CN104282894A - Preparation method of porous Si/C composite microsphere - Google Patents
Preparation method of porous Si/C composite microsphere Download PDFInfo
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- CN104282894A CN104282894A CN201310282713.7A CN201310282713A CN104282894A CN 104282894 A CN104282894 A CN 104282894A CN 201310282713 A CN201310282713 A CN 201310282713A CN 104282894 A CN104282894 A CN 104282894A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 36
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title abstract 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 26
- 239000000661 sodium alginate Substances 0.000 claims abstract description 26
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims abstract description 20
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000701 coagulant Substances 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 10
- 229920000053 polysorbate 80 Polymers 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- NWGKJDSIEKMTRX-MDZDMXLPSA-N Sorbitan oleate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(O)C1OCC(O)C1O NWGKJDSIEKMTRX-MDZDMXLPSA-N 0.000 claims description 8
- 235000013312 flour Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003995 emulsifying agent Substances 0.000 abstract description 2
- 238000001879 gelation Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 238000003763 carbonization Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910021435 silicon-carbon complex Inorganic materials 0.000 description 4
- 239000011867 silicon-carbon complex material Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001424 field-emission electron microscopy Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 241000555268 Dendroides Species 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a porous Si / C composite microsphere, and belongs to the technical field of electrode materials for lithium ion batteries. The process comprises the following steps: using silicon-dispersed sodium alginate aqueous solution as a water phase, using isooctane solution, which is dissolved with an emulsifier, as an oil phase, emulsifying uniformly the water phase and the oil phase by stirring, then adding a coagulant for crosslinking gelation of sodium alginate droplets, then freeze drying, and finally carbonizing in the inert gas atmosphere to obtain the porous Si / C composite microsphere. The porous Si / C composite microsphere prepared by the method is used as cathode materials of the lithium ion batteries, and has good electrochemical cycling stability and rate capability. The preparation method has the advantages of no need of expensive equipment, simple process, convenient operation, and easy scale production.
Description
Technical field
The present invention relates to a kind of preparation method of porous Si/C complex microsphere, belong to technical field of lithium ion battery electrode.
Background technology
The demand of fast development to height ratio capacity, long circulation life and high security power lithium-ion battery of electric automobile is day by day urgent.In lithium ion battery negative material, (theoretical specific capacity is up to 4200 mAh × g with the incomparable capacity advantage of other material for silicon
-1) and high security obtain the extensive concern of researcher.But silicon-based anode volumetric expansion in cyclic process, up to 300%, easily causes material efflorescence, lose and collector electrical contact, cause its cycle performance to decline rapidly.Current one of method of silicon based anode material performance of improving is by silicon materials nanometer, prepares nanosphere, nanotube, nanofiber etc.; Two is that silicon is placed in cushioning frame, the volumetric expansion of dispersion and buffering silicon, wherein material with carbon element because its change in volume in charge and discharge process is relatively little, cyclical stability and conductivity more excellent, be the comparatively ideal cushioning frame material of silicon.
At document (1) Nature Materials, 2010, in 9:353-358, A. burnt dendroid carbon black granules is skeleton by the people such as Magasinki, utilize silane for silicon source is at chemical vapor deposited silicon nano particle above, recycling propylene gas does carbon source, secondary chemical vapor carbon deposition, granulation is carried out to primary particle simultaneously, namely obtain the silicon-carbon complex microsphere that average grain diameter is 20 microns.This material is used for lithium ion battery negative pole and has good electrochemical cycle stability, and after circulating 100 weeks under the multiplying power of 1C, specific capacity can also be stabilized in 1500 mAh × g
-1.But the preparation process of this material relates to twice chemical vapour deposition (CVD), cost is high and power consumption is large, adopts silane to be gas silicon source simultaneously, and toxicity is large, inflammable and explosive, and operating procedure is complicated.
At document (2) The Journal of Physical Chemistry C, 2011, in 115:14148-14154, the people such as Ya-Xia Yin have prepared Si-C composite material using sodium alginate as carbon source, owing to containing carboxyl in sodium alginate molecule, can form hydrogen bond with the hydroxyl of silicon face, be beneficial to the dispersion of nano silica fume, in addition, after sodium alginate carbonization, there is high conductance, there is loose structure simultaneously.Its preparation method is utilize electrojet instrument to be ejected in copper chloride solution by the mixed liquor of silicon and sodium alginate to impel its quick-gelatinizing, carbonization again after freeze drying, obtains the silicon-carbon complex microsphere that average grain diameter is 50 microns.This material is used for lithium ion battery negative, at 50 mA × g
-1current density under circulation 50 weeks afterwards capacity from 2500 mAh × g
-1drop to 1000 mAh × g
-1.The method needs electrojet instrument, and productive rate is low, it is high to consume energy, and adds production cost.
