CN103794795A - Boron doped graphene composite electrode material and preparation method thereof, and lithium ion battery and preparation method thereof - Google Patents
Boron doped graphene composite electrode material and preparation method thereof, and lithium ion battery and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 147
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 117
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000007772 electrode material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 51
- 239000010439 graphite Substances 0.000 claims abstract description 51
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 40
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 66
- 229910052744 lithium Inorganic materials 0.000 claims description 66
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 48
- 229910019142 PO4 Inorganic materials 0.000 claims description 48
- 239000010452 phosphate Substances 0.000 claims description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 19
- 230000004888 barrier function Effects 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000011883 electrode binding agent Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 13
- 238000001914 filtration Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 abstract 3
- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000004758 underpotential deposition Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000012286 potassium permanganate Substances 0.000 description 7
- 229960002163 hydrogen peroxide Drugs 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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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- 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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
A boron doped graphene composite electrode materials includes boron doped graphene, lithium hexafluorophosphate and N-methyl pyrrolidone; and the boron doped graphene and lithium hexafluorophosphate are dispersed in N-methyl pyrrolidone. The preparation method is as below: oxidizing graphite to obtain graphite oxide; dispersing graphite oxide in deionized water, conducting ultrasound treatment for 2-4 h, filtering and drying to obtain graphene oxide; mixing the graphene oxide with boron trioxide, placing the mixture in an inert gas atmosphere, heating to 800-1300 DEG C, insulating for 0.5-2 h, cooling to room temperature to obtain a mixture, removing residual boron trioxide, washing and drying to obtain boron doped graphene; and placing boron doped graphene and lithium hexafluorophosphate in N-methyl pyrrolidone, conducting ultrasonic treatment, and then stirring in vacuum to obtain the boron doped graphene composite electrode material, which is not easy to agglomerate and has high energy storage capacity. The invention also provides a lithium ion battery using the boron doped graphene composite electrode material and a preparation method thereof.
Description
Technical field
The present invention relates to graphene combination electrode material field, particularly relate to boron doped graphene combination electrode material and preparation method thereof and use lithium ion battery of this boron doped graphene combination electrode material and preparation method thereof.
Background technology
Nineteen nineties, material with carbon element has promoted greatly developing of ultracapacitor, lithium ion battery as the use of energy storage material.And Graphene is as a kind of new carbon, since within 2004, being found, due to its two-dimentional monolayer structure and excellent physical property, as high theoretical specific area, excellent mechanical strength, good pliability and high conductivity etc., bring dramatic change to the material in the fields such as the energy.
Graphene is very easy to derivatization, and its derivative is also subject to researcher's extensive concern, and Graphene derivative mainly contains nitrogen-doped graphene and boron doped graphene at present.Wherein boron doped graphene, due to the outer few electronics of boron atom ratio carbon atom, is the doping of P-type, compares Graphene and has better energy-storage property.The boron content of boron doped graphene is higher, and energy-storage property is better, and the current potential of underpotential deposition lithium is higher, more than 1V vsLi/Li+, can not form SEI film, and therefore boron doped graphene is a kind of material of desirable underpotential deposition lithium.But this material is easily reunited, cause the site of its underpotential deposition not make full use of, and also poor with the wettability of electrolyte, the stored energy capacitance obtaining is not high.
Summary of the invention
Based on this, be necessary to provide boron doped graphene combination electrode material that a kind of difficult reunion and stored energy capacitance are higher and preparation method thereof and used lithium ion battery of boron doped graphene combination electrode material and preparation method thereof.
A preparation method for boron doped graphene combination electrode material, comprises boron doped graphene, lithium hexafluoro phosphate and 1-METHYLPYRROLIDONE; Described boron doped graphene and described lithium hexafluoro phosphate are dispersed in described 1-METHYLPYRROLIDONE.
In an embodiment, the mass ratio of described boron doped graphene and described lithium hexafluoro phosphate is 2:1 ~ 25:1 therein, and the mass ratio of described 1-METHYLPYRROLIDONE and described lithium hexafluoro phosphate is 500:1 ~ 5000:1.
