CN106099108A - A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material - Google Patents
A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material Download PDFInfo
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- CN106099108A CN106099108A CN201610764551.4A CN201610764551A CN106099108A CN 106099108 A CN106099108 A CN 106099108A CN 201610764551 A CN201610764551 A CN 201610764551A CN 106099108 A CN106099108 A CN 106099108A
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- graphite
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- absorbent charcoal
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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
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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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- 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
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Abstract
The invention discloses the preparation method of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material, step is: A, washed by plant material, loads in canister and seals, inserts in Muffle furnace, 450～650 DEG C of heated at constant temperature, naturally cool to room temperature and obtain black solid activated carbon；B, by the black solid activated carbon obtained and mass ratio be the graphite of 3:1～1:1 in ball grinder, be separately added into hydrochloric acid, 0.1～0.5M sulphuric acid, 0.5～1.2M acetic acid, water that appropriate, concentration is 0.2～1.0M successively；Under the conditions of ratio of grinding media to material is equal to 1:10～1:20, ball milling 0.5～2 hours, i.e. pickling, washing；The most each ball milling of sulphuric acid, hydrochloric acid, acetic acid washs 3～5 times, and the value of water for ball milling washing to eluate pH is 6.8-7.2；C, by washed graphite/Mixture of Activated Carbon sucking filtration, drying under atmospheric environment.Technique is simple, and abundant raw materials, the manufacturing cycle is short, and energy consumption is low, has good economic benefit, environmental benefit and good social benefit.
Description
Technical field
The present invention relates to battery material technical field, be more particularly to a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material
Preparation method.
Background technology
Lithium ion battery mainly by anode pole piece, cathode pole piece, barrier film, electrolyte and battery container (include stainless steel case,
Plastic housing and aluminum plastic film flexible package etc.) part composition.Wherein, cathode pole piece is mainly by negative electrode active material, additive and bonding
Agent forms.The negative electrode active material manufacturing lithium ion battery negative electrode is usually mainly " natural negative pole graphite " or " modified stone
Ink " or " Delanium ", and CNT, Graphene etc., the synthetic technology of graphite material, the processing of material and electrochemistry
Can wait, relative contrast is more stable, ripe, the source of native graphite also compared with horn of plenty thus cheap, but be also lithium-ion electric
One of the critical material in pond, is one of material of having a major impact of the impact of the combination property on lithium ion battery.
Simultaneous interpretation unified alkaline Mn cell, secondary accumulator battery (such as lead-acid battery, Ni-MH battery, nickel-cadmium cell etc.) compare, because of
Have that single battery voltage height, specific capacity height, good cycle, storge quality be excellent for lithium ion battery, specific energy and specific energy
Numerous distinguishing features such as density is high, and be widely used in electric tool, movable electrical appliances, model plane, unmanned plane, electric automobile dynamic
Power power supply and the various fields such as portable power source, emergency power supply.Along with entering of related application technical field electric equipment and device
Step and development, it is desirable to lithium ion battery has thin, light, high-energy high-power density, high cycle performance and high security.
In recent years, the correlational study of lithium ion battery negative material is concentrated mainly on the modification to native graphite, New Type of Carbon
Nanotube, Graphene, amorphous carbon and numerous metal-oxides etc..Wherein, graphite is the earliest for lithium ion battery
Carbon negative pole material, its good conductivity, degree of crystallinity is high, has complete layered crystal structure, the embedding of suitable lithium ion and abjection.
CNT is formed the material of " have and be similar to graphite laminate structure " by single or multiple lift coaxial carbon plate layer.
The sp of CNT2Hybrid structure and high draw ratio are that it brings a series of excellent properties.This special microcosmic knot
Structure makes that the insert depth of lithium ion is little, stroke is short and embedded location many (in pipe and the gap of interlayer, hole etc.), simultaneously because of carbon
Nanotube conductive performance is fine, has the conduction of preferable electronics and ion transport capacity, is suitable as lithium ion battery negative material.
Therefore, CNT is as lithium ion battery negative material, it is clear that than traditional graphite electrode advantageously.But use carbon nanometer
Pipe there is also weak point directly as lithium ion battery negative material: 1) irreversible capacity is relatively big first, and first charge-discharge is imitated
Rate ratio is relatively low；2) carbon nanometer tube negative pole lacks stable voltage platform；3) there is current potential hysteresis in CNT.Additionally, carbon
The synthesis cost of nanotube is the highest.These all limit the CNT actual application as lithium ion battery negative material.
Graphene (Graphene) be one only by carbon atom with sp2The flat thin of hybrid orbital composition hexangle type lattice
Film, that is the two-dimensional material of only one of which carbon atom thickness.Comparing other Carbon Materials such as CNT, Graphene has uniqueness
Microstructure, this makes Graphene have bigger specific surface area and cellular void structure, has higher storage lithium ability.This
Outward, material itself has the mechanical property of good chemical stability, high electron mobility and excellence so that it is as electrode material
Material has outstanding advantage.Similar with CNT, pure grapheme material owing to circulating that coulombic efficiency is low first, charge and discharge platform relatively
High and cyclical stability is poor, synthesis cost is high, commercial value shortcoming etc. defect, can not replace the most commercial raw material of wood-charcoal
Material is directly used as lithium ion battery negative material.
Metal oxide-carbon is (such as: SnO, VO2、TiO2、LixFe2O3、Li4Mn2O12、Li4Ti5O12Cover material with carbon element etc.) material
As the negative pole of lithium ion battery, owing in organic electrolyte solution, carbon surface formation can allow electronics and lithium ion pass freely through
Passivation layer, while this passivation layer ensure that the cycle performance that electrode is good, electric CR Critical first charge-discharge can be caused
The loss of irreversible capacity, the most even can cause structure change and the poor electric contact of electrode interior.It addition, also may be used under high temperature
Battery failure can be caused because of the decomposition of protective layer or produce safety problem.
In order to improve above-mentioned deficiency or the defect of lithium ion battery negative material, produce function admirable, high security
Lithium ion battery, those skilled in the relevant art mainly research and develop Novel cathode material for lithium ion battery.Document " self-supporting WS2/
The electrostatic spinning preparation of carbon fibre composite and the application [J] as lithium ion battery negative material thereof " (Science Bulletin,
2016,61 (8): 912) describe utilize electrostatic spinning technique be prepared for one " two dimension WS2Nanometer sheet is uniformly embedded in carbon nanometer
Fibrous composite ", document claims, and composite membrane shaped material prepared by this technology need not conductive agent, bonding agent, can be directly used as
Lithium ion battery negative, can be directly from making flexible battery device.Document " Corchorus olitorius L. base carbon fibre/MnO/C lithium ion battery negative
The preparation of material and chemical property [J] thereof " (Chinese Journal of Inorganic Chemistry, 2016,32 (5): 811-817) describe with Corchorus olitorius L. fine
Dimension, potassium permanganate and polymer pyrroles are raw material, prepare " carbon fiber/MnO/C " lithium ion battery through the most numerous and diverse step and bear
The technology of pole material.Carbon fiber/MnO/C material structurally has effective electron channel and the polynary collaborative effect on composition
Should, show higher specific capacity, good cycle performance and high rate performance as lithium cell cathode material.The document is not
There are practicable technological parameter and the process conditions etc. providing secure lithium ion battery.Document " metatitanic acid high temperature solid-state method
Prepare lithium ion battery negative material spinelle Li4Ti5O12[J] " (electronic original part and material, 2016,35 (3): 19-21) report
" spinel-type Li is synthesized with solid reaction process4Ti5O12Negative material "." the spinel-type Li of document report4Ti5O12Negative pole
Material " first charge-discharge capacity be 158.63mAh/g, (electric current) efficiency is 98.7%.Document " ZnFe2O4Lithium ion battery is born
The preparation of pole material and Electrochemical Properties [J] " (Journal of Inorganic Materials, 2016,31 (1): 34-38) have studied and use ZnFe chlorine
Compound is that the hydro-thermal-solid reaction process of raw material prepares " ZnFe2O4Negative material " technology and the content such as chemical property.This article
Offer the ZnFe of synthesis2O4Negative material is nanometer porous spherical particle, has higher reversible specific capacity and more stable following
Ring performance.