Summary of the invention
The object of the present invention is to provide a kind of easy method preparing porous Si/C complex microsphere, it is characterized in that, using the sodium alginate aqueous solution of dispersed silicon as aqueous phase, to the isooctane solution of emulsifying agent be dissolved with as oil phase, make the two emulsification even at stirring condition, add coagulant subsequently and make sodium alginate drop cross-linked gel, then freeze drying, finally carbonization obtains porous Si/C complex microsphere under an inert atmosphere.The technological process of the inventive method as shown in Figure 1, comprises following concrete steps.
(1) prepare mass concentration be the sodium alginate aqueous solution of 5 ~ 10 g/L as aqueous phase, the ratio being 1:2 ~ 4:5 according to the mass ratio of silica flour and sodium alginate takes silica flour, joins in sodium alginate aqueous solution, and stirring makes it be uniformly dispersed; Preparation mass concentration be the sorbester p17 isooctane solution of 30 ~ 50 g/L as oil phase, the volume ratio of aqueous phase and oil phase is 1:2 ~ 2:1; Under the mixing speed of 500 ~ 1500 revs/min, in sorbester p17 isooctane solution, instillation is dispersed with the sodium alginate soln of silicon, emulsification 10 ~ 30 minutes; Then instillation accounts for the Tween 80 aqueous solution that the mass concentration of aqueous phase and oil phase cumulative volume 1% ~ 3% is 40 ~ 70 g/L, continues emulsification 5 ~ 10 minutes; Then instillation accounts for the copper chloride coagulant aqueous solution that the mass concentration of aqueous phase and oil phase cumulative volume 1% ~ 5% is 100 ~ 180 g/L, makes its gel solidification 10 ~ 30 minutes; Centrifugation, absolute ethanol washing 3 ~ 5 times, to remove isooctane, washed product is placed in liquid nitrogen flash freezing, then freeze drying obtains compound powder in 20 ~ 30 hours.
(2) compound powder step (1) obtained under an inert atmosphere, with 5 ~ 10
othe ramp of C/ minute is to 800 ~ 1000
oc carburizing reagent 2 ~ 4 hours, then cools to room temperature with the furnace.Wherein inert gas is the one in nitrogen or argon gas.
(3) be the hydrofluoric acid solution that 1:200 ~ 1:100 is placed in that mass fraction is 5 ~ 10% by the carbonized product of step (2) according to solid-to-liquid ratio, soak 0.5 ~ 1.5 hour, obtain suspension, centrifugation, absolute ethanol washing 3 ~ 5 times is to remove hydrofluoric acid, 50 ~ 100
oc vacuumize 10 ~ 20 hours, namely obtains porous Si/C complex microsphere.
The XRD spectra of porous Si/C complex microsphere as shown in Figure 2, except containing except silicon and carbon in material, also contains the cuprous oxide be transformed by coagulant copper chloride; Adopt German Supra 55 type field emission microscopy observation sample topography, as shown in Figure 3, compound is spheric granules to the stereoscan photograph of porous Si/C complex microsphere, and particle diameter is between 2-15 micron, and silicon grain adheres to the surfaces externally and internally of soft carbon film; Adopt NEC company JEM-2100 type high resolution transmission electron microscopy to observe the structure of silicon-carbon complex microsphere as shown in Figure 4, nano silicon particles is inlayed or is adhered on carbon film.
Porous Si/C complex microsphere the inventive method synthesized, as lithium ion battery negative material, mixes by the mass ratio of 60:30:10 with commercially available acetylene black conductor and sodium alginate binding agent, is coated on copper foil of affluxion body, in vacuum drying oven 80
oc is dried, and the thickness of compressing tablet to 30 ~ 70 mm, obtain the electrode slice that diameter is 1 cm, in 120 with sheet-punching machine
odry 24 hours of C vacuum (<10 Pa).Using metal lithium sheet as to electrode, adopt Celgard 2400 barrier film, 1 mol × L
-1liPF
6+ EC+DMC+DEC (EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at German M.Braun company Unlab type dry argon gas glove box (H
2o < 1 ppm, O
2< 1 ppm) in be assembled into experimental cell, adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test, discharge and recharge cut-ff voltage scope is 0.01 V ~ 1.5 V (vs. Li
+/ Li), probe temperature is 25
oc, as shown in Figure 5 and Figure 6, the specific capacity head of porous Si/C complex microsphere can reach 2280.5 mAh × g in week to test result
-1, efficiency is 67% first, at 200 mA × g
-1current density under circulation 100 weeks afterwards specific capacity still can reach 1100 mAh × g
-1, and coulombic efficiency remains on more than 98% always; This material also has excellent high rate performance, at 2 A × g
-1current density under, specific capacity still can reach 650 mAh × g
-1.
