CN103730643A - Silicon and graphene composite electrode material, preparing method thereof and lithium ion battery - Google Patents
Silicon and graphene composite electrode material, preparing method thereof and lithium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 56
- 239000010703 silicon Substances 0.000 title claims abstract description 56
- 239000007772 electrode material Substances 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title abstract description 18
- 239000002131 composite material Substances 0.000 title abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 52
- 239000010439 graphite Substances 0.000 claims description 52
- 238000002360 preparation method Methods 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000012286 potassium permanganate Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- QYKABQMBXCBINA-UHFFFAOYSA-N 4-(oxan-2-yloxy)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1OC1OCCCC1 QYKABQMBXCBINA-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 238000009832 plasma treatment Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910010941 LiFSI Inorganic materials 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 46
- 239000000463 material Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 210000002381 plasma Anatomy 0.000 abstract 1
- 239000011800 void material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003376 silicon Chemical class 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
Classifications
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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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a graphene and a preparing method thereof. The preparing method comprises the following steps: (a) preparing oxidized grapheme; (b) preparing grapheme; (c) preparing a silicon and graphene composite electrode material. The invention further relates to a lithium ion battery which is prepared by using the silicon and graphene composite electrode material as a negative electrode material of the lithium ion battery. The prepared silicon and graphene composite electrode material is characterized in that silicon is deposited on modified grapheme which is processed by plasmas, the silicon is optimally deposited at the flaw part of the grapheme, the volume of the silicon expands when energy is stored by the silicon, the expansion can be just buffered by a certain void space at the flaw part, and the volume of the whole material cannot be increased. Therefore, the silicon and graphene composite material has excellent circulating performance when being used as the negative electrode material of the lithium ion battery. The preparing method has the advantages of simple technology and easiness in the realization of large-scale production.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to a kind of silicon
/graphene combination electrode material and preparation method thereof.The invention still further relates to and adopt the prepared ion lithium battery of this electrode material.
Background technology
Lithium ion battery is as a kind of novel energy-storing device, and lot of domestic and international scientific research institution and enterprise fall over each other research.Along with the development of various electronic products, the performance of lithium ion battery more and more can not meet the demand of various consumer products.At present the negative material of lithium ion battery is mainly used graphite, and the theoretical capacity of graphite is only up to 372mAh/g, and this has limited the performance of lithium ion battery greatly.Recently, researcher finds that silicon is as negative material, there is very high stored energy capacitance, the highest theoretical capacity can reach 4200mAh/g, for the raising of performance of lithium ion battery provides a kind of very effective method, but it is that silicon change in volume in the process of embedding lithium and de-lithium is larger that silicon exists a problem as negative material, this can cause electrode material powdered, make lithium ion battery along with the increase stored energy capacitance of cycle-index declines very fast, thereby shortened the life-span of lithium ion battery, therefore these defects are that silicon materials apply to an electrode material major issue urgently to be resolved hurrily.Graphene is a kind of two-dimentional monolayer material, has excellent flexibility, silicon materials and Graphene carry out compound can effectively reduce silicon materials expand and contraction process in destruction to electrode material, thereby the cycle performance of raising device.At present often preparation process is comparatively loaded down with trivial details for the silicon/graphene composite material of report, need first prepare grapheme material, then mix with silicon materials, and this composite material during as lithium electric material volumetric expansion still very large.
Summary of the invention
The object of the invention is to solve the problem and shortage that above-mentioned prior art exists, provide a kind of silicon/graphene combination electrode material and preparation method thereof the lithium ion battery prepared with adopting this electrode material.Silicon/graphene combination electrode material of the present invention, on modified graphene after plasma treatment, carry out siliceous deposits, silicon preferential deposition, at the fault location of Graphene, has excellent cycle performance while making this silicon/graphene combination electrode material as lithium ion battery negative material.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: a kind of preparation method of silicon/graphene combination electrode material, comprise the steps: that (a) prepares graphene oxide: graphite oxide is dispersed in deionized water, ultrasonic rear filtration, obtains graphene oxide after oven dry filtrate; (b) prepare Graphene: prepared graphene oxide in step (a) is placed under inert atmosphere and is rapidly heated and peels off and obtain Graphene to high temperature, then to the Graphene plasma treatment obtaining, obtain the Graphene after modification; (c) prepare silicon/graphene combination electrode material: the pressure environment that the Graphene after modification prepared in step (b) is placed in to 80～100Pa; be filled with silicon tetrahydride gas; be warming up to again 700～900 ° of C; and keep 1～3 hour; finally the protection at inert gas drops to room temperature, obtains silicon/graphene combination electrode material.
