the electric conductivity of overall electrode material；And appropriate Kynoar is introduced as the binding agent for preparing slurry, it is viscous by it
The cooperation Stability Analysis of Structures for keeping sulfur electrode material, makes sulfur-bearing dusty material be bonded together.The content of adhesive is crossed conference and made
Electric conductivity into sulfur-bearing positive electrode is not high, the specific discharge capacity of this utilization rate that can reduce sulphur and sulfur electrode.Meanwhile, sulfur electrode
The content of middle adhesive can not be too small, otherwise, and positive pole easily comes off containing sulfur powder in battery charge and discharge process from collector, makes
The specific discharge capacity of utilization rate and sulfur electrode into sulphur declines.Comprehensive each side factor, the final preferred composite materials of the present invention with
Conductive carbon black, the mixing quality ratio of Kynoar are 8: 1: 1.
Brief description of the drawings
The Flied emission of composite after the attached sulphur of activated carbon with high specific surface area for the biomass derived that Fig. 1 is prepared for the present invention
Scanning electron microscope sem figure.
The Flied emission of composite after the attached sulphur of activated carbon with high specific surface area for the biomass derived that Fig. 2 is prepared for the present invention
Transmission electron microscope TEM schemes.
The X-ray of composite after the attached sulphur of activated carbon with high specific surface area for the biomass derived that Fig. 3 is prepared for the present invention
Diffraction XRD.
The X-ray of composite after the attached sulphur of activated carbon with high specific surface area for the biomass derived that Fig. 4 is prepared for the present invention
Photoelectron spectroscopy XPS schemes.
Composite after the attached sulphur of activated carbon with high specific surface area for the biomass derived that Fig. 5 is prepared for the present invention is applied to
In lithium-sulfur cell, the cyclic voltammetry curve figure of test.
Composite after the attached sulphur of activated carbon with high specific surface area for the biomass derived that Fig. 6 is prepared for the present invention is applied to
In lithium-sulfur cell, the constant current charge-discharge curve map of test.
Composite after the attached sulphur of activated carbon with high specific surface area for the biomass derived that Fig. 7 is prepared for the present invention is applied to
In lithium-sulfur cell, the cyclic curve figure of test.
When Fig. 8 is attached sulfur content 40: 60,30: 70 and 20: 80, the lithium-sulfur cell cycle performance curve comparison figure obtained respectively.
Embodiment
The experimentation of the present invention is described in detail below, it is intended to make design cycle, the purpose of design of the present invention
And its innovative point and advantage more understand.
First, activated carbon is prepared：
Example 1：
1st, carbonize：
Weigh dry palm husk as raw material to be placed in silica crucible, place into tube furnace and heat, under nitrogen closed environment, with
Charing process 2h under the conditions of temperature in tube furnace is risen to 500 ± 20 DEG C by 5 DEG C/min heating rate.
Stand and be cooled to after normal temperature after end and taken out, the palm shell carbonized material for obtaining black is crushed, and is sieved, and is obtained
The palm shell powder of the charing of particle diameter≤10 μm, it is standby.
2nd, impregnate：
The palm shell powder for weighing charing is mixed with KOH according to 3: 1 mass ratio, is added appropriate distilled water, is placed in after stirring
Dried in 100 ± 10 DEG C of baking ovens, obtain the palm shell powder containing activator.
3rd, activate：
Palm shell powder containing activator is placed in nickel crucible, placed into tube furnace, under conditions of blanket of nitrogen, with 5 DEG C/
Temperature in tube furnace is risen to 800 DEG C by min heating rate, and keeping temperature activates 1 h.Then cool down, obtain the palm of activation
Material.
4th, drying is washed：
The palm material of activation is rinsed to neutrality with aqueous hydrochloric acid solution and deionized water, to remove the activation remained in activated carbon
Agent, then dried through suction filtration, the activated carbon with high specific surface area of black powder solid particle, i.e. biomass derived is obtained, and divide
Not Biao Ji for：Activated carbon 1#, activated carbon 2#, activated carbon 3#.
The concentration of above aqueous hydrochloric acid solution is 1 M, and its pH value is 6~8.
Example 2：
1st, carbonize：
Weigh dry palm husk as raw material to be placed in silica crucible, place into tube furnace and heat, under nitrogen closed environment, with
Charing process 3h under the conditions of temperature in tube furnace is risen to 500 ± 20 DEG C by 5 DEG C/min heating rate.