A preparation method for boron doped graphene combination electrode material, comprising:
Graphite is oxidized, obtains graphite oxide;
Described graphite oxide is dispersed in deionized water, ultrasonic 2 hours ~ 4 hours, filter, dry, obtain graphene oxide;
Described graphene oxide is mixed under the atmosphere that is placed on inert gas with diboron trioxide, be warming up to 800 ° of C ~ 1300 ° C and be incubated 0.5 hour ~ after 2 hours, be cooled to room temperature, obtain mixture, remove residual diboron trioxide, washing, dry, obtain boron doped graphene; And
Described boron doped graphene and described lithium hexafluoro phosphate are placed in to 1-METHYLPYRROLIDONE ultrasonic processing, then under vacuum, stir, obtain boron doped graphene combination electrode material.
In an embodiment, the mass ratio of described boron doped graphene and described lithium hexafluoro phosphate is 2:1 ~ 25:1 therein, and the mass ratio of described 1-METHYLPYRROLIDONE and described lithium hexafluoro phosphate is 500:1 ~ 5000:1.
In an embodiment, the mass ratio of described graphite oxide and diboron trioxide is 0.5:1 ~ 4:1 therein.
Therein in an embodiment, described in remove residual diboron trioxide step be that sodium hydroxide solution that described mixture is placed in to 3mol/L stirs after 2 hours ~ 4 hours and filters.
A kind of lithium ion battery, comprise battery container and be housed in electrode slice in described battery container, to electrode, barrier film and electrolyte;
Described electrode slice comprises boron doped graphene combination electrode material claimed in claim 1;
Described is lithium sheet to electrode;
Described electrode, barrier film and electrode slice are cascading.
A preparation method for lithium ion battery, comprising:
Described boron doped graphene combination electrode material, binding agent and conductive agent are mixed, obtain slurry;
Described slurry is coated on Copper Foil, and drying, slicing treatment make electrode slice;
Provide lithium sheet as to electrode;
Stack gradually assembling according to the described order to electrode, barrier film and described electrode slice and obtain battery core; And
At described battery core outer cladding battery container, and inject electrolyte in described battery container, after sealing, obtain lithium ion battery.
Therein in an embodiment, the mass ratio 85:5:10 of described boron doped graphene combination electrode material, binding agent and conductive agent; Described binding agent is made up of carboxymethyl cellulose and butadiene-styrene rubber, and described conductive agent is acetylene black.
In an embodiment, described electrolyte is lithium hexafluoro phosphate/propene carbonate (LiPF therein
6/ PC).
Above-mentioned boron doped graphene combination electrode material and preparation method thereof with used in lithium ion battery of boron doped graphene combination electrode material and preparation method thereof, boron doped graphene is mixed in 1-METHYLPYRROLIDONE with lithium hexafluoro phosphate, obtain boron doped graphene combination electrode material.Due to boron doped graphene and lithium hexafluoro phosphate, the dispersiveness in 1-METHYLPYRROLIDONE is all very good, and lamella and the sheet interlayer of lithium hexafluoro phosphate in boron doped graphene, can prevent the reunion of sheet interlayer.And in this composite material, contain lithium hexafluoro phosphate, electrolyte is also lithium hexafluoro phosphate, so electrolyte is better to the wettability of composite material.Therefore the site of the underpotential deposition of boron doped graphene combination electrode material can make full use of, thereby effectively improves the energy storage site of boron doped graphene.This material shows excellent energy-storage property while being used as lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the boron doped graphene combination electrode material of an execution mode flow chart;
Fig. 2 is the preparation method's of the lithium ion battery of an execution mode flow chart.
Embodiment
Below in conjunction with execution mode and accompanying drawing, the preparation method to boron doped graphene combination electrode material and the preparation method of lithium ion battery are described in further detail.
The boron doped graphene combination electrode material of one execution mode, comprises boron doped graphene and lithium hexafluoro phosphate; Boron doped graphene and lithium hexafluoro phosphate are dispersed in 1-METHYLPYRROLIDONE.
In this enforcement, the mass ratio of boron doped graphene and lithium hexafluoro phosphate can be 2:1 ~ 25:1.The mass ratio of 1-METHYLPYRROLIDONE and lithium hexafluoro phosphate can be 500:1 ~ 5000:1.