" zinc replaces spinelle Li additionally, document2MnTi3O8Lithium ion battery negative material microstructure and electrochemistry
Can impact [J] " (non-ferrous metal engineering, 2015,5 (6): 1-6) synthesize Li by sol-gel process2MnTi3O8Aqueous precursor gel
Material, adds ZnAc2, prepare zinc through high-temperature calcination and replace spinelle Li2MnTi3O8Lithium ion battery negative material.Document
Claim: the zinc of synthesis replaces spinelle Li2MnTi3O8Lithium ion battery negative material specific capacity after 36 charge and discharge cycles
It is respectively 199.4mAh/g and 260.2mAh/g." lamellar titanosilicate compound is as lithium ion battery negative energy storage material for document
Material [J] " (Chinese Journal of Inorganic Chemistry, 2015,31 (12): 2425-2431) have studied and use lamellar titanosilicate Na4Ti2Si8O22·
4H2O (Na-JDF-L1) prepares lithium ion battery negative material through ion exchange.Main by by TiO2Be incorporated into Li (Na)-
In JDF-L1, it is effectively improved coulombic efficiency first and the multiplying power discharging property of material.Document " multilevel hierarchy SnO2 nano flower conduct
High performance lithium ionic cell cathode material [J] " (Science Bulletin, 2015,60 (9): 892-895) describe " flower-shape nano SnO2”
The solvent-thermal method technology of preparing of negative material.Flower-shape nano SnO prepared by the document2The reversible capacity of negative material is
350.7mAh/g。
Document " lithium ion battery negative material Li4Ti5O12Synthesis and performance study [J] " (electrochemistry, 2015,21
(2): 181-186) describe with TiO2, Quilonorm (SKB) be raw material, solid phase synthesis lithium ion battery negative Li4Ti5O12The side of material
Method.Report synthesis Li4Ti5O1210C high magnification first discharge specific capacity reach 143.0mAh/g.Document " three-dimensional multistage hole class
Graphene carries iron sesquioxide lithium ion battery negative material [J] " (electrochemistry, 2015,21 (1): 66-71), with numerous and diverse from
The synthetic technologys such as son exchange, liquid phase reactor, solid phase roasting, synthesize and have studied the load iron sesquioxide conduct of three-dimensional porous Graphene
The performance of lithium ion battery negative material.Document claims: the Fe of synthesis2O3The first discharge specific capacity of-3D HPG material is up to
1745mAh/g, 50 times recycle ratio capacity is maintained at 1095mAh/g.Document " uniform load nickel oxide nanoparticle porous hard carbon ball
Preparation and high performance lithium ionic cell cathode material application [J] " (Acta PhySico-Chimica Sinica, 2015,31 (2): 268-276) be situated between
Continued a kind of technology utilizing hydro-thermal method to prepare lithium ion battery negative material.It is said that the composite of document report synthesis
Under 100mA/g electric current density charge condition, initial charge specific capacity is 764mAh/g, and after circulation in 100 weeks, charge specific capacity keeps
At 777mAh/g；Under 800mA/g electric current density charge condition, charging capacity 380mAh/g.
Both at home and abroad many patents also disclose that relevant activated carbon is for for lithium ion battery electrode material correlation technique；But have
The patented technology of the synthesis and application of closing activated carbon negative electrode material discloses less.United States Patent (USP) " Rechargeable lithium
battery including positive electrode including activated carbon and
Electrolyte containing propylene carbonate [P] " (number of patent application 9,153,842,2015.10.6)
Disclose one " to include positive pole, include the chargeable lithium cell of the electrolyte that activated carbon comprises Allyl carbonate ", this patent skill
Art discloses the manufacturing process formula etc. of lithium battery body, and applied activated carbon uses as positive electrode or anode additive, but
The contents such as the open manufacturing technology relating to activated carbon.United States Patent (USP) " Cell assembly for an energy
Storage device with activated carbon electrodes [P] " (number of patent application 7,881,042,
2011.2.1) open a kind of " battery component of the energy storage device of active carbon resistance rod ".United States Patent (USP)
“Electrochemical battery including a product of activated carbon fiber as an
Electrode [P] " a kind of disclosed in (number of patent application 4,510,216,1985.6.9) " include that NACF is as electrode
The electrochemical cell of product " electrochemical cell that manufactures for electrode material with modified and unmodified NACF of technology
(referring to: description Abstract part).
Chinese invention patent " preparation method [p] of a kind of composite prepared based on activated carbon " (number of patent application
2015 10720807.7) preparation method of " a kind of composite prepared based on activated carbon " is disclosed.This patent of invention institute is public
It is raw material that the technology of opening is mainly activated carbon, silicon dioxide, polymer, nickel nitrate, bonding agent and too acid butyl ester etc., with activated carbon
Based on prepare purifying water process material.Chinese invention patent " a kind of activated carbon nanofiber and preparation method thereof [P] " (patent
Application number 201610179105.7) disclose the technology of preparing of a kind of cylindrical " a kind of activated carbon nanofiber ".This invention is special
Technology concrete measure disclosed in profit is: with polyacrylonitrile as carbon source, DMF is solvent, is former with phosphorous acid
Position activator.By warm and fine for a certain amount of polypropylene phosphorous acid (H3PO3) be dissolved in DMF after mixing after form forerunner
After body fluid, prepare precursor fibre by method of electrostatic spinning, then under the protection of high temperature inert gas, carry out carbonization, had
High-specific surface area, the activated carbon nanofiber of high porosity.NACF prepared by the disclosure technology can be excellent as performance
Good catalyst and catalyst carrier, electrode of super capacitor etc. (referring to its specification digest).Chinese invention patent " a kind of stone
Ink alkene doping polyacrylonitrile center hole activated carbon fiber and preparation method thereof [P] " (number of patent application 201610058563.5) offer
A kind of Graphene doping polyacrylonitrile center hole activated carbon fiber and preparation method thereof.Technology concrete scheme disclosed in this patent
It is: prepare Graphene doping blend spinning stock solution；Use wet spinning technology to carry out spinning, impregnate in catalysis expanding agent solution
5～24 hours, put in activation furnace after drying at 80～120 DEG C, little in 200～300 DEG C of pre-oxidation 2～5 in air atmosphere
Time, activation, take out after furnace cooling, obtain Graphene doping polyacrylonitrile center hole activated carbon fiber.It is said that what this invention prepared
The Graphene that Graphene doping polyacrylonitrile center hole activated carbon fiber is excellent owing to the addition of electric conductivity, and have suitably
Central hole structure, preferable electric conductivity, be especially suitable for doing the electrode of ultracapacitor.(referring to its summary part).Chinese invention is special
Profit " mesoporous activated Carbon fibe of electrode of super capacitor polyacrylonitrile and preparation method thereof [P] " (number of patent application
201610060357.8) technology of preparing of one " the mesoporous activated Carbon fibe of electrode of super capacitor polyacrylonitrile " is disclosed,
Its step includes: add in solvent by pore creating material organic compound and/or high polymer, then stirs 3～24 at 50～80 DEG C
Hour, obtain the solution containing pore creating material；Polyacrylonitrile pulp is mixed with the described solution containing pore creating material, mixed
Spinning solution；Use wet spinning technology to carry out spinning, obtain mixing precursor；Mixing precursor is soaked in catalysis expanding agent solution
Stain 5～24 hours, put in activation furnace after drying at 80～120 DEG C pre-oxidize, activate, carbonization, obtain electrode of super capacitor
With the mesoporous activated Carbon fibe of polyacrylonitrile.The mesoporous activated Carbon fibe of polyacrylonitrile that the present invention prepares is the most mesoporous owing to having
Structure, and have higher-strength concurrently, it is suitable for doing the electrode of ultracapacitor.(referring to its summary).