Stand and be cooled to after normal temperature after end and taken out, the palm shell carbonized material for obtaining black is crushed, and is sieved, and is obtained
The palm shell powder of the charing of particle diameter≤10 μm, it is standby.
2nd, impregnate：
The palm shell powder for weighing charing is mixed with KOH according to 5: 1 mass ratio, is added appropriate distilled water, is placed in after stirring
Dried in 100 ± 10 DEG C of baking ovens, obtain the palm shell powder containing activator.
3rd, activate：
Palm shell powder containing activator is placed in nickel crucible, placed into tube furnace, under conditions of blanket of nitrogen, with 5 DEG C/
Temperature in tube furnace is risen to 1000 DEG C by min heating rate, and keeping temperature activates 1 h.Then cool down, obtain the palm of activation
Material.
4th, drying is washed：
The palm material of activation is rinsed to neutrality with aqueous hydrochloric acid solution and deionized water, to remove the activation remained in activated carbon
Agent, then dried through suction filtration, the activated carbon with high specific surface area of black powder solid particle, i.e. biomass derived is obtained, and divide
Not Biao Ji for：Activated carbon 4#, activated carbon 5#, activated carbon 6#.
The concentration of above aqueous hydrochloric acid solution is 1 M, and its pH value is 6~8.
Example 3：
The activated carbon with high specific surface area of biomass derived is prepared in the method similar with upper example, and is respectively labeled as：It is living
Property charcoal 7#, activated carbon 8#, activated carbon 9#.
2nd, apply：
Embodiment 1：
1st, the preparation of carbon-sulphur composite：
Activated carbon made from example 1 and sulphur are mixed, wherein, the mass ratio of activated carbon and sulphur is set to 40: 60,30: 70 and 20:
80。
Then mixture is kept into 12 h in sealed ptfe autoclave in 155 DEG C of heating, it is ground, obtain
The palm shell activated carbon and the composite of sulphur of black, and correspondence markings are AC/S-60, AC/S-70 and AC/S-80 respectively.
2nd, the preparation of electrode slice：
It is in mass ratio 8: 1: 1, by the composite of palm shell activated carbon and sulphur, conductive carbon black（Super P, are used as conductive agent）
And Kynoar（5 % PVDF, are used as binding agent）It is blended in 1-METHYLPYRROLIDONE（NMP, is used as dispersant）In solvent,
Grind and stir and prepare slurry.Slurry is coated on aluminium foil by using coating device, is placed in vacuum drying chamber at 50 DEG C
2 h are dried, dried electrode slice is taken out, is struck out a diameter of 9 mm electrode slice, be used as working electrode.
3rd, the assembling of battery：
Using 2032 type button batteries argon atmosphere glove box（Universal 2440/750, MIKROUNA）（Oxygen
Pressure and water partial pressure<1 ppm）It is middle to be assembled.Electrolyte solution is 1 M LiN（CF3SO2）2（LiTFSI）It is dissolved in dimethoxy second
Alkane（DME）And dioxolanes（DOL）Mixed liquor, negative pole is metal lithium sheet, and barrier film is Celgard-2250 type polypropylene screens.
Embodiment 2：
Take activated carbon made from example 2 and sulphur to mix, battery is assembled into as described in Example 1.
Embodiment 3：
Take activated carbon made from example 3 and sulphur to mix, battery is assembled into as described in Example 1.
3rd, product property：
Fig. 1 is combined after illustrating the attached sulphur of activated carbon with high specific surface area 5# of the biomass derived prepared in the embodiment of the present invention 2
The field emission scanning electron microscope SEM figures of material, the activated carbon after overactivation occurs in that flourishing and abundant random hole, and attached
There is no the aggregation for finding volume sulphur on the surface of composite after sulphur, this shows sulphur in heating process by capillary force
It is completely coupled in porous carbon matrix.
Fig. 2 is illustrated after the attached sulphur of activated carbon with high specific surface area 5# of the biomass derived prepared in the embodiment of the present invention 2
The Flied emission transmission electron microscope TEM figures of composite, in attached sulphur 60%（w）Afterwards, the TEM image of composite shows amorphous sulphur
Phase component is trapped within the duct of Activated carbon matrix, and big volume sulphur is not observed in the composite, shows elementary sulfur
It is dispersed in porous carbon matrix.