Above-mentioned boron doped graphene and lithium hexafluoro phosphate are dispersed in and in 1-METHYLPYRROLIDONE, form boron doped graphene combination electrode material, overcome the shortcoming that boron doped graphene lamella is easily reunited, the site of its underpotential deposition can be made full use of, thus the energy storage site of effectively improving boron doped graphene; And due to the existence of lithium hexafluoro phosphate, make the wettability of boron doped graphene combination electrode material and electrolyte obtain larger raising, while making this material as lithium ion battery negative material, there is excellent energy-storage property.
Refer to Fig. 1, the preparation method of the boron doped graphene combination electrode material of an execution mode comprises the following steps:
S101, is oxidized graphite, obtains graphite oxide.
Its concrete steps are: graphite is added in the mixed solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), mixes in bath at frozen water, keeping temperature is to stir under the condition about 0 ° of C; Then add at leisure potassium permanganate to mixed solution, because potassium permanganate has strong oxidizing property under acid condition, can be oxidized graphite; Again mixed solution is heated to 85 ° of C and reacts, and be incubated 30 minutes, in this insulating process, can further be oxidized graphite; Add deionized water, continue to keep 85 ° of C temperature 30 minutes; Then add hydrogen peroxide to mixed solution, remove excessive potassium permanganate, obtain graphite oxide solution; Graphite oxide solution is carried out to suction filtration, obtains solids, and with watery hydrochloric acid and deionized water to solids cyclic washing, remove impurity, by solids in vacuum drying chamber at 60 ° of C temperature dry 12 hours, obtain graphite oxide.
In the present embodiment, graphite can be 99.5% graphite.The mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of red fuming nitric acid (RFNA) is 65%.The mass fraction of hydrogen peroxide is 30%.
S102, is dispersed in graphite oxide in deionized water, and ultrasonic 2 hours ~ 4 hours, filter, dry, obtain graphene oxide.
Its concrete steps are: the graphite oxide that S101 is made is dispersed in and in deionized water, forms graphite oxide solution; Graphite oxide solution is carried out after ultrasonic processing, graphite oxide solution being filtered, obtain solids; Drying solid thing obtains graphene oxide.
In the present embodiment, the concentration of graphite oxide can be 0.5g/L ~ 1.0g/L, and ultrasonic power can be 500W, and ultrasonic time can be 2 hours ~ 4 hours.Dry process is for being placed in solids 60 ° of C of vacuum tank dry 12 hours.
S103, mixes graphene oxide under the atmosphere that is placed on inert gas with diboron trioxide, is warming up to 800 ° of C ~ 1300 ° C and is incubated 0.5 hour ~ after 2 hours, is cooled to room temperature, obtain mixture, remove residual diboron trioxide, washing, dry, obtain boron doped graphene.
In the present embodiment, the mass ratio of graphene oxide and diboron trioxide can be 0.5:1 ~ 4:1.Inert gas can be argon gas or neon, and the flow velocity of inert gas can be 100mL/min ~ 400mL/min.Heating rate in temperature-rise period can be 10 ° of C/min ~ 30 ° C/min.The step of removing residual diboron trioxide can be for after the graphene oxide diboron trioxide reaction of S102, the sodium hydroxide solution that the mixture of acquisition is placed in to 3mol/L stirs 2 hours ~ 4 hours, responseless diboron trioxide is dissolved, then filter.Drying steps can, for the filtrate after deionized water washing is placed in to 60 ° of C vacuum drying ovens dry 12 hours, obtain boron doped graphene.
S104, is placed in 1-METHYLPYRROLIDONE by boron doped graphene and lithium hexafluoro phosphate, ultrasonic processing mixture, and vacuum stirring, obtains boron doped graphene combination electrode material.
In the present embodiment, first boron doped graphene is added in 1-METHYLPYRROLIDONE, the concentration of boron doped graphene in 1-METHYLPYRROLIDONE can be 1g/L ~ 10g/L.Again humidity lower than 5% condition under, lithium hexafluoro phosphate is added in 1-METHYLPYRROLIDONE, avoid material water suction.The concentration of lithium hexafluoro phosphate in 1-METHYLPYRROLIDONE can be 0.2g/L ~ 2g/L.Ultrasonic processing can be the diligent rate supersonic wave cleaning machine that is 500W to mixture ultrasonic 6 hours.The time of vacuum stirring can be 6 hours.In boron doped graphene combination electrode material, the mass ratio of boron doped graphene and lithium hexafluoro phosphate can be 2:1 ~ 25:1, and the mass ratio of 1-METHYLPYRROLIDONE and lithium hexafluoro phosphate can be 500:1 ~ 5000:1.