In described step (a), it is 0.5～2mg/ml that described graphite oxide is dispersed in the solubility obtaining in deionized water; Described ultrasonic power is 500W, and ultrasonic time is 1～3 hour; The temperature of described oven dry is 60 ° of C, and the time is 12 hours.
In described step (b), the flow of described inert gas is 200～400ml/ minute, and heating rate is 15～30 ° of C/ minute; Described graphene oxide needs to keep 0.5～2 hour after being warmed up to 700～900 ° of C; The power of described plasma treatment is 50～150W, and the processing time is 2～3 hours.
In described step (c), the flow of described silicon tetrahydride gas is 200 ~ 400ml/ minute, and heating rate is 5 ~ 15 ° of C/ minute.
In described step (a), the preparation method of graphite oxide used comprises: it is in the mixed solution that forms of red fuming nitric acid (RFNA) that 98% the concentrated sulfuric acid and mass fraction are 65% that the graphite of purity 99.5% is joined to mass fraction, stir in backward described mixed solution and add potassium permanganate heated oxide, add again the hydrogenperoxide steam generator of mass fraction 30% to stir to remove potassium permanganate, then described mixed solution is carried out to suction filtration, more obtain described graphite oxide after dry to the washing of suction filtration thing with watery hydrochloric acid and deionized water successively; The mass volume ratio of described graphite, the described concentrated sulfuric acid, described red fuming nitric acid (RFNA), described potassium permanganate and described hydrogen peroxide is 1g:85-95ml:20-25ml:4-6g:6-10ml; Described being dried is to carry out in the vacuum drying oven under 60 ° of C, and the described dry time is 12 hours.
The present invention also comprises the silicon/graphene combination electrode material that utilizes above-mentioned preparation method to make.
The invention still further relates to a kind of lithium ion battery, this lithium ion battery comprises by electrode, barrier film, negative plate is the battery core of stacked composition in order, for installing the closed shell of described battery core, and the electrolyte of filling in described closed shell, described negative plate comprises collector and is coated in the slurry on this collector, described slurry comprises the negative electrode material that 85:5:10 mixes in mass ratio, play the butadiene-styrene rubber of binding agent effect and the mixture of sodium carboxymethylcellulose, and the acetylene black that plays conductive agent effect, described negative electrode material is above-mentioned silicon/graphene combination electrode material.
Solute in described electrolyte is LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2), LiFSI (LiN (SO
2f)
2) in a kind of; Solvent in described electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile; The concentration of described electrolyte is 1mol/L.
Compared with prior art, silicon/graphene combination electrode material that the present invention is prepared, on modified graphene after plasma treatment, carry out siliceous deposits, silicon preferential deposition is at the fault location of Graphene, in energy storage, can there is volumetric expansion in silicon, but can there is certain room to make it to cushion at fault location, and be unlikely to cause whole material volume to become large.While therefore this silicon/graphene composite material being used as lithium ion battery negative material, there is excellent cycle performance.Preparation method's technique of the present invention is simple, easily realizes large-scale production.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.
the preparation of Graphene:concrete preparation technology's flow process of Graphene of the present invention is as follows: graphite → graphite oxide → graphene oxide → Graphene → silicon/graphene combination electrode material.
In the present invention, the preparation process of Graphene is roughly divided into following steps.