Chinese invention patent " a kind of porous activated carbon fiber material based on spider silk and application [P] " (number of patent application
201511033803.8) " a kind of porous activated carbon fiber material based on spider silk and application " technology is disclosed.Its preparation side
Method comprises the following steps: to collect the Aranea in environment, removes impurity therein；Successively with deionized water, hydrochloric acid, EtOH Sonicate
Clean 20～40min, then clean up with ultra-pure water, be dried；By dry spider web 200～400 DEG C of pre-carbonizations, treat its natural cooling
Mix with activating reagent to room temperature, be ground, then through 700～1000 DEG C of carbonizations, obtain porous activated carbon fiber.The present invention
The porous activated carbon fiber material of preparation can be as microorganism fuel cell cathode catalyst and electrode material.Chinese invention patent
" preparation method [P] of a kind of activated carbon nano fiber " (number of patent application 201510566866.3) discloses a kind of nano active
The preparation method of Carbon fibe.It is said: this technical purpose is to solve that existing activated carbon nano fiber preparation technology is loaded down with trivial details, cost is high
Problem, method particularly includes: prepare standby Bacterial cellulose；Prepare potassium hydroxide/Bacterial cellulose；Prepare potassium hydroxide/thin
Fungin presoma；It is subsequently placed in tube furnace and carries out high temperature pyrolysis, obtain activated carbon nano fiber.The present invention utilizes hydrogen-oxygen
Change potassium/Bacterial cellulose is as presoma, and a step prepares activated carbon nano fiber, is produced on a large scale, and decreases processing step,
Method is the most energy-conservation, and raw material environmental protection is cheap and easy to get；Twice lyophilization is used to avoid the hydrolysis of Bacterial cellulose, the most again
Do not destroy Bacterial cellulose microstructure；Gained NACF is used as the electrode material of ultracapacitor, has well
Capacitance characteristic (refers to its summary).Chinese invention patent " the system of a kind of Bacterial cellulose/NACF/graphene film material
Preparation Method and application [P] thereof " (number of patent application 201510566811.2) disclose Bacterial cellulose/NACF/graphite
The preparation method and applications of alkene membrane material.Concrete technical method disclosed in this patented technology is: prepare standby bacterial fibers
Element, prepares NACF dispersion liquid；Prepare Bacterial cellulose slurry；Prepare composite dispersion liquid, Bacterial cellulose is starched
Material vacuum filtration film forming, be subsequently adding composite dispersion liquid continue sucking filtration be dried, make Bacterial cellulose/NACF/
Graphene film material, this materials application is in ultracapacitor.The present invention is produced on a large scale, and preparation technology is simple, low cost, lead
Film material stability and mechanical property are good, are prepared as ultracapacitor and have good capacitive character.Additionally, similar middle promulgated by the State Council
Bright patented technology " preparation method and applications [P] of a kind of Bacterial cellulose/NACF/CNT membrane material " is (specially
Profit application number 201510566765.6) disclose the preparation side of a kind of Bacterial cellulose/NACF/CNT membrane material
Method and application thereof.Technical measures disclosed in this patent are: method is: prepares standby Bacterial cellulose, prepares NACF
Dispersion liquid；Prepare Bacterial cellulose slurry；Prepare composite dispersion liquid, by Bacterial cellulose slurry vacuum filtration film forming, so
Rear addition composite dispersion liquid continues sucking filtration and is dried, and makes Bacterial cellulose/NACF/CNT membrane material, should
Materials application is in ultracapacitor.The present invention is produced on a large scale, and preparation technology is simple, low cost, conducting membrane material stability
And mechanical property is good, it is prepared as ultracapacitor and there is good capacitive character." one-step method prepares nano active to Chinese invention patent
The method [P] of Carbon fibe " (number of patent application 201510566814.6) disclose one and " prepare the side of activated carbon nano fiber
Method ".Its concrete grammar is: prepare standby Bacterial cellulose；Prepare potassium hydroxide/Bacterial cellulose presoma；It is subsequently placed in pipe
Formula stove carries out high temperature pyrolysis, obtains activated carbon nano fiber.The present invention utilizes potassium hydroxide/Bacterial cellulose as forerunner
Body, a step prepares activated carbon nano fiber, decreases processing step, and method is simple, is produced on a large scale, and cheaper starting materials is easy to get；
Select alcohol solvent to replace aqueous solvent to avoid the hydrolysis of cellulose, the most do not destroy Bacterial cellulose microstructure simultaneously；By institute
Obtain NACF and be used as the electrode material of ultracapacitor, there is good capacitance characteristic (referring to its summary).Chinese invention
Patent " polysaccharide-modified activated carbon is as the preparation method [P] of electrode material for super capacitor " (number of patent application
201510490434.9) disclose the polysaccharide-modified activated carbon preparation method as electrode material for super capacitor.The disclosure skill
Art is specifically: first polysaccharide hydro-thermal reaction prepares carbon ball, then carbon ball is mixed with potassium hydroxide soaks, and allows potassium hydroxide fill
Dividing diffuses in material with carbon element, final high temperature calcining mixt so that activation of potassium hydroxide carbon ball, prepares absorbent charcoal material；Profit
The polysaccharide-modified absorbent charcoal material prepared by this method has abundant grade pore structure, and bigger specific surface area, as super
Capacitor electrode material electrode capacity is up to 510F/g.It is said that the disclosure technology has, technological operation is simple, repeatability is high, one-tenth
This cheap feature (refers to its summary)." biomass pomelo peel derives activated carbon as super capacitor electrode to Chinese invention patent
The preparation method [P] of pole material " (number of patent application 201510490433.4) disclose the derivative activity of a kind of biomass pomelo peel
Charcoal is as the preparation method of electrode material for super capacitor, and this technology is: first lightly-carbonized for pomelo peel hydro-thermal have many
The pomelo peel of pore structure, then pomelo peel hydrothermal product is mixed with potassium hydroxide soak, allow potassium hydroxide fully diffuse into
Enter pomelo peel, final high temperature calcining mixt so that activation of potassium hydroxide carbon ball, prepare the cellular work with grade pore structure
Property Carbon Materials；The Alveolate activated carbon utilizing this method to prepare has an abundant grade pore structure, bigger specific surface area, as
Electrode material for super capacitor electrode capacity is up to 300F/g, it is said: this patented technology method has that technological operation is simple, repeats
Property feature high, with low cost (referring to its summary).Chinese invention patent " flexible nitrogen-dopped activated carbon combination electrode material and
Preparation method [P] " (number of patent application 201510445900.1) disclose one " flexible nitrogen-dopped activated carbon combination electrode material
And preparation method thereof ".Its preparation method be divide stripping by many for silkworm cocoon thin slices after, then carry out pf resin of low molecular weight compound and
High-temperature activation processes, final prepared flexible nitrogen-dopped activated carbon combination electrode material.The disclosure technology journey: the carbon compound electric of preparation
Pole material has high wettability, has some strength and plastic deformation ability, and its charge-conduction performance and capacitive property are significantly
Improve.
Chinese invention patent " preparation method [P] of a kind of stabilizing activity charcoal/nanoscale Pd/Fe composite particles " (patent
Application number 201610284705.X) disclose one " preparation method of stabilizing activity charcoal/nanoscale Pd/Fe composite particles ".
Its preparation method is under inert gas shielding, makes soluble ferrite at alkali-metal boron hydride and the bar of ul-trasonic irradiation
Under part and stir react, make Fe2+ change into nanometer nulvalent iron particle；Add solubility palladium salt to react, contained
There is the reactant liquor of nanoscale Pd/Fe particle；Add activated carbon granule, then stirring carry out load-reaction under ul-trasonic irradiation,
Obtain stabilizing activity charcoal/nanoscale Pd/Fe composite particles.It is said: combination electrode material prepared by the disclosure technology has grain
Footpath is little, the big and finely dispersed effect of specific surface area.Material prepared by this technology is mainly used in sewage treatment area.Chinese invention
Patent " the activated carbon catalysis granule electrode of Supported Co oxide and preparation method [P] " (number of patent application 201610271420.2)
Disclose one " the activated carbon catalysis granule electrode of Supported Co oxide and preparation method ".Its material prepared is also used for sewage
Process field.Chinese invention patent " preparation method [P] of activated carbon " (number of patent application 201510383207.6) discloses one
Plant " preparation method of activated carbon ".This preparation method includes: preoxidation process: DCL/Direct coal liquefaction Colophonium carries out pre-oxidation anti-
Should, obtain pre-oxidizing Colophonium；Carbonization process: pre-oxidation Colophonium is mixed with activator, carries out carbonization reaction, obtain carbonization drip
Blue or green；Activation process: carbonization Colophonium is carried out the activation that heats up, obtains activated carbon.First carry out pre-oxidizing by DCL/Direct coal liquefaction Colophonium
Journey, this can make the small-molecule substance in above-mentioned Colophonium cross-link with macromolecular substances, form dystectic pre-oxidation Colophonium,
Thus it is melted to be conducive to suppression DCL/Direct coal liquefaction Colophonium to occur in carbonization process.The most above-mentioned pre-oxidation Colophonium is again through carbonization
The process of process and fast activating has prepared the activated carbon with high specific surface area.