In the preparation method of above-mentioned boron doped graphene combination electrode material, boron doped graphene is mixed in 1-METHYLPYRROLIDONE with lithium hexafluoro phosphate, obtain boron doped graphene combination electrode material.Boron doped graphene is a kind of material of desirable underpotential deposition lithium, but this material is easily reunited.In 1-METHYLPYRROLIDONE, mix with lithium hexafluoro phosphate by boron doped graphene, overcome the shortcoming that boron doped graphene lamella is easily reunited, the site of its underpotential deposition can be made full use of, thus the energy storage site of effectively improving boron doped graphene; And due to the existence of lithium hexafluoro phosphate, the wettability of this material and electrolyte is improved greatly, while making this material as lithium ion battery negative material, there is excellent energy-storage property.Meanwhile, above-mentioned preparation method's technique is simple, is applicable to large-scale industrial production.
The lithium ion battery of one execution mode, comprise battery container and be housed in electrode slice in battery container, to electrode, barrier film and electrolyte; Electrode slice boron doped graphene combination electrode material; Be lithium sheet to electrode; Electrode, barrier film and electrode slice are cascading.
In the present embodiment, barrier film can be three layers of barrier film of polypropylene-polyethylene-polypropylene (PP-PE-PP).
In above-mentioned lithium ion battery, electrode slice comprises boron doped graphene combination electrode material, this material mixes with lithium hexafluoro phosphate by boron doped graphene in 1-METHYLPYRROLIDONE, overcome the shortcoming that boron doped graphene lamella is easily reunited, the site of its underpotential deposition can be made full use of, thus the energy storage site of effectively improving boron doped graphene; And due to the existence of lithium hexafluoro phosphate, the wettability of this material and electrolyte is improved greatly, make this lithium ion battery there is excellent energy-storage property.
Refer to Fig. 2, the preparation method of the lithium ion battery of an execution mode comprises the following steps:
S201, mixes boron doped graphene combination electrode material, binding agent and conductive agent, obtains slurry.
In the present embodiment, the mass ratio of boron doped graphene combination electrode material, binding agent and conductive agent can be 85:5:10.Binding agent is made up of carboxymethyl cellulose and butadiene-styrene rubber.Conductive agent is acetylene black.
S202, is coated in slurry on Copper Foil, and drying, slicing treatment make electrode slice.
In the present embodiment, dry run can be to be dried 2 hours prior to 80 ° of C, then is dried 2 hours in 250 ° of C.
S203, provides lithium sheet as to electrode.
In the present embodiment, lithium sheet can directly be bought acquisition.
S204, obtains battery core according to the order of electrode, barrier film and electrode slice being stacked gradually to assembling.
Wherein, barrier film can be tri-layers of barrier film of PP-PE-PP.
S205 at battery core outer cladding battery container, and injects electrolyte in battery container, obtains lithium ion battery after sealing.
In the present embodiment, electrolyte can be LiPF
6/ PC.
Preparation method's step of above-mentioned electrochemical capacitor is simple, operate controlled, be applicable to large-scale industrial production.
Describe below in conjunction with specific embodiment.
Embodiment 1
(1) preparation of graphite oxide: take purity and be 99.5% graphite 1g, in the mixed solution that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that to add by 90mL mass fraction be 98% and 25mL mass fraction are 65% forms, mixed solution is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixed solution, add 6g potassium permanganate at leisure again, stir 1 hour; Then mixed solution is heated to 85 ° of C and keeps 30 minutes; Add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C; Add the hydrogenperoxide steam generator of 10mL mass fraction 30%, stir 10 minutes; Mixed solution is carried out to suction filtration, then with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively, wash altogether three times, finally by solids dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, the concentration of graphite oxide solution is 0.5g/L, under the condition that is 500W at power with supersonic wave cleaning machine, graphite oxide solution is carried out filtering after ultrasonic 2 hours, filtrate is dried to 12 hours in the vacuum drying oven of 60 ° of C, obtains graphene oxide.