(1) prepare graphite oxide: it is in the mixed solution that forms of red fuming nitric acid (RFNA) that 98% the concentrated sulfuric acid and mass fraction are 65% that the graphite of purity 99.5% is joined to mass fraction, stir in backward described mixed solution and add potassium permanganate heated oxide, add again the hydrogenperoxide steam generator of mass fraction 30% to stir to remove potassium permanganate, then mixed solution is carried out to suction filtration, after suction filtration thing being washed, is dried with watery hydrochloric acid and deionized water successively again, obtain graphite oxide, graphite oxide is dry in vacuum drying oven under 60 ° of C, and be 12 hours drying time.Wherein, the mass volume ratio of graphite, the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate and hydrogen peroxide is: 1g:85-95ml:20-25 ml:4-6g:6-10ml.
(2) prepare graphene oxide: the prepared graphite oxide of step (1) is dispersed in deionized water, graphite oxide solubility is 0.5～2mg/ml, under 500W ultrasonic power, after ultrasonic 1～3 hour, filter, after drying filtrate, obtain graphene oxide, the temperature of drying is 60 ° of C, and the time is 12 hours.
(3) prepare Graphene: to be just placed in flow be under the atmosphere of inert gases of 200～400ml/ minute to the prepared graphene oxide of step (2), ambient temperature to 700～900 ° C with 15～30 ° of heating rate rising graphene oxides of C/ minute, keep peeling off after 0.5～2 hour, be down to afterwards room temperature and be placed under the inert, plasma that power is 50～150W and react after 2～3 hours and obtain the Graphene after modification.
(4) prepare silicon/graphene combination electrode material: the pressure environment that the Graphene after the prepared modification of step (3) is placed in to 80～100Pa; be filled with silicon tetrahydride gas; be warming up to again 700～900 ° of C; and keep 1～3 hour; finally the protection at inert gas drops to room temperature, obtains silicon/graphene combination electrode material.
The reaction equation that above step (4) occurs is: SiH
4→ Si+2H
2↑.
the preparation of lithium ion battery:the present invention also comprises the lithium ion battery of silicon/graphene combination electrode material of preparing containing said method, this lithium ion battery comprise by electrode, barrier film, negative electrode plate in order the stacked battery core forming, for installing the closed shell of battery core, and filling is at the electrolyte of described closed shell.
Wherein, to electrode, it is lithium sheet, negative electrode plate comprises collector and is coated in the slurry on this collector, and this slurry is to be mixed by above-mentioned silicon/graphene combination electrode material, the acetylene black that plays the butadiene-styrene rubber (english abbreviation SBR) of binding agent effect and the mixture of sodium carboxymethylcellulose (english abbreviation CMC) and play conductive agent effect.
Below introduce the roughly step of using this silicon/graphene combination electrode material to be made into lithium ion battery: first, the ratio that is 85:5:10 according to mass ratio, silicon/graphene combination electrode material, binding agent butadiene-styrene rubber are mixed with mixture and the conductive agent acetylene black of sodium carboxymethylcellulose, obtain slurry.
Secondly, slurry is coated on collector, drying, slicing treatment, make negative electrode plate.
Finally, using lithium sheet as to electrode, by lithium sheet, barrier film, negative electrode plate in order stack of laminations dress up battery core, then use battery housing seal battery core, in the liquid injection port on battery container, inject electrolyte subsequently, sealing liquid injection port, obtains lithium ion battery.
Wherein, the electrolyte in electrolyte adopts the common electrolyte of lithium ion battery, as LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2), LiFSI (LiN (SO
2f)
2) etc., the mixing of one or more in solvent employing dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile; Electrolytical concentration is generally 1mol/L.