Chinese invention patent " preparation method [P] of rice husk matrix activated carbon " (number of patent application 201310535792.8) is open
One rice husk prepares " method of activated carbon ".Specific practice is: cleaned by rice husk, dry, pulverize, and 100～120 DEG C are dried
After, carbonization at a temperature of 300～450 DEG C；Cooling, grinds, and 100 mesh sieve；Rice hull carbon after sieving and NaOH are by quality
Mix than 1:3, add deionized water and soak 3h at ambient temperature；It is dried at 100～120 DEG C, is subsequently placed in microwave reactor
In, set microwave power 600～900W, in reactor, be passed through N2, 15min post-heating to 400～800 DEG C activation 30～
60min, furnace cooling；Deionization is used again after soaking 8h with the HCL (should be HCl, i.e. hydrochloric acid, this explanation is noted) of mass fraction 5%
Water washing, to neutral, be dried 24h in drying baker, prepare finished product.
Chinese invention patent " a kind of high intensity, low ash pressed active carbon preparation method [P] " (number of patent application
201410787638.4) disclose the preparation method of " a kind of high intensity, low ash pressed active carbon ".Its concrete steps comprise:
The additional adhesive easily cracked is sent in kneader in proportion with powdered active carbon and is stirred mixing, obtain mixing charcoal
Powder；In solvent-borne type phenolic resin, add alcohol organic solvent by quality ratio requirement, obtain diluent；Powdered carbon will be mixed with dilute
Release liquid to send in proportion kneader carries out heated and stirred kneading, form compound；Uniform and with viscosity mixing will be mediated
Material molding extruder carries out extruding pelletization, it is thus achieved that particulate material；By solid for prepared particulate material stage drying at 90～160 DEG C
Change 1～3h, after anaerobic high-temperature heat treatment, then obtain pressed active carbon finished product.Preparation method of the present invention, has stream
Journey is short, energy consumption is low, and the feature that the pressed active carbon product intensity prepared is high, structural stability is good.Chinese invention patent is " a kind of
Water process biological activated carbon preparation technology flow process [P] " (number of patent application 201510741069.4) disclose one " water process
With biological activated carbon " preparation technology flow process.The disclosure technology includes following methods step, former water analysis, adds seed activity
Charcoal, screening microorganism, microorganism cultivation, by test run trace analysis and microorganism are safeguarded, the most formally coming into operation, the present invention ties
Close biodegradation and two processes of activated carbon adsorption, not only remove pollutant efficiency than simple biodegradation and simple activity charcoal
Absorption improves a lot, and is also greatly prolonged service life, environmental protection, activated carbon can play certain bio-regeneration and make
With.
In addition, document " activated carbon impact [J] on ternary battery capacitor chemical property " (Guangdong chemical industry, 2016,
43 (325): 82-83) report: activated carbon application in battery capacitor positive electrode.Document result of study shows: just
The increase of pole active substance charcoal incorporation, the capacity of Soft Roll monomer sample reduces, and high rate performance improves, cycle performance is steady
Fixed.Document " microbiological fuel cell MnO2And the preparation of activated carbon mixed catalyst and performance study thereof " (regenerative resource,
2016,34 (2): 311-316) report: prepare for microorganism interest concessions cell cathode by mechanical mixture and chemical mixing mode
MnO2Mixed catalyst with activated carbon conductive material.Document result of study shows: two kinds of mixed catalysts are all in mixing
Mass ratio is to have optimum performance during 1:1.Document " modification of lead carbon battery activated carbon and application " (battery, 2015,45 (4):
202-205) report: with plumbi nitras and citric acid as raw material, through being thermally treated resulting in technology and the application of modified activated carbon.Should
Document claims: the lead carbon battery manufactured with modified activated carbon and conventional lead acid battery ratio, its rapid charge characteristic, high magnification part lotus
Electricity state cycle performance all be improved significantly.Document " activated carbon optimizes biological-cathode and promotes biological fuel cell electricity generation performance "
(ACTA Scientiae Circumstantiae, 2015,35 (7): 2059-2063) reports: add activated carbon granule, strengthens biological fuel cell performance
Research.Its result of study shows: negative electrode adds activated carbon can improve rapidly fuel cell output voltage and power density.Literary composition
Offer " activated carbon and TiO2Mixed catalytic Ni substrate biological-cathode microbiological fuel cell performance study " (regenerative resource, 2015,
33 (4): 612-617) report: with Foamed Nickel as matrix, column type active carbon particles and TiO2Mixture of powders coated electrode
Performance.Its result of study shows: activated carbon and TiO2Dual chamber cathode type biological fuel cell is produced electricity by mixed coating nickel base electrode
Catalytic effect good.Document " preparation of activated carbon and the application in lead-acid battery thereof " (accumulator, 2015,52 (2): 95-
100) Reporting of Overview: during 2000-2014, part document is about the preparation method of activated carbon and answering in lead-acid battery thereof
With.Document " corn straw prepares the activated carbon research for lithium-sulfur cell " (Light Engineering Institutes Of Zhengzhou's journal (natural science edition),
2014,29 (5): 1-5) report: the method preparing activated carbon with corn straw.Specific practice is: take a certain amount of dry jade
Rice straw, the skin heart does not separates, and is crushed to 0.5cm once, standby after putting into 60 DEG C of air dry oven 2d.Weigh dry corn stalk
Stalk and ZnCl2Solution is than for 1:7, wherein ZnCl2The concentration of solution is 20%, puts in microwave oven, 900W's after soaking 24h
Process 7min under microwave power, take out sample, with the HCl pickling 8h of 20%, after wash with water to neutrality, put in vacuum drying oven
110 DEG C of dry 2h, grind and i.e. obtain activated carbon.Its lithium-sulfur cell applied research result shows: the circulation of sulfur absorbent charcoal composite material
Performance and specific capacity etc. all show well." heat treatment temperature supports SiO to activated carbon to documentxComposite is as lithium-ion electric
The impact of pond negative electricity chemical property " (China West Normal University's journal (natural science edition), 2014,35 (2): 178-184) report
: heat treatment temperature supports SiO to activated carbonxComposite is as the impact of lithium ion battery negative chemical property.It grinds
Study carefully result to show: the activated carbon being sent out synthesis by sol-gel process and heat treatment supports SiOxComposite, in heat treatment temperature
When being 900 DEG C, the chemical property of composite is best.First discharge specific capacity is 1228mAh/g, and coulombic efficiency is 53%.
After 200 circulations, reversible specific capacity is maintained at 389mAh/g.Document " research of Activated Carbon Modification microbiological fuel cell " (water
Treatment technology, 2014,40 (4): 16-18) Reporting of Overview: utilize Activated Carbon Modification charcoal cloth as microbiological fuel cell sun
Pole, and compare with the anode of multi-walled carbon nano-tubes modification and the charcoal cloth of unmodified.Its result of study shows: Activated Carbon Modification
Electrode has the most excellent chemical property.Document " storage of submarine fuel cell AIP hydrogen fuel activated carbon cryogenic absorption " is (too
Sun energy journal, 2011,32 (4): 583-588) Reporting of Overview: activated carbon is answering that submarine fuel cell AIP hydrogen fuel adsorbs
With.Its result of study shows: the mass density of activated carbon cryogenic absorption hydrogen storage system and storage H_2-producing properties can meet submarine FC-
The requirement of AIP system.Document " Direct Carbon Fuel Cells activated carbon prepared by Quercus acutissima Carr. sawdust " (solar energy journal, 2011,32 (3):
402-407) Reporting of Overview: with Quercus acutissima Carr. sawdust as raw material, the method preparing DCFC activated carbon.The concrete grammar of document report
Be: low ash Quercus acutissima Carr. sawdust is placed in tube furnace, 400 DEG C, nitrogen protection under carbonization, after 1h, natural cooling obtains carbonized material,
By carbonized material and K2CO3By certain alkali charcoal than mixing, add dipping 12h after a small amount of distilled water stirs, dry the most in an oven
Dry；The tube furnace of the mixture stream of nitrogen gas amount that is placed in 200mL/min dried activates, activation temperature be 800～
1000 DEG C, activate 60～180min, naturally cool to room temperature；Then become neutrality with distilled water cyclic washing to filtrate, dry.Its
Result of study shows: activated carbon has higher specific surface area and good porosity.