(3) preparation of boron doped graphene: get the graphene oxide obtaining in (2) and mix with diboron trioxide, wherein the mass ratio of graphene oxide and diboron trioxide is 4:1, the mixture mixing is placed under the argon gas atmosphere that flow velocity is 400mL/min, with 20 ° of C/min heating rates, mixture temperature is around risen to 800 ° of C, and keep 0.5 hour; Then under the argon shield that is 400mL/min at flow velocity, be naturally down to room temperature; mixture is placed in to the sodium hydroxide solution of 3mol/L; stir 4 hours; filter; with deionized water washing and filtering thing; filtrate after washing is placed in to 60 ° of C vacuum drying ovens dry 12 hours, obtains boron doped graphene.
(4) preparation of boron doped graphene combination electrode material: get the boron doped graphene obtaining in (3) and add in 1-METHYLPYRROLIDONE, the concentration of boron doped graphene is 2g/L, add lithium hexafluoro phosphate in humidity in lower than 5% environment again, the concentration of lithium hexafluoro phosphate is 0.2g/L, and wherein the mass ratio of 1-METHYLPYRROLIDONE and lithium hexafluoro phosphate is 5000:1.Under the condition that is 500W at power with supersonic wave cleaning machine ultrasonic 6 hours, then the mixed liquor after ultrasonic is placed under vacuum environment to mechanical agitation 6 hours, obtain boron doped graphene combination electrode material.
Embodiment 2
(1) preparation of graphite oxide: take purity and be 99.5% graphite 3g, in the mixed solution that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that to add by 285mL mass fraction be 98% and 72mL mass fraction are 65% forms, mixture is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixture, add 12g potassium permanganate at leisure again, stir 1 hour; Then mixture is heated to 85 ° of C and keeps 30 minutes; Add afterwards 150mL deionized water to continue to keep 30 minutes under 85 ° of C; Add the hydrogenperoxide steam generator of 18mL mass fraction 30%, stir 10 minutes; Mixture is carried out to suction filtration, then with 200mL watery hydrochloric acid and 30mL deionized water, solids is washed respectively successively, wash altogether three times, by solids dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, the concentration of graphite oxide solution is 1g/L, under the condition that is 500W at power with supersonic wave cleaning machine, graphite oxide solution is carried out filtering after ultrasonic 2 hours, filtrate is dried to 12 hours in the vacuum drying oven of 60 ° of C, obtains graphene oxide.
(3) preparation of boron doped graphene: the graphene oxide obtaining in (2) is mixed with diboron trioxide, and wherein the mass ratio of graphene oxide and diboron trioxide is 2:1; Be to be placed under the argon gas atmosphere that flow velocity is 200mL/min by the mixture mixing, with 15 ° of C/min heating rates, mixture temperature around risen to 900 ° of C, and keep 1 hour; Then under the argon shield that is 200mL/min at flow velocity, be naturally down to room temperature; mixture is placed in to the sodium hydroxide solution of 3mol/L; stir 4 hours; filter; with deionized water washing and filtering thing; filtrate after washing is placed in to 60 ° of C vacuum drying ovens dry 12 hours, obtains boron doped graphene.
(4) preparation of boron doped graphene combination electrode material: get the boron doped graphene obtaining in (3) and add in 1-METHYLPYRROLIDONE, the concentration of boron doped graphene is 5g/L, add lithium hexafluoro phosphate in humidity in lower than 5% environment again, the concentration of lithium hexafluoro phosphate is 0.2g/L, and wherein the mass ratio of 1-METHYLPYRROLIDONE and lithium hexafluoro phosphate is 5000:1.Under the condition that is 500W at power with supersonic wave cleaning machine ultrasonic 6 hours, then the mixed liquor after ultrasonic is placed under vacuum environment to mechanical agitation 6 hours, obtain boron doped graphene combination electrode material.