Fig. 3 illustrates the activated carbon with high specific surface area 5# and attached sulphur of the biomass derived prepared in the embodiment of the present invention 2
The X-ray diffraction XRD of composite afterwards, the XRD spectrum of activated carbon shows about 25 ° and 43 °, and this corresponds to amorphous carbon
's（002）With（100）Diffraction pattern.Fig. 3 also illustrates activated carbon made from example 2 not to be had after attached sulphur in the XRD of composite
It was found that the obvious peak crystallization related to sulphur, shows that sulphur is in high degree of dispersion state in hole.
Fig. 4 is illustrated after the attached sulphur of activated carbon with high specific surface area 5# of the biomass derived prepared in the embodiment of the present invention 2
The x-ray photoelectron power spectrum XPS figures of composite.The surface-element of prepared carbon material composition is carried out point by XPS
Analysis, prepared carbon material substantially contains N, S, tri- kinds of elements of P, while carrying out the composite after attached sulphur also contains higher S
Element, so that S element dopings are proved into prepared composite, attached sulphur success, elementary sulfur is evenly distributed on porous carbon-based
In the skeleton of matter.
Fig. 5,6,7 respectively show the activated carbon with high specific surface area of the biomass derived prepared in the embodiment of the present invention 2
Composite is applied to the electrochemical property test curve map of lithium-sulfur cell after the attached sulphur of 5#.
Fig. 5 is cyclic voltammetry curve figure, and in first circulates, it was observed that two reduction peaks and an oxidation peak, this is
Due to the multistep reaction mechanism of sulphur and lithium.In second circulates, two peaks of negative electrode and anode or it will be evident that this gives the credit to the
The polarization of electrode material in one circulation.
Fig. 6 is constant current charge-discharge curve map, gives the activated carbon under 200 mA/g during initial two circulate
The exemplary voltages capacity of combination electrode after attached sulphur, discharge curve shows two typical platforms in 2.3 and 2.1V, and it can be
The two-step reaction of sulphur and lithium is assigned in discharge process.For the combination electrode after the attached sulphur of activated carbon, initial discharge is obtained
Capacity is 945 mAh/g.
Fig. 7 is cyclic curve figure, activated carbon/cycle performance figure of the sulphur combination electrode under 200 mA/g, recycling 100
Secondary, discharge capacity is that 822 mAh/g are remained in that, shows good cycling stability.During initial cycle, the coulombic efficiency of battery is kept
More than 95%.
In addition, in the case of other conditions all identicals, only changing the quality of activated carbon and sulphur in preparation work electrode
Than, such as 40: 60,30: 70 and 20: 80, the lithium-sulfur cell performance obtained respectively is difference.
Because the specific surface area and larger pore volume of porous carbon superelevation cause the utilization rate of cycle performance of battery and sulphur to have
It is obviously improved, but high carbon sulphur mass ratio not necessarily corresponds to high specific discharge capacity.
The lithium-sulfur cell cycle performance curve comparison figure that Fig. 8 is obtained respectively when being attached sulfur content 40: 60,30: 70 and 20: 80.
When sulphur load capacity is 60%, the initial discharge capacity of the battery can be issued to 945mAh/g in 200mmA/g high current density,
Recycling 100 times, discharge capacity remains in that for 822mAh/g, and the coulombic efficiency of battery is positively retained at more than 95%, shows to follow
Ring stability is good.And attached sulfur content is 70% and 80% lithium-sulfur cell, discharge capacity decreases, because sulfur content is too high, is combined
The resistivity of thing is also accordingly raised, and this can cause the utilization rate of sulphur to decline.For to a certain extent, carbon-sulfur compound is improved conductive
Performance can just improve increase respective battery specific discharge capacity.
It can be seen that：The present invention prepares the palm shell activated carbon of superior performance under suitable alkali charcoal ratio and heating-up temperature,
By characterizing and testing the Properties of Activated Carbon prepared under different ratio condition of different temperatures, optimum performance condition is obtained, and carry out
Attached sulphur is applied in lithium-sulfur cell.
Claims (9)
1. a kind of preparation method of the activated carbon with high specific surface area of biomass derived, it is characterised in that comprise the following steps：
1）It will be crushed after palm shell in a nitrogen environment charing process, obtain the palm shell powder of charing；
2）After the palm shell powder of charing is mixed with activator, then dry, palm fibre of the acquirement containing activator is placed at 100 ± 10 DEG C
Palmitic acid shell powder；
3）Palm shell powder containing activator is placed in nitrogen atmosphere, activated under 800~1000 DEG C of temperature conditionss, through cold
But, the palm material of activation is obtained；
4）The palm material of activation is rinsed to neutrality with aqueous hydrochloric acid solution and deionized water, then through drying, obtains biomass derived
Activated carbon with high specific surface area.