Comprehensive domestic and international existing about activated carbon, the preparation of NACF and the feature of application technology, it is therefore apparent that existing
With the presence of technology defect will be apparent below or deficiency:
First, the technology of existing synthesis LITHIUM BATTERY activated carbon, is the most all the most numerous and diverse, it is more difficult to realize industrialization
Produce and large-scale application.
Second, in the technology path of existing synthesizing activity charcoal, it is used mostly nitrogen as protective gas, to avoid charcoal by oxygen
Change；Obviously, the technology path of nitrogen protection necessarily substantially increase should the manufacture cost of material of very low cost activated carbon, with
Time too increase equipment and production technology cost.
3rd, due to the restriction of the manufacturing process technology of activated carbon, the application of activated carbon mainly in fuel cell field, urge
Change and water-treatment technology field.
4th, due to the restriction of existing manufacture LITHIUM BATTERY activated carbon technology so that activated carbon purity is low, structural instability and
The single grade of pattern is the most not enough so that prior art from the activated carbon made be difficult to meet battery plus-negative plate material, particularly lithium from
The basic demand of sub-cell negative electrode material, thus significantly limit the absorbent charcoal material extensive application in field of lithium ion battery.
Summary of the invention
In order to fundamentally solve the major limitation existing for existing manufacture LITHIUM BATTERY activated carbon and the phase of activated carbon application
Pass problem, it is an object of the invention to there are provided the preparation method of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material, with one
Utilize biomass raw material (specifically: rice hulls or Pericarppium arachidis hypogaeae or bamboo bar or walnut shell or Semen coryli heterophyllae (i.e. " Hawaii
Really ") shell or happy shell etc., hereinafter referred to as " plant material ") it is raw material, the technology of the preparation LITHIUM BATTERY activated carbon of more efficient.
Technique is simple, abundant raw materials, and the manufacturing cycle is short, and energy consumption is low, adds chemical property and the application practicality preparing material.
The intensive large-scale industrial being advantageously implemented absorbent charcoal material produces, and has good economic benefit, environmental benefit and good
Social benefit.
In order to realize above-mentioned purpose, the present invention by the following technical solutions:
The preparation method of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material, the steps include:
Plant material is washed by the first step, loads sealing in canister and (seals reservation one diameter and be about 2～5mm
Breeder tube, below omits), insert in Muffle furnace, 450～650 DEG C of heated at constant temperature 4～8 hours, naturally cool to room temperature (about 25
～28 DEG C, as follows, omit) and obtain black solid activated carbon；
The black solid activated carbon that the first step is obtained by second step and graphite mixing for 10:1～1:1 ratio in mass ratio
Compound is placed in ball grinder, the most respectively with (hydrochloric acid, sulphuric acid, aqueous acetic acid or water volume are to flood black solid thing in right amount
Matter is " in right amount ", below omits), concentration be 0.2～1.2M hydrochloric acid, sulphuric acid, acetum (be aqueous solution, as follows,
Slightly), water；Pellet mass ratio (gross mass of activated carbon and graphite mixture and the mass ratio of ball milling ball, as follows, slightly) it is equal to
Under the conditions of 1:10～1:20, difference ball milling 0.5～3 hours, i.e. " ball milling pickling ", " ball milling washing "；Sulphuric acid, hydrochloric acid, acetic acid are molten
Liquid respectively each ball milling acid elution 3～5 times, the value of ball milling water washing to eluate pH is about 6.8-7.2；
3rd step by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 45～85 DEG C dry 4～8 hours
I.e. obtain a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material.
The preparation method of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material, it is simply that be prepared from according to as above step.
In order to the present invention is better achieved, described plant material be respectively rice hulls or Pericarppium arachidis hypogaeae or bamboo bar or
One of which in walnut shell, happy shell or hazelnut shell.
In order to the present invention is better achieved, the water described in the first step, second step is deionized water or pure water or distilled water
Or the one of which in redistilled water.
By prepared LITHIUM BATTERY graphite/absorbent charcoal composite material according to the manufacturing process system of general lithium ion cell electrode
Become the cathode pole piece of lithium ion battery, be combined into lithium ion battery, limit voltage in 1～20C charge-discharge magnification, charging be
4.2V, under the conditions of discharge cut-off voltage is 2.8V discharge and recharge, battery is carried out charge-discharge performance test.
The present invention compared with prior art, has the advantage that and beneficial effect:
1, a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material prepared by presently disclosed techniques, owing to particle diameter is distributed more widely,
Porosity is high, specific surface area big (referring to: Figure of description, hereinafter referred to as " figure x "), as lithium ion battery negative activity material
Material, has good Lithium-ion embeding and abjection amount, is manufactured into lithium ion battery and has higher charge/discharge capacity, fills for the first time
The highest specific discharge capacity of discharge cycles is all more than 500mAh/g (referring to each embodiment of description, each figure, table 1).
2, a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material prepared by presently disclosed techniques, owing to have employed multiple acid
Ball milling washing process (refers to the concrete preparation process of description) so that a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of preparation
Inorganic salt impurities content is relatively low, and the lithium ion battery negative of manufacture has excellent electrochemistry cycle performance and good high magnification
Charge-discharge performance.Under 1C, 5C and 20C charge-discharge mechanism, high charge-discharge circulation specific discharge capacity be respectively as follows: 519.5,
517.6 and 455mAh/g (referring to description table 1, embodiment 5, embodiment 6), respectively 1.35 times (1C) of comparative example 7
With 1.61 times (referring to: table 1)；1.81 times (5C) and 1.95 times (20C) for comparative example 8；Under 1C charge-discharge mechanism the 300th
Secondary cyclic discharge capacity conservation rate meansigma methods is 95.9%, is up to 99.0%；600th cyclic discharge capacity conservation rate
Average out to 89%, up to 92.6% (referring to description table 1 and each embodiment)；250th circulation under 5C charge-discharge mechanism
Discharge capacitance meansigma methods is 95.6%, is up to 96.8%；500th cyclic discharge capacity conservation rate average out to
91%, up to 95.6% (referring to description table 1 and each embodiment)；Under 20C charge-discharge mechanism, the 200th circulation electric discharge is held
Amount conservation rate meansigma methods is 95.6%, is up to 97.3%；300th cyclic discharge capacity conservation rate average out to
90.9%, up to 94.1% (referring to description table 1 and each embodiment).
3, a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material prepared by presently disclosed techniques, not only particle diameter is distributed in 0.1
～15 μ m (referring to: each embodiment of description and Figure of description), it is easy to electrode production process increases active substance
Compactedness, increases the available capacity of electrode plates, can make full use of the adsorptivity of activated carbon simultaneously, substantially increase electrode
Absorption to electrolyte so that the lithium ion battery of manufacture is prone to activation, and the lithium ion battery significantly reducing manufacture is filling
Polarization resistance during discharge cycles, substantially increases lithium ion battery current efficiency during charge and discharge cycles, increases
High power charging-discharging efficiency and charge and discharge circulation electrical stability energy (referring to: embodiment 3, table 1, Fig. 9) of lithium ion battery are added.
4, a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material prepared by presently disclosed techniques, processing step is simple, equipment
Uncomplicated, raw material is easy to get, pollution-free, by-product is easily recycled that (scrub raffinate main chemical compositions is the chlorine of solubility
Compound, sulfate and acetate, it is easy to recycle or produce waste water and be prone to harmless treatment), and need not noble gas guarantor
Protect or vacuum technique, significantly reduce technical costs and the equipment cost preparing material, it is easy to accomplish large-scale production and wide
General application.
5, prepared by presently disclosed techniques, and owing to the raw material used is plant refuse, thus preparation cost is relatively low,
It is particularly well-suited to manufacture lithium-ion-power cell, and can be applicable to the both positive and negative polarity additive as other type chemical battery, tool
There are good application prospect and preferable economic benefit and society and environmental benefit.