Embodiment 3
(1) preparation of graphite oxide: take purity and be 99.5% graphite 5g, in the mixed solution that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that to add by 420mL mass fraction be 98% and 120mL mass fraction are 65% forms, mixture is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixture, add 20g potassium permanganate at leisure again, stir 1 hour; Then mixture is heated to 85 ° of C and keeps 30 minutes; Add afterwards 300mL deionized water to continue to keep 30 minutes under 85 ° of C; Add the hydrogenperoxide steam generator of 40mL mass fraction 30%, stir 10 minutes; Mixture is carried out to suction filtration, then with 400mL watery hydrochloric acid and 800mL deionized water, solids is washed respectively successively, wash altogether three times, last solids is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, the concentration of graphite oxide solution is 1g/L, under the condition that is 500W at power with supersonic wave cleaning machine, graphite oxide solution is carried out filtering after ultrasonic 3 hours, filtrate is dried to 12 hours in the vacuum drying oven of 60 ° of C, obtains graphene oxide.
(3) preparation of boron doped graphene: the graphene oxide obtaining in (2) is mixed with diboron trioxide, wherein the mass ratio of graphene oxide and diboron trioxide is 1:1, be to be placed under the neon atmosphere that flow velocity is 300mL/min by the mixture mixing, with 30 ° of C/min heating rates, mixture temperature is around risen to 1100 ° of C, and keep 2 hours, then under the neon that is 300mL/min at flow velocity protection, be naturally down to room temperature, mixture is placed in to the sodium hydroxide solution of 3mol/L, stir 4 hours, filter, with deionized water washing and filtering thing, filtrate after washing is placed in to 60 ° of C vacuum drying ovens dry 12 hours, obtain boron doped graphene.
(4) preparation of boron doped graphene combination electrode material: get the boron doped graphene obtaining in (3) and add in 1-METHYLPYRROLIDONE, the concentration of boron doped graphene is 10g/L; Add lithium hexafluoro phosphate in humidity in lower than 5% environment, the concentration of lithium hexafluoro phosphate is 2g/L, and wherein the mass ratio of 1-METHYLPYRROLIDONE and lithium hexafluoro phosphate is 500:1.Under the condition that is 500W at power with supersonic wave cleaning machine ultrasonic 6 hours, then the mixed liquor after ultrasonic is placed under vacuum environment to mechanical agitation 6 hours, obtain boron doped graphene combination electrode material.
Embodiment 4
(1) preparation of graphite oxide: take purity and be 99.5% graphite 1g, in the mixed solution that the red fuming nitric acid (RFNA) that the concentrated sulfuric acid that to add by 90mL mass fraction be 98% and 25mL mass fraction are 65% forms, mixed solution is placed in to frozen water and mixes to bathe under environment and stir 20 minutes; In mixed solution, add 6g potassium permanganate at leisure again, stir 1 hour; Then mixed solution is heated to 85 ° of C and keeps 30 minutes; Add afterwards 92mL deionized water to continue to keep 30 minutes under 85 ° of C; Add the hydrogenperoxide steam generator of 9mL mass fraction 30%, stir 10 minutes; Mixed solution is carried out to suction filtration, then with 100mL watery hydrochloric acid and 150mL deionized water, solids is washed respectively successively, wash altogether three times, finally by solids dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) preparation of graphene oxide: the graphite oxide obtaining in (1) is dispersed in deionized water, the concentration of graphite oxide solution is 1g/L, under the condition that is 500W at power with supersonic wave cleaning machine, graphite oxide solution is carried out filtering after ultrasonic 4 hours, filtrate is dried to 12 hours in the vacuum drying oven of 60 ° of C, obtains graphene oxide.
(3) preparation of boron doped graphene: the graphene oxide obtaining in (2) is mixed with diboron trioxide, wherein the mass ratio of graphene oxide and diboron trioxide is 0.5:1, be to be placed under the argon gas atmosphere that flow velocity is 100mL/min by the mixture mixing, with 10 ° of C/min heating rates, mixture temperature is around risen to 1300 ° of C, and keep 2 hours; Then under the argon shield that is 100mL/min at flow velocity, be naturally down to room temperature; mixture is placed in to the sodium hydroxide solution of 3mol/L; stir 2 hours; filter; with deionized water washing and filtering thing; filtrate after washing is placed in to 60 ° of C vacuum drying ovens dry 12 hours, obtains boron doped graphene.