2. preparation method according to claim 1, it is characterised in that：The step 1）The temperature environment of middle charing process is
500±20℃。
3. preparation method according to claim 1, it is characterised in that：The step 2）Described in activator be KOH.
4. preparation method according to claim 3, it is characterised in that：The step 2）Described in the palm shell powder that carbonizes with
KOH mixing quality ratio is 3~5: 1.
5. preparation method according to claim 3, it is characterised in that：The step 3）The time of middle activation is 1 h.
6. the activated carbon with high specific surface area for the biomass derived that the method as described in claim 1 preparation is obtained is in lithium-sulfur cell
In application, it is characterised in that：First the activated carbon and sulphur are mixed and carry out attached reaction of Salmon-Saxl, palm shell activated carbon and sulphur is obtained
Composite；Again by the composite of palm shell activated carbon and sulphur and conductive carbon black, Kynoar mixed dissolution in nitrogen-methyl
In pyrrolidones, mixed slurry is formed；Then mixed slurry is coated on aluminium foil, through drying, the positive pole of lithium-sulfur cell is made
Material.
7. application according to claim 6, it is characterised in that：The mixing quality ratio of the activated carbon and sulphur be 1: 1.5~
4。
8. the application according to claim 6 or 7, it is characterised in that：The attached reaction of Salmon-Saxl is carried out under the conditions of 155 DEG C.
9. application according to claim 6, it is characterised in that：The composite and conductive carbon black, Kynoar
Mixing quality ratio is 8: 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710555280.6A CN107140633A (en) | 2017-07-10 | 2017-07-10 | A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710555280.6A CN107140633A (en) | 2017-07-10 | 2017-07-10 | A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107140633A true CN107140633A (en) | 2017-09-08 |
Family
ID=59776286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710555280.6A Pending CN107140633A (en) | 2017-07-10 | 2017-07-10 | A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107140633A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108109853A (en) * | 2017-12-25 | 2018-06-01 | 武汉大学 | The preparation method and application of superelevation specific surface porous carbon biomass electrode material |
| CN108365210A (en) * | 2018-04-12 | 2018-08-03 | 桂林电子科技大学 | A kind of activated carbon carbon-sulfur materials and its preparation method and application |
| CN109755505A (en) * | 2018-12-17 | 2019-05-14 | 同济大学 | A kind of positive electrode and preparation method thereof for lithium-sulfur rechargeable battery |
| CN110127662A (en) * | 2019-05-26 | 2019-08-16 | 天津大学 | A method of assist charing Small molecule organic solvents to prepare porous charcoal using alkali metal |
| CN110357071A (en) * | 2019-07-18 | 2019-10-22 | 北华航天工业学院 | A kind of three-dimensional network carbon nanomaterial and its application |
| CN110707291A (en) * | 2019-10-21 | 2020-01-17 | 青岛科技大学 | Method for preparing lithium-sulfur battery anode by utilizing recycled carbon material |
| CN113277508A (en) * | 2021-05-20 | 2021-08-20 | 福建农林大学 | Preparation method and application of methylene blue adsorbing high-specific-surface-area activated carbon |
| CN113577981A (en) * | 2021-08-11 | 2021-11-02 | 浙江大学 | Oxygen-containing microporous activated carbon, preparation thereof and application thereof in selective adsorption of ethane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045077A (en) * | 2014-05-27 | 2014-09-17 | 陈永 | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof |
| CN104241651A (en) * | 2014-09-03 | 2014-12-24 | 上海大学 | Method for preparing sulphur-supported porous carbon lithium battery electrode material by using waste polyurethane plastic |
| CN106629723A (en) * | 2016-12-30 | 2017-05-10 | 扬州大学 | Biomass-based N, S and P-containing co-doped porous carbon and application thereof |
-
2017
- 2017-07-10 CN CN201710555280.6A patent/CN107140633A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045077A (en) * | 2014-05-27 | 2014-09-17 | 陈永 | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof |
| CN104241651A (en) * | 2014-09-03 | 2014-12-24 | 上海大学 | Method for preparing sulphur-supported porous carbon lithium battery electrode material by using waste polyurethane plastic |
| CN106629723A (en) * | 2016-12-30 | 2017-05-10 | 扬州大学 | Biomass-based N, S and P-containing co-doped porous carbon and application thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108109853A (en) * | 2017-12-25 | 2018-06-01 | 武汉大学 | The preparation method and application of superelevation specific surface porous carbon biomass electrode material |