Accompanying drawing explanation
Fig. 1 is the SEM photograph (10K times) of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 1 preparation.
Fig. 2 is the grain size distribution of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 1 preparation.
Fig. 3 is the XRD figure of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 1 preparation.
Fig. 4 is the SEM photograph (10K times) of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 2 preparation.
Fig. 5 is the XRD figure of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 2 preparation.
Fig. 6 is the SEM photograph (10K times) of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 3 preparation.
Fig. 7 is the grain size distribution of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 3 preparation.
Fig. 8 is the XRD figure of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 3 preparation.
Fig. 9 is a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material charge/discharge capacity of embodiment 3 preparation.
Figure 10 is the SEM photograph (10K times) of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 4 preparation.
Figure 11 is the XRD figure of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 4 preparation.
Figure 12 is the SEM photograph (10K times) of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 5 preparation.
Figure 13 is the XRD figure of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 5 preparation.
Figure 14 is the SEM photograph (10K times) of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 6 preparation.
Figure 15 is the grain size distribution of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 6 preparation.
Figure 16 is the XRD figure of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material of embodiment 6 preparation.
Detailed description of the invention
Embodiment 1:
A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material, its step and process conditions are:
Rice hulls distilled water water is cleaned by the first step, loads in canister and seals, inserts in Muffle furnace, 450 DEG C of constant temperature
Heat 4 hours, naturally cool to room temperature, i.e. obtain black solid activated carbon；
The black solid activated carbon that the first step is obtained by second step and graphite are that the mixture of 10:1 ratio is put in mass ratio
In ball grinder, it is the hydrochloric acid of 0.2M, sulphuric acid, acetum, distilled water by appropriate, concentration the most respectively；Pellet quality
Than under the conditions of equal to 1:10, ball milling 3,2,1,0.5 hour respectively, i.e. ball milling acid elution 3 or 4 or 5 times, ball milling water washs to washing out
The value of liquid pH is about 6.8 or 6.9 or 7 or 7.1 or 7.2；
3rd step by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 45 DEG C of drying within 8 hours, i.e. obtain
A kind of LITHIUM BATTERY graphite/absorbent charcoal composite material.
With SEM and laser particle size analysis, the pattern of the graphite/absorbent charcoal composite material prepared by observation and particle diameter；Use XRD
The X-ray diffraction feature of test graphite/absorbent charcoal composite material；And by prepared LITHIUM BATTERY graphite/absorbent charcoal composite material
Make the cathode pole piece of lithium ion battery according to the manufacturing process of general lithium ion cell electrode, be combined into lithium ion battery,
1C, 5C charge-discharge magnification, charging limit voltage and are 4.2V, under the conditions of discharge cut-off voltage is 2.8V discharge and recharge, carry out battery
Charge-discharge performance is tested.SEM and laser particle size analysis test result show: the graphite/absorbent charcoal composite material of preparation is not for advise
Polymorph then, particle diameter (refers to: Fig. 1, Fig. 2) between 0.5～2.5 μm；XRD result proves: the graphite/activated carbon of preparation is multiple
Condensation material is graphite and graphite oxide mixed crystal (referring to: Fig. 3)；Graphite/the absorbent charcoal composite material of preparation is negative electrode active
The lithium ion battery of material manufacture initial discharge specific capacity under the conditions of 1C rate charge-discharge is 412.5mAh/g, the highest electric discharge
Specific capacity is 456.8mAh/g；300 charge and discharge cycles specific discharge capacities are up to 452.3mAh/g, capability retention (with
High specific discharge capacity compares) it is 99.01%；600 times the highest specific discharge capacity of charge and discharge cycles is 399.7mAh/g, and capacity keeps
Rate is 87.5%；Under the conditions of 5C rate charge-discharge, first discharge specific capacity is 398.1mAh/g, and the highest specific discharge capacity reaches
419.9mAh/g；250 times the highest specific discharge capacity of charge and discharge cycles is 405.6mAh/g, and capability retention is 96.6%；500 times
The highest specific discharge capacity of charge and discharge cycles is 376.9mAh/g, and capability retention is 89.8% (referring to: table 1).
Embodiment 2:
A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material, its step and process conditions are:
Pericarppium arachidis hypogaeae redistilled water water is cleaned by the first step, loads in canister and seals, inserts in Muffle furnace, 550 DEG C
Heated at constant temperature 6 hours, naturally cools to room temperature, i.e. obtains black solid activated carbon；
The black solid activated carbon that the first step is obtained by second step and graphite are that the mixture of 8:1 ratio is put in mass ratio
In ball grinder, it is the hydrochloric acid of 0.4M, sulphuric acid, acetum, redistilled water by appropriate, concentration the most respectively；Pellet
Under the conditions of mass ratio is equal to 1:15, ball milling 2,1,0.5,3 hours, i.e. " ball milling pickling ", " ball milling washing " respectively；Sulphuric acid, hydrochloric acid,
Acetic acid respectively each ball milling acid elution 3 or 4 or 5 times, the value of ball milling water washing to eluate pH be about 6.8 6.9 or 7 or 7.1 or
7.2；
3rd step by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 55 DEG C of drying within 7 hours, i.e. obtain
A kind of LITHIUM BATTERY graphite/absorbent charcoal composite material.
With pattern and the particle diameter of the graphite/absorbent charcoal composite material prepared by SEM observation；Graphite/activated carbon is tested with XRD
The X-ray diffraction feature of composite；And by prepared LITHIUM BATTERY graphite/absorbent charcoal composite material according to general lithium ion
The manufacturing process of battery electrode makes the cathode pole piece of lithium ion battery, is combined into lithium ion battery, in 5C, 20C discharge and recharge times
Rate, charging limit voltage and are 4.2V, under the conditions of discharge cut-off voltage is 2.8V discharge and recharge, battery are carried out charge-discharge performance survey
Examination.SEM test result shows: the graphite/absorbent charcoal composite material of preparation is irregular polymorph, and particle diameter is in 0.5～10 μm
Between (referring to: Fig. 4)；XRD result proves: the graphite/absorbent charcoal composite material of preparation is graphite and graphite oxide mixed crystal
(referring to: Fig. 5)；The lithium ion battery that graphite/absorbent charcoal composite material is negative electrode active material manufacture of preparation fills in 5C multiplying power
Initial discharge specific capacity under discharging condition is 366.1mAh/g, and the highest specific discharge capacity is 439.3mAh/g；250 discharge and recharges
Circulation specific discharge capacity is up to 421.9mAh/g, and capability retention (comparing with the highest specific discharge capacity) is 96%；Fill for 500 times
The highest specific discharge capacity of discharge cycles still reaches 402.2mAh/g, and capability retention is 91.6%；20C rate charge-discharge condition
Under, first discharge specific capacity is 358.3mAh/g, and the highest specific discharge capacity reaches 418.4mAh/g；200 times charge and discharge cycles is put
Electricity specific capacity is up to 407.1mAh/g, and capability retention (comparing with the highest specific discharge capacity) is 97.3%；300 discharge and recharges
Circulating the highest specific discharge capacity is 390.5mAh/g, and capability retention is 88.9% (referring to: table 1).
Embodiment 3:
A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material, its step and process conditions are:
Bamboo rod is washed with deionized water only by the first step, loads in canister and seals, inserts in Muffle furnace, 650 DEG C of perseverances
Temperature heating 4 hours, naturally cools to room temperature, i.e. obtains black solid activated carbon；
The black solid activated carbon that the first step is obtained by second step and graphite are that the mixture of 6:1 ratio is put in mass ratio
In ball grinder, it is the hydrochloric acid of 0.6M, sulphuric acid, acetum, deionized water by appropriate, concentration the most respectively；Pellet matter
Under the conditions of amount ratio is equal to 1:20, ball milling 1,0.5,3,2 hours, i.e. " ball milling pickling ", " ball milling washing " respectively；Sulphuric acid, hydrochloric acid, vinegar
Acid solution each ball milling respectively washs 3 or 4 or 5 times, and the value of ball milling water washing to eluate pH is about 7；
3rd step by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 65 DEG C of drying within 6 hours, i.e. obtain
A kind of LITHIUM BATTERY graphite/absorbent charcoal composite material.