Preparation process with 1～4 pair of Graphene of the present invention of embodiment is specifically described below.
embodiment 1: the preparation method in the embodiment of the present invention 1 comprises the steps: that (1) prepare graphite oxide: take purity and be 99.5% graphite 1g and add in the mixed solution being comprised of the 95ml concentrated sulfuric acid (mass fraction is 98%) and 25ml red fuming nitric acid (RFNA) (mass fraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 6g potassium permanganate at leisure again, stir 1 hour, then mixture 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, finally add 10ml hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml watery hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens, (2) prepare graphene oxide: the graphite oxide of step (1) gained is placed in to deionized water, the solubility of graphite oxide is 1mg/ml, the ultrasonic machine that is 500W with power carries out ultrasonic 2 hours, filtration obtains solid filtering thing, the vacuum drying oven that solid filtering thing is placed in to 60 ° of C is dried 12 hours, obtains graphene oxide, (3) prepare Graphene: it is under the argon atmosphere of 400ml/ minute that the graphene oxide of step (2) gained is placed in to flow, with 30 ° of heating rates of C/ minute, the ambient temperature of graphene oxide is risen to 700 ° of C, keep 2 hours, then at argon atmosphere, drop to room temperature, and be to process 2 hours under 100W helium plasma at power, obtain the Graphene after modification, (4) silicon/graphene composite material: it is 100Pa environment that the Graphene of step (3) gained is placed in to pressure, be filled with silicon tetrahydride (flow velocity: 400ml/ minute) gas, with 5 ° of heating rates of C/ minute, Graphene ambient temperature is around risen to 900 ° of C again, and keep 1 hour, finally at argon gas (flow velocity: 200ml/ minute) protection drops to room temperature, obtains silicon/graphene combination electrode material.
embodiment 2: the preparation method in the embodiment of the present invention 2 comprises the steps: that (1) prepare graphite oxide: take purity and be 99.5% graphite 1g and add in the mixed solution being comprised of the 85ml concentrated sulfuric acid (mass fraction is 98%) and 20ml red fuming nitric acid (RFNA) (mass fraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 4g potassium permanganate at leisure again, stir 1 hour, then mixture 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, finally add 6ml hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml watery hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens, (2) prepare graphene oxide: step (1) gained graphite oxide is placed in to deionized water, the solubility of graphite oxide is 0.5mg/ml, the ultrasonic machine that is 500W with power carries out ultrasonic 1 hour, filtration obtains solid filtering thing, by obtaining solid filtering thing and be placed in dry 12 hours of the vacuum drying oven of 60 ° of C, obtain graphene oxide, (3) prepare Graphene: it is under the argon atmosphere of 300ml/ minute that step (2) gained graphene oxide is placed in to flow, with 25 ° of heating rates of C/ minute, the ambient temperature of graphene oxide is risen to 800 ° of C, keep 1 hour, then at argon atmosphere, drop to room temperature, and be to process 2 hours under 50W helium plasma at power, obtain the Graphene after modification, (4) prepare silicon/graphene composite material: it is 100Pa environment that the modified graphene of step (3) gained is placed in to pressure, be filled with silicon tetrahydride (flow velocity: 300ml/ minute) gas, with 10 ° of heating rates of C/ minute, Graphene ambient temperature is around risen to 800 ° of C again, and keep 2 hours, final argon gas (flow velocity: 200ml/ minute) protection drops to room temperature, obtains silicon/graphene combination electrode material.
embodiment 3: the preparation method in the embodiment of the present invention 3 comprises the steps: that (1) prepare graphite oxide: take purity and be 99.5% graphite 1g and add in the mixed solution being comprised of the 87ml concentrated sulfuric acid (mass fraction is 98%) and 22ml red fuming nitric acid (RFNA) (mass fraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 5g potassium permanganate at leisure again, stir 1 hour, then mixture 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, finally add 7ml hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml watery hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens, (2) prepare graphene oxide: the graphite oxide of step (1) gained is placed in to deionized water, the solubility of graphite oxide is 2mg/ml, the ultrasonic machine that is 500W with power carries out ultrasonic 3 hours, filtration obtains solid filtering thing, by obtaining solid filtering thing and be placed in dry 12 hours of the vacuum drying oven of 60 ° of C, obtain graphene oxide, (3) prepare Graphene: it is under the argon atmosphere of 400ml/ minute that the graphene oxide of step (2) gained is placed in to flow, with 20 ° of heating rates of C/ minute, the ambient temperature of graphene oxide is risen to 900 ° of C, keep 0.5 hour, then at argon atmosphere, drop to room temperature, and be to process 3 hours under 100W helium plasma at power, obtain the Graphene after modification, (4) prepare silicon/graphene composite material: it is 80Pa environment that the modified graphene of step (3) gained is placed in to pressure, be filled with silicon tetrahydride (flow velocity: 400ml/ minute) gas, with 5 ° of heating rates of C/ minute, Graphene ambient temperature is around risen to 700 ° of C again, and keep 2 hours, final argon gas (flow velocity: 200ml/ minute) protection drops to room temperature, obtains silicon/graphene combination electrode material.