(4) preparation of boron doped graphene combination electrode material: get the boron doped graphene obtaining in (3) and add in 1-METHYLPYRROLIDONE, the concentration of boron doped graphene is 1g/L; Add lithium hexafluoro phosphate in humidity in lower than 5% environment, the concentration of lithium hexafluoro phosphate is 0.5g/L; Wherein the mass ratio of 1-METHYLPYRROLIDONE and lithium hexafluoro phosphate is 2000:1.Under the condition that is 500W at power with supersonic wave cleaning machine ultrasonic 6 hours, then the mixed liquor after ultrasonic is placed under vacuum environment to mechanical agitation 6 hours, obtain boron doped graphene combination electrode material.
Embodiment 5
(1) ratio that is 85:5:10 according to mass ratio, mixture and the acetylene black of boron doped graphene combination electrode material, carboxymethyl cellulose and butadiene-styrene rubber prepared by embodiment 1 mix, and obtain slurry.
(2) slurry obtaining in (1) is coated on Copper Foil, through the dry 2 hours slicing treatment of dry 2 hours, the 250 ° C of 80 ° of C, makes electrode slice.
(3) providing lithium sheet is to electrode.
(4) stack gradually and be assembled into battery core according to the order of the electrode slice obtaining in lithium sheet, tri-layers of barrier film of PP-PE-PP, (2).
(5) use again the battery core obtaining in battery housing seal (4), in battery container, inject LiPF toward the liquid injection port being arranged on battery container subsequently
6/ PC electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment (6)
(1) ratio that is 85:5:10 according to mass ratio, mixture and the acetylene black of boron doped graphene combination electrode material, carboxymethyl cellulose and butadiene-styrene rubber prepared by embodiment 2 mix, and obtain slurry.
(2) slurry obtaining in (1) is coated on Copper Foil, through the dry 2 hours slicing treatment of dry 2 hours, the 250 ° C of 80 ° of C, makes electrode slice.
(3) providing lithium sheet is to electrode.
(4) stack gradually and be assembled into battery core according to the order of the electrode slice obtaining in lithium sheet, tri-layers of barrier film of PP-PE-PP, (2).
(5) use again the battery core obtaining in battery housing seal (4), in battery container, inject LiPF toward the liquid injection port being arranged on battery container subsequently
6/ PC electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment 7
(1) ratio that is 85:5:10 according to mass ratio, mixture and the acetylene black of boron doped graphene combination electrode material, carboxymethyl cellulose and butadiene-styrene rubber prepared by embodiment 3 mix, and obtain slurry.
(2) slurry obtaining in (1) is coated on Copper Foil, through the dry 2 hours slicing treatment of dry 2 hours, the 250 ° C of 80 ° of C, makes electrode slice.
(3) providing lithium sheet is to electrode.
(4) stack gradually and be assembled into battery core according to the order of the electrode slice obtaining in lithium sheet, tri-layers of barrier film of PP-PE-PP, (2).
(5) use again the battery core obtaining in battery housing seal (4), in battery container, inject LiPF toward the liquid injection port being arranged on battery container subsequently
6/ PC electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment 8
(1) ratio that is 85:5:10 according to mass ratio, mixture and the acetylene black of boron doped graphene combination electrode material, carboxymethyl cellulose and butadiene-styrene rubber prepared by embodiment 4 mix, and obtain slurry.
(2) slurry obtaining in (1) is coated on Copper Foil, through the dry 2 hours slicing treatment of dry 2 hours, the 250 ° C of 80 ° of C, makes electrode slice.
(3) providing lithium sheet is to electrode.
(4) stack gradually and be assembled into battery core according to the order of the electrode slice obtaining in lithium sheet, tri-layers of barrier film of PP-PE-PP, (2).
(5) use again the battery core obtaining in battery housing seal (4), in battery container, inject LiPF toward the liquid injection port being arranged on battery container subsequently
6/ PC electrolyte, sealing liquid injection port, obtains lithium ion battery.
Lithium ion battery to embodiment 5 ~ 8 preparations carries out charge-discharge test, and voltage range is 1.2V-3V vsLi/Li+.Result is as shown in table 1.