| CN108365210A (en) * | 2018-04-12 | 2018-08-03 | 桂林电子科技大学 | A kind of activated carbon carbon-sulfur materials and its preparation method and application |
| CN109755505A (en) * | 2018-12-17 | 2019-05-14 | 同济大学 | A kind of positive electrode and preparation method thereof for lithium-sulfur rechargeable battery |
| CN110127662A (en) * | 2019-05-26 | 2019-08-16 | 天津大学 | A method of assist charing Small molecule organic solvents to prepare porous charcoal using alkali metal |
| CN110127662B (en) * | 2019-05-26 | 2022-02-01 | 天津大学 | Method for preparing porous carbon by using alkali metal-assisted carbonization small-molecule organic solvent |
| CN110357071A (en) * | 2019-07-18 | 2019-10-22 | 北华航天工业学院 | A kind of three-dimensional network carbon nanomaterial and its application |
| CN110707291A (en) * | 2019-10-21 | 2020-01-17 | 青岛科技大学 | Method for preparing lithium-sulfur battery anode by utilizing recycled carbon material |
| CN113277508A (en) * | 2021-05-20 | 2021-08-20 | 福建农林大学 | Preparation method and application of methylene blue adsorbing high-specific-surface-area activated carbon |
| CN113577981A (en) * | 2021-08-11 | 2021-11-02 | 浙江大学 | Oxygen-containing microporous activated carbon, preparation thereof and application thereof in selective adsorption of ethane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107140633A (en) | A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived | |
| Yan et al. | Process optimization for producing hierarchical porous bamboo-derived carbon materials with ultrahigh specific surface area for lithium-sulfur batteries | |
| Li et al. | Hierarchical porous carbon materials derived from self-template bamboo leaves for lithium–sulfur batteries | |
| CN106450102B (en) | Lithium-sulfur cell of the graphite modified diaphragm for lithium-sulfur cell and preparation method thereof with composition | |
| Xia et al. | Nitrogen and oxygen dual-doped hierarchical porous carbon derived from rapeseed meal for high performance lithium–sulfur batteries | |
| CN110438798A (en) | A kind of lithium-sulfur cell self-supporting positive electrode and its method for manufacturing electric spinning | |
| CN109081340B (en) | Pine-based biomass activated carbon, preparation method thereof and application thereof in electrochemical energy storage | |
| CN103390752B (en) | Graphene-based matrix material, its preparation method and the application in lithium-sulfur cell thereof | |
| CN109817963B (en) | Fe7Se8Preparation method and application of nano particle/nitrogen-doped carbon nanofiber composite material | |
| CN105977474B (en) | A kind of straightforward procedure improving carbon sulphur complex lithium sulphur anode cyclical stability | |
| CN109473655A (en) | Antimony nanoparticle/nitrogen-doped carbon nanometer necklace composite material (Sb/N-CNN) preparation method and applications | |
| Ding et al. | Fabrication of a sandwich structured electrode for high-performance lithium–sulfur batteries | |
| CN107946553B (en) | High-graphitization three-dimensional carbon nanotube graphene composite material and preparation and application thereof | |
| Huang et al. | Controlled synthesis of three-dimensional porous carbon aerogel via catalysts: effects of morphologies toward the performance of lithium-sulfur batteries | |
| CN105206814A (en) | Method for preparing high performance lithium ion battery negative electrode material porous carbon covering exposed (001) active crystal titanium dioxide nanocubes | |
| CN109817923A (en) | A kind of nitrogen-doped porous carbon material and its preparation method and application | |
| CN110600713A (en) | Porous carbon doped anode material, preparation method thereof and alkali metal ion battery | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN108321438A (en) | Full graphite lithium-sulfur cell and preparation method thereof | |
| CN105529490A (en) | Preparation method for lithium-sulfur battery | |
| CN113363463B (en) | Sludge/biomass co-pyrolysis coke-coated lithium iron phosphate cathode material and preparation method and application thereof | |
| Li et al. | Preparation of biochar from different biomasses and their application in the Li-S battery | |
| CN108963237B (en) | Preparation method of sodium ion battery negative electrode material | |
| CN112374484B (en) | S/CeO for preparing lithium-sulfur battery positive electrode material 2 Method for preparing porous biomass carbon | |
| CN112786869A (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170908 |