embodiment 4: the preparation method in the embodiment of the present invention 4 comprises the steps: that (1) prepare graphite oxide: take purity and be 99.5% graphite 1g and add in the mixed solution being comprised of the 92ml concentrated sulfuric acid (mass fraction is 98%) and 24ml red fuming nitric acid (RFNA) (mass fraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 5g potassium permanganate at leisure again, stir 1 hour, then mixture 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, finally add 8ml hydrogenperoxide steam generator (mass fraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml watery hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens, (2) prepare graphene oxide: the graphite oxide of step (1) gained is placed in to deionized water, the solubility of graphite oxide is 1mg/ml, the ultrasonic machine that is 500W with power carries out ultrasonic 3 hours, filtration obtains solid filtering thing, by obtaining solid filtering thing and be placed in dry 12 hours of the vacuum drying oven of 60 ° of C, obtain graphene oxide, (3) prepare Graphene: it is under the argon atmosphere of 200ml/ minute that the graphene oxide of step (2) gained is placed in to flow, with 15 ° of heating rates of C/ minute, the ambient temperature of graphene oxide is risen to 700 ° of C, keep 2 hours, then at argon atmosphere, drop to room temperature, and be to process 2.5 hours under 150W helium plasma at power, obtain the Graphene after modification, (4) prepare silicon/graphene composite material: it is 80Pa environment that the modified graphene of step (3) gained is placed in to pressure, be filled with silicon tetrahydride (flow velocity: 200ml/ minute) gas, with 15 ° of heating rates of C/ minute, Graphene ambient temperature is around risen to 850 ° of C again, and keep 3 hours, final argon gas (flow velocity: 200ml/ minute) protection drops to room temperature, obtains silicon/graphene composite material.
Preparation process with 5 pairs of lithium ion batteries of the present invention of embodiment is specifically described below.
embodiment 5:(1) ratio that is 85:5:10 according to mass ratio, mixes silicon/graphene combination electrode material, the butadiene-styrene rubber (SBR) of embodiment 1 preparation with mixture binding agent and the conductive agent acetylene black of sodium carboxymethylcellulose (CMC), obtain slurry; (2) slurry is coated on Copper Foil, drying, slicing treatment, make negative electrode plate.
Using lithium sheet as to electrode, by lithium sheet, barrier film, (2) prepared negative electrode plate in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward the LiPF that injects 1mol/L in the liquid injection port on battery container
6/ dimethyl carbonate electrolyte, sealing liquid injection port, obtains lithium ion battery, carries out charge-discharge test, voltage range 0.1V ~ 3V vs Li/Li
+.
Embodiment 6～8 is identical with the method for embodiment 5, and the negative electrode material just adopting is respectively that embodiment 2～4 is out prepared, and electrolyte is respectively just the LiBF of 1mol/L
4liTFSI/propene carbonate electrolyte of/diethyl carbonate electrolyte, 1mol/L, LiFSI/ethylene carbonate+acetonitrile electrolyte of 1mol/L.