The lithium ion battery that table 1 is embodiment 5 ~ 8 carries out the specific capacity of charge-discharge test under 1C electric current
| Sample | Specific capacity (mAh/g) |
| Embodiment 5 | 486 |
| Embodiment 6 | 539 |
| Embodiment 7 | 689 |
| Embodiment 8 | 812 |
Lithium ion battery prepared by the employing this method specific capacity under 1C electric current all, more than 450mAh/g, is up to 812mAh/g, has excellent energy-storage property.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a boron doped graphene combination electrode material, is characterized in that, comprises boron doped graphene, lithium hexafluoro phosphate and 1-METHYLPYRROLIDONE; Described boron doped graphene and described lithium hexafluoro phosphate are dispersed in described 1-METHYLPYRROLIDONE.
2. boron doped graphene combination electrode material according to claim 1, it is characterized in that, the mass ratio of described boron doped graphene and described lithium hexafluoro phosphate is 2:1 ~ 25:1, and the mass ratio of described 1-METHYLPYRROLIDONE and described lithium hexafluoro phosphate is 500:1 ~ 5000:1.
3. a preparation method for boron doped graphene combination electrode material, is characterized in that, comprising:
Graphite is oxidized, obtains graphite oxide;
Described graphite oxide is dispersed in deionized water, ultrasonic 2 hours ~ 4 hours, filter, dry, obtain graphene oxide;
Described graphene oxide is mixed under the atmosphere that is placed on inert gas with diboron trioxide, be warming up to 800 ° of C ~ 1300 ° C and be incubated 0.5 hour ~ after 2 hours, be cooled to room temperature, obtain mixture, remove residual diboron trioxide, washing, dry, obtain boron doped graphene; And
Described boron doped graphene and described lithium hexafluoro phosphate are placed in to 1-METHYLPYRROLIDONE ultrasonic processing, then under vacuum, stir, obtain boron doped graphene combination electrode material.
4. the preparation method of boron doped graphene combination electrode material according to claim 3, it is characterized in that, the mass ratio of described boron doped graphene and described lithium hexafluoro phosphate is 2:1 ~ 25:1, and the mass ratio of described 1-METHYLPYRROLIDONE and described lithium hexafluoro phosphate is 500:1 ~ 5000:1.
5. the preparation method of boron doped graphene combination electrode material according to claim 3, is characterized in that, the mass ratio of described graphite oxide and diboron trioxide is 0.5:1 ~ 4:1.
6. the preparation method of boron doped graphene combination electrode material according to claim 3, it is characterized in that, described in remove residual diboron trioxide step be that sodium hydroxide solution that described mixture is placed in to 3mol/L stirs after 2 hours ~ 4 hours and filters.
7. a lithium ion battery, is characterized in that, comprise battery container and be housed in electrode slice in described battery container, to electrode, barrier film and electrolyte;
Described electrode slice comprises boron doped graphene combination electrode material claimed in claim 1;
Described is lithium sheet to electrode;
Described electrode, barrier film and electrode slice are cascading.
8. a preparation method for lithium ion battery, is characterized in that, comprising:
Boron doped graphene combination electrode material, binding agent and conductive agent described in claim 1 are mixed, obtain slurry;
Described slurry is coated on Copper Foil, and drying, slicing treatment make electrode slice;
Provide lithium sheet as to electrode;
Stack gradually assembling according to the described order to electrode, barrier film and described electrode slice and obtain battery core; And
At described battery core outer cladding battery container, and inject electrolyte in described battery container, after sealing, obtain lithium ion battery.
9. the preparation method of lithium ion battery according to claim 8, is characterized in that, the mass ratio 85:5:10 of described boron doped graphene combination electrode material, binding agent and conductive agent; Described binding agent is made up of carboxymethyl cellulose and butadiene-styrene rubber, and described conductive agent is acetylene black.
10. the preparation method of lithium ion battery according to claim 8, is characterized in that, described electrolyte is LiPF
6/ PC.
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| CN106532024A (en) * | 2016-12-10 | 2017-03-22 | 浙江大学 | Preparation method for graphene-loaded nanometer boron used as negative electrode material of lithium ion battery |
| CN108598542A (en) * | 2018-04-04 | 2018-09-28 | 苏州舒广袖新能源科技有限公司 | A kind of all-vanadium flow battery based on boron doping carbon nanotube |
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| CN105833893B (en) * | 2016-05-15 | 2018-12-28 | 台州学院 | The preparation method of boron nitrogen-doped graphene carried palladium catalyst |
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