Pattern and the particle diameter of graphite/absorbent charcoal composite material prepared by institute's test is observed with SEM and laser particle size analyzer；
The X-ray diffraction feature of graphite/absorbent charcoal composite material is tested with XRD；And by multiple for prepared LITHIUM BATTERY graphite/activated carbon
Condensation material makes the cathode pole piece of lithium ion battery according to the manufacturing process of general lithium ion cell electrode, is combined into lithium-ion electric
Pond, 1C, 5C, 20C charge-discharge magnification, charging limit voltage be 4.2V, under the conditions of discharge cut-off voltage is 2.8V discharge and recharge, right
Battery carries out charge-discharge performance test.SEM and laser particle size analysis test result show: the graphite of preparation/activated carbon composite wood
Material is irregular polymorph, and particle diameter (refers to: Fig. 6, Fig. 7) between 0.1～15 μm；XRD result proves: the graphite of preparation/
Absorbent charcoal composite material is graphite and graphite oxide mixed crystal (referring to: Fig. 8)；Graphite/the absorbent charcoal composite material of preparation is
The lithium ion battery of negative electrode active material manufacture initial discharge specific capacity under the conditions of 1C rate charge-discharge is 432.6mAh/g,
The highest specific discharge capacity is 488.4mAh/g；300 charge and discharge cycles specific discharge capacities are up to 461.8mAh/g, and capacity keeps
Rate (comparing with the highest specific discharge capacity) is 94.6%；600 times the highest specific discharge capacity of charge and discharge cycles is 452.2mAh/g, holds
Amount conservation rate is 92.6%；Under the conditions of 5C rate charge-discharge, first discharge specific capacity is 422.6mAh/g, the highest specific discharge capacity
Reach 459.7mAh/g；250 charge and discharge cycles specific discharge capacities are up to 427.9mAh/g, and capability retention (is put with the highest
Electricity specific capacity compares) it is 93.1%；500 times the highest specific discharge capacity of charge and discharge cycles is 411.1mAh/g, and capability retention is
89.4% (referring to: table 1)；1C discharge and recharge 200 times charge and discharge cycles capability retention army more than 96%, 5C charge and discharge cycles capacity
Conservation rate is all more than 95%；The 600th circulation volume conservation rate of 20C discharge and recharge is more than 86% (referring to: Fig. 9).
Embodiment 4:
The preparation method of a kind of LITHIUM BATTERY graphite/absorbent charcoal composite material, the steps include:
Walnut shell material pure water is cleaned by the first step, loads in canister and seals, inserts in Muffle furnace, and 550 DEG C of constant temperature add
Heat 4 or 5 or 7 or 8 hours, naturally cools to room temperature, i.e. obtains black solid activated carbon；
The black solid activated carbon that the first step is obtained by second step and graphite are that the mixture of 4:1 ratio is put in mass ratio
In ball grinder, it is the hydrochloric acid of 0.8M, sulphuric acid, acetum, deionized water by appropriate, concentration the most respectively；Pellet matter
Measure under the conditions of being equal to 1:10 than (quality of activated carbon and graphite and the mass ratio of ball), respectively ball milling 0.5,3,1,2 hours, i.e.
" ball milling pickling ", " ball milling washing "；Sulphuric acid, hydrochloric acid, acetum each ball milling respectively washs 3 or 4 or 5 times, and ball milling water washs extremely
The value of eluate pH is about 7；
3rd step by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 75 DEG C of drying within 5 hours, i.e. obtain
A kind of LITHIUM BATTERY graphite/absorbent charcoal composite material.
With pattern and the particle diameter of the graphite/absorbent charcoal composite material prepared by SEM observation；Graphite/activated carbon is tested with XRD
The X-ray diffraction feature of composite；And by prepared LITHIUM BATTERY graphite/absorbent charcoal composite material according to general lithium ion
The manufacturing process of battery electrode makes the cathode pole piece of lithium ion battery, is combined into lithium ion battery, in 5C, 20C discharge and recharge times
Rate, charging limit voltage and are 4.2V, under the conditions of discharge cut-off voltage is 2.8V discharge and recharge, battery are carried out charge-discharge performance survey
Examination.SEM test result shows: the graphite/absorbent charcoal composite material of preparation is irregular polymorph, and particle diameter is in 0.1～10 μm
Between (referring to: Figure 10)；XRD result proves: the graphite/absorbent charcoal composite material of preparation is graphite and graphite oxide mixed crystal
(referring to: Figure 11)；The lithium ion battery that graphite/absorbent charcoal composite material is negative electrode active material manufacture of preparation fills in 5C multiplying power
Initial discharge specific capacity under discharging condition is 389.5mAh/g, and the highest specific discharge capacity is 425.3mAh/g；250 discharge and recharges
Circulation specific discharge capacity is up to 411.5mAh/g, and capability retention (comparing with the highest specific discharge capacity) is 96.8%；500 times
The highest specific discharge capacity of charge and discharge cycles is 406.7mAh/g, and capability retention is 95.6%；Under the conditions of 20C rate charge-discharge,
First discharge specific capacity is 372.3mAh/g, and the highest specific discharge capacity reaches 402.1mAh/g；200 charge and discharge cycles electric discharge ratios
Capacity is up to 390.9mAh/g, and capability retention (comparing with the highest specific discharge capacity) is 97.2%；300 charge and discharge cycles
The highest specific discharge capacity is 378.2mAh/g, and capability retention is 94.1% (referring to: table 1).
Embodiment 5:
A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material, its step and process conditions are:
Hawaii shell is washed by the first step, loads in canister and seals, inserts in Muffle furnace, and 650 DEG C of constant temperature add
Heat 8 hours, naturally cools to room temperature, i.e. obtains black solid activated carbon；
The black solid activated carbon that the first step is obtained by second step and graphite are that the mixture of 2:1 ratio is put in mass ratio
In ball grinder, being separately added into appropriate, concentration successively is the hydrochloric acid of 1.0M, sulphuric acid, acetum, distilled water；Pellet quality
Under the conditions of being equal to 1:15 than (quality of activated carbon and graphite and the mass ratio of ball), ball milling 0.5,1,2,3 hours, i.e. " ball respectively
Mill pickling ", " ball milling washing "；Sulphuric acid, hydrochloric acid, acetic acid each ball milling respectively washs 3 or 4 or 5 times, and ball milling water washs to eluate pH
Value be about 7；
3rd step by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 85 DEG C of drying within 4 hours, i.e. obtain
A kind of LITHIUM BATTERY graphite/absorbent charcoal composite material.
With pattern and the particle diameter of the graphite/absorbent charcoal composite material prepared by SEM observation；Graphite/activated carbon is tested with XRD
The X-ray diffraction feature of composite；And by prepared LITHIUM BATTERY graphite/absorbent charcoal composite material according to general lithium ion
The manufacturing process of battery electrode makes the cathode pole piece of lithium ion battery, is combined into lithium ion battery, in 1C, 5C discharge and recharge times
Rate, charging limit voltage and are 4.2V, under the conditions of discharge cut-off voltage is 2.8V discharge and recharge, battery are carried out charge-discharge performance survey
Examination.SEM test result shows: the graphite/absorbent charcoal composite material of preparation is irregular polymorph, and particle diameter is in 0.5～10 μm
Between (referring to: Figure 12)；XRD result proves: the graphite/absorbent charcoal composite material of preparation is graphite and graphite oxide mixed crystal
(referring to: Figure 13)；The lithium ion battery that graphite/absorbent charcoal composite material is negative electrode active material manufacture of preparation fills in 1C multiplying power
Initial discharge specific capacity under discharging condition is 434.2mAh/g, and the highest specific discharge capacity is 519.5mAh/g；300 discharge and recharges
Circulation specific discharge capacity is up to 488.3mAh/g, and capability retention (comparing with the highest specific discharge capacity) is 94%；Fill for 600 times
The highest specific discharge capacity of discharge cycles is 451.7mAh/g, and capability retention is 86.9%；Under the conditions of 5C rate charge-discharge, first
Specific discharge capacity is 423.5mAh/g, and the highest specific discharge capacity reaches 499.6mAh/g；200 charge and discharge cycles specific discharge capacities
Being up to 481.4mAh/g, capability retention (comparing with the highest specific discharge capacity) is 96.3%；300 times charge and discharge cycles is the highest
Specific discharge capacity is 450.5mAh/g, and capability retention is 90.1%；(referring to: table 1).