Following table 1 is embodiment 1～4 key process parameter.
| table 1 | graphite oxide | graphene oxide | graphene | silicon/graphene composite material |
| embodiment 1 | 99.5% graphite: 98% concentrated sulfuric acid: 65% red fuming nitric acid (RFNA): potassium permanganate: 30% hydrogen peroxide=1g:95ml:25ml:6g:10ml. | the solubility of graphite oxide: 1mg/ml; Ultrasonic time: 2 hours. | heating rate: 30 ° of C/ minute; Final temperature: 700 ° of C; The final temperature retention time: 2 hours; Plasma power: 100W; Processing time: 2 hours. | pressure: 100Pa; Silicon tetrahydride flow velocity: 400ml/ minute; Heating rate: 5 °/minute; Maximum temperature: 900 ° of C; The maximum temperature retention time: 1 hour. |
| embodiment 2 | 99.5% graphite: 98% concentrated sulfuric acid: 65% red fuming nitric acid (RFNA): potassium permanganate: 30% hydrogen peroxide=1g:85ml:20ml:4g:6ml. | the solubility of graphite oxide: 0.5mg/ml; Ultrasonic time: 1 hour. | heating rate: 25 ° of C/ minute; Final temperature: 800 ° of C; The final temperature retention time: 1 hour; Plasma power: 50W; Processing time: 2 hours. | pressure: 100Pa; Silicon tetrahydride flow velocity: 300ml/ minute; Heating rate: 10 °/minute; Maximum temperature: 800 ° of C; The maximum temperature retention time: 2 hours. |
| embodiment 3 | 99.5% graphite: 98% concentrated sulfuric acid: 65% red fuming nitric acid (RFNA): potassium permanganate: 30% hydrogen peroxide=1g:87ml:22ml:5g:7ml. | the solubility of graphite oxide: 2mg/ml; Ultrasonic time: 3 hours. | heating rate: 20 ° of C/ minute; Final temperature: 900 ° of C; The final temperature retention time: 0.5 hour; Plasma power: 100W; Processing time: 3 hours. | pressure: 80Pa; Silicon tetrahydride flow velocity: 400ml/ minute; Heating rate: 5 °/minute; Maximum temperature: 700 ° of C; The maximum temperature retention time: 2 hours. |
| embodiment 4 | 99.5% graphite: 98% concentrated sulfuric acid: 65% red fuming nitric acid (RFNA): potassium permanganate: 30% hydrogen peroxide=1g:92ml:24ml:5g:8ml. | the solubility of graphite oxide: 1mg/ml; Ultrasonic time: 3 hours. | heating rate: 15 ° of C/ minute; Final temperature: 700 ° of C; The final temperature retention time: 2 hours; Plasma power: 150W; Processing time: 2 hours. | pressure: 80Pa; Silicon tetrahydride flow velocity: 200ml/ minute; Heating rate: 15 °/minute; Maximum temperature: 850 ° of C; The maximum temperature retention time: 3 hours. |
Table 2 encloses for embodiment 5 ~ 8 carries out charge-discharge test the 2nd circle and the 301st under 0.5C electric current the stored energy capacitance obtaining.
| Table 2 | Specific capacity (the 2nd circle) mAh/g | Specific capacity (the 301st circle) mAh/g |
| Embodiment 5 | 2085 | 1745 |
| Embodiment 6 | 1775 | 1485 |
| Embodiment 7 | 1889 | 1526 |
| Embodiment 8 | 2154 | 1674 |
The stored energy capacitance of silicon/graphene combination electrode material prepared by employing this method is all more than 1775mAh/g, be up to 2154mAh/g, there is higher stored energy capacitance, crucial is that the rear capability retention of circulation 300 circle is all more than 75%, can reach 83%, higher than current Silicon Based Anode Materials for Lithium-Ion Batteries than electric capacity conservation rate.
Compared with prior art, silicon/graphene combination electrode material that the present invention is prepared, on modified graphene after plasma treatment, carry out siliceous deposits, silicon preferential deposition is at the fault location of Graphene, in energy storage, can there is volumetric expansion in silicon, but can there is certain room to make it to cushion at fault location, and be unlikely to cause whole material volume to become large.While therefore this silicon/graphene composite material being used as lithium ion battery negative material, there is excellent cycle performance.Preparation method's technique of the present invention is simple, easily realizes large-scale production.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, therefore protection scope of the present invention should be as the criterion with the desired protection range of claims.
Claims (10)
1. a preparation method for silicon/graphene combination electrode material, is characterized in that, comprises the steps:
(a) prepare graphene oxide: graphite oxide is dispersed in deionized water, and ultrasonic rear filtration, obtains graphene oxide after oven dry filtrate;
(b) prepare Graphene: prepared graphene oxide in step (a) is placed under inert atmosphere and is rapidly heated and peels off and obtain Graphene to high temperature, then to the Graphene plasma treatment obtaining, obtain the Graphene after modification;
(c) prepare silicon/graphene combination electrode material: the pressure environment that the Graphene after modification prepared in step (b) is placed in to 80～100Pa; be filled with silicon tetrahydride gas; be warming up to again 700～900 ° of C; and keep 1～3 hour; finally the protection at inert gas drops to room temperature, obtains silicon/graphene combination electrode material.
2. preparation method according to claim 1, is characterized in that, in described step (a), it is 0.5～2mg/ml that described graphite oxide is dispersed in the solubility obtaining in deionized water; Described ultrasonic power is 500W, and ultrasonic time is 1～3 hour; The temperature of described oven dry is 60 ° of C, and the time is 12 hours.
3. preparation method according to claim 1, is characterized in that, in described step (b), the flow of described inert gas is 200～400ml/ minute, and heating rate is 15～30 ° of C/ minute; Described graphene oxide needs to keep 0.5～2 hour after being warmed up to 700～900 ° of C; The power of described plasma treatment is 50～150W, and the processing time is 2～3 hours.
4. preparation method according to claim 1, is characterized in that, in described step (c), the flow of described silicon tetrahydride gas is 200～400ml/ minute, and heating rate is 5～15 ° of C/ minute.
5. preparation method according to claim 1, it is characterized in that, in described step (a), the preparation method of graphite oxide used comprises: it is in the mixed solution that forms of red fuming nitric acid (RFNA) that 98% the concentrated sulfuric acid and mass fraction are 65% that the graphite of purity 99.5% is joined to mass fraction, stir in backward described mixed solution and add potassium permanganate heated oxide, add again the hydrogenperoxide steam generator of mass fraction 30% to stir to remove potassium permanganate, then described mixed solution is carried out to suction filtration, after dry to the washing of suction filtration thing with watery hydrochloric acid and deionized water successively again, obtain described graphite oxide.
6. preparation method according to claim 5, is characterized in that, the mass volume ratio of described graphite, the described concentrated sulfuric acid, described red fuming nitric acid (RFNA), described potassium permanganate and described hydrogen peroxide is 1g:85-95ml:20-25 ml:4-6g:6-10ml.
7. preparation method according to claim 5, is characterized in that, described being dried is to carry out in the vacuum drying oven under 60 ° of C, and the described dry time is 12 hours.
8. silicon/graphene combination electrode material that the arbitrary described preparation method of a claim 1 to 7 makes.
9. a lithium ion battery, comprise by electrode, barrier film, negative electrode plate is the battery core of stacked composition in order, for installing the closed shell of described battery core, and the electrolyte of filling in described closed shell, described Graphene electrodes sheet comprises collector and is coated in the slurry on this collector, described slurry comprises the negative electrode material that 85:5:10 mixes in mass ratio, play the butadiene-styrene rubber of binding agent effect and the mixture of sodium carboxymethylcellulose, and the acetylene black that plays conductive agent effect, it is characterized in that, described negative electrode material is silicon/graphene combination electrode material claimed in claim 8.
10. lithium ion battery according to claim 9, is characterized in that, the solute in described electrolyte is LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2), LiFSI (LiN (SO
2f)
2) in a kind of; Solvent in described electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile; The concentration of described electrolyte is 1mol/L.
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