Embodiment 6:
A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material, its step and process conditions are:
Happy shell is washed by the first step, loads in canister and seals, inserts in Muffle furnace, 650 DEG C of heated at constant temperature
4 hours, naturally cool to room temperature, i.e. obtain black solid activated carbon；
The black solid activated carbon that the first step is obtained by second step and graphite are that the mixture of 1:1 ratio is put in mass ratio
In ball grinder, be separately added into successively appropriate (hydrochloric acid, sulphuric acid, acetic acid or water volume to flood black solid material for " in right amount ",
Hereinafter omit), concentration be the hydrochloric acid of 1.2M, sulphuric acid, acetum, distilled water；Pellet mass ratio (activated carbon and the quality of graphite
Mass ratio with ball) equal under the conditions of 1:10～1:20, ball milling 0.5～3 hours respectively, i.e. " ball milling pickling ", " ball milling washing "；
The most each ball milling of sulphuric acid, hydrochloric acid, acetic acid washs 3 or 4 or 5 times, and the value of ball milling water washing to eluate pH is about 7；
3rd step by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 65 DEG C of drying within 8 hours, i.e. obtain
A kind of LITHIUM BATTERY graphite/absorbent charcoal composite material.
With pattern and the particle diameter of the graphite/absorbent charcoal composite material prepared by SEM observation；Graphite/activated carbon is tested with XRD
The X-ray diffraction feature of composite；And by prepared LITHIUM BATTERY graphite/absorbent charcoal composite material according to general lithium ion
The manufacturing process of battery electrode makes the cathode pole piece of lithium ion battery, is combined into lithium ion battery, in 5C, 20C discharge and recharge times
Rate, charging limit voltage and are 4.2V, under the conditions of discharge cut-off voltage is 2.8V discharge and recharge, battery are carried out charge-discharge performance survey
Examination.SEM test result shows: the graphite/absorbent charcoal composite material of preparation is irregular polymorph, and particle diameter is in 0.1～15 μm
Between (referring to: Figure 14, Figure 15)；XRD result proves: the graphite/absorbent charcoal composite material of preparation is that graphite and graphite oxide mix
Synthetic body (refers to: Figure 16)；Graphite/the absorbent charcoal composite material of preparation is that the lithium ion battery of negative electrode active material manufacture is at 5C
Initial discharge specific capacity under the conditions of rate charge-discharge is 462.9mAh/g, and the highest specific discharge capacity is 517.6mAh/g；250 times
Charge and discharge cycles specific discharge capacity is up to 491.7mAh/g, and capability retention (comparing with the highest specific discharge capacity) is 95%；
500 times the highest specific discharge capacity of charge and discharge cycles still reaches 463.3mAh/g, and capability retention is 91.77%；500 charge and discharges
It is 399.7mAh/g that electricity circulates the highest specific discharge capacity, and capability retention is 89.5%；Under the conditions of 20C rate charge-discharge, first
Specific discharge capacity is 431mAh/g, and the highest specific discharge capacity reaches 455mAh/g；200 the highest specific discharge capacities of charge and discharge cycles
Still reaching 420mAh/g, capability retention is 92.3%；300 times the highest specific discharge capacity of charge and discharge cycles is 408.9mAh/
G, capability retention is 89.9% (referring to: table 1).
Embodiment 7:
A kind of preparation method of LITHIUM BATTERY graphite/absorbent charcoal composite material, its step and process conditions are:
The first step, by commercial battery level graphite, loads in canister and seals, insert in Muffle furnace, 550 DEG C of heated at constant temperature 6
Hour, naturally cool to room temperature, i.e. obtain black solid material；
The black solid material that the first step is obtained by second step and mass ratio be the graphite of 5:1 in ball grinder, divide successively
Not with the hydrochloric acid of appropriate 0.6M, sulphuric acid, acetic acid, distilled water；Under the conditions of ratio of grinding media to material is equal to 1:15, ball milling 0.5,1,2,3 hours, i.e.
" pickling ", " washing "；The most each ball milling of sulphuric acid, hydrochloric acid, acetum washs 3～5 times, and water for ball milling is washed to eluate pH
Value approximates 7；
3rd step by washed graphite comparative sample sucking filtration, under atmospheric environment 75 DEG C of drying within 6 hours, i.e. obtain a kind of battery
Level graphite/modified graphite material.
The contrast material of preparation is that the lithium ion battery of negative electrode active material manufacture is at the beginning of under the conditions of 1C rate charge-discharge
Beginning specific discharge capacity is 355.5mAh/g, and the highest specific discharge capacity is 386.2mAh/g；300 charge and discharge cycles specific discharge capacities
Being up to 365.6mAh/g, capability retention (comparing with the highest specific discharge capacity) is 92.3%；600 times charge and discharge cycles is the highest
Specific discharge capacity is 302.7mAh/g, and capability retention is 78.4%；Under the conditions of 5C rate charge-discharge, first discharge specific capacity is
298.6mAh/g, the highest specific discharge capacity is 312.1mAh/g, and 250 times charge and discharge cycles specific discharge capacity is up to
261.1mAh/g, capability retention (comparing with the highest specific discharge capacity) is 83.6%；500 charge and discharge cycles the highest electric discharge ratios
Capacity still reaches 240.8mAh/g, and capability retention is 77.2% (referring to: table 1).
Embodiment 8:
Directly make lithium ion battery with commercial graphite negative material according to the manufacturing process of general lithium ion cell electrode
Cathode pole piece, be combined into lithium ion battery, 5C, 20C charge-discharge magnification, charging limit voltage be 4.2V, electric discharge cut-off electricity
Under the conditions of pressure is for 2.8V discharge and recharge, battery is carried out charge-discharge performance test.Commercial graphite material is negative electrode active material manufacture
Lithium ion battery initial discharge specific capacity under the conditions of 5C rate charge-discharge be 248.2mAh/g, the highest specific discharge capacity is
286.6mAh/g；300 charge and discharge cycles specific discharge capacities are up to 235.3mAh/g, and capability retention is (with the highest electric discharge ratio
Capacity Ratio is relatively) it is 82.1%；600 times the highest specific discharge capacity of charge and discharge cycles is 214.2mAh/g, and capability retention is
74.4%；Under the conditions of 20C rate charge-discharge, first discharge specific capacity is 208.5mAh/g, and the highest specific discharge capacity is
233.9mAh/g, 250 charge and discharge cycles specific discharge capacities are up to 185.4mAh/g, and capability retention is (with the highest electric discharge ratio
Capacity Ratio is relatively) it is 79.3%；300 times the highest specific discharge capacity of charge and discharge cycles is only 176.4mAh/g, and capability retention is
75.4% (referring to: table 1).
Composite charge-discharge performance test result (unit: mAh/g) prepared by table 1 present invention
Indicate: the highest specific discharge capacity of *；% cyclic discharge capacity conservation rate.
Claims (1)
1. a preparation method for LITHIUM BATTERY graphite/absorbent charcoal composite material, the steps include:
A, plant material is washed, load in canister and seal, insert in Muffle furnace, 450～650 DEG C of heated at constant temperature 4～8
Hour, naturally cool to 25～28 DEG C and obtain black solid activated carbon；
B, the black solid activated carbon that the first step is obtained and mass ratio be the graphite of 3:1～1:1 in ball grinder, distinguish successively
Add hydrochloric acid, 0.1～0.5M sulphuric acid, 0.5～1.2M acetic acid, water that concentration is 0.2～1.0M；Ratio of grinding media to material is equal to 1:10～1:20
Under the conditions of, ball milling 0.5～2 hours, pickling, washing；The most each ball milling of sulphuric acid, hydrochloric acid, acetic acid washs 3～5 times, and water polo is worn away
The value washed to eluate pH is 6.8-7.2；
C, by washed graphite/Mixture of Activated Carbon sucking filtration, under atmospheric environment 45～85 DEG C dry 4～8 hours, obtain
A kind of LITHIUM BATTERY graphite/absorbent charcoal composite material；
Described plant material be respectively in rice hulls or Pericarppium arachidis hypogaeae or bamboo bar or walnut shell or hazelnut shell wherein one
Kind；
Described water is the one of which in distilled water or pure water or deionized water.
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