Distinguishing feature and the advantage of the inventive method are: adopt simple emulsification-gelation process can obtain the Si/C complex microsphere with loose structure, use it for lithium ion battery negative material and have good electrochemical cycle stability and high rate performance.The inventive method does not need expensive instrument and equipment, and technique is simple, easy to operate, is convenient to large-scale production.
Accompanying drawing explanation
Fig. 1 is the process flow diagram adopting the inventive method to prepare porous Si/C complex microsphere.
Fig. 2 is the XRD spectra of porous Si/C complex microsphere prepared by embodiment 1.Abscissa is angle, and unit is: degree (
o); Ordinate is diffracted intensity, and unit is: absolute unit (a.u.).
Fig. 3 be embodiment 1 prepare porous Si/C complex microsphere sweep emission scan electromicroscopic photograph.
Fig. 4 is the high-resolution-ration transmission electric-lens photo of porous Si/C complex microsphere prepared by embodiment 1.
Fig. 5 is electrochemistry cycle performance and the coulombic efficiency curve of porous Si/C complex microsphere prepared by embodiment 1.Abscissa is circulating cycle number, and unit is: week; Left side ordinate is specific discharge capacity, and unit is: MAH × gram
-1(mAh × g
-1), right side ordinate is coulombic efficiency, and unit is: percentage (%).The specific discharge capacity of curve a-porous Si/C complex microsphere and the relation curve of circulating cycle number; The coulombic efficiency of curve b-porous Si/C complex microsphere and the relation curve of circulating cycle number.
Fig. 6 is the high rate performance curve of porous Si/C complex microsphere prepared by embodiment 1.Abscissa is circulating cycle number, and unit is: week; Ordinate is specific discharge capacity, and unit is: MAH × gram
-1(mAh × g
-1).
Embodiment
Embodiment 1: take 0.3 g sodium alginate and 0.17 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, take 1.2 g sorbester p17s is dissolved in 40 mL isooctane solutions simultaneously, take 0.09 g Tween 80 to be dissolved in the 2 mL aqueous solution, take 0.269 gCuCl
2be dissolved in 2 mL water.Proceed in there-necked flask by sorbester p17 isooctane solution, under the mechanical agitation of 500 revs/min, instillation is dispersed with the sodium alginate soln of silicon, emulsification 15 minutes, then instills the Tween 80 aqueous solution, then continues emulsification 5 minutes, then instill CuCl
2the aqueous solution, makes its gel solidification 15 minutes.By cured product centrifugation, and with absolute ethanol washing 4 times to remove isooctane, cured product is placed in liquid nitrogen flash freezing, then moves in freeze drier dry 25 hours.
Above-mentioned dried compound powder is laid in aluminium oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5
othe heating rate of C/ minute is raised to 800
oc, is incubated and carries out carbonization in 4 hours.
It is the hydrofluoric acid solution of 5% that the silicon-carbon compound powder obtained after the above-mentioned carbonization of 0.24 g is placed in 30 mL mass fractions, soaks 0.5 hour, centrifugation, and absolute ethanol washing 4 times, to remove hydrofluoric acid, is then placed in 50
odry 20 hours of the vacuum drying oven of C, namely obtains porous Si/C complex microsphere.
The XRD spectra of porous Si/C complex microsphere as shown in Figure 2, except containing except silicon and carbon in material, also contains the cuprous oxide be transformed by coagulant copper chloride; Adopt German Supra 55 type field emission microscopy observation sample topography, as shown in Figure 3, compound is spheric granules to the stereoscan photograph of porous Si/C complex microsphere, and particle diameter is between 2-15 micron, and silicon grain adheres to the surfaces externally and internally of soft carbon film; Adopt NEC company JEM-2100 type high resolution transmission electron microscopy to observe the structure of silicon-carbon complex microsphere as shown in Figure 4, nano silicon particles is inlayed or is adhered on carbon film.
Porous Si/C complex microsphere the inventive method synthesized, as lithium ion battery negative material, mixes by the mass ratio of 60:30:10 with commercially available acetylene black conductor and sodium alginate binding agent, is coated on copper foil of affluxion body, in vacuum drying oven 80
oc is dried, and the thickness of compressing tablet to 30 ~ 70 mm, obtain the electrode slice that diameter is 1 cm, in 120 with sheet-punching machine
odry 24 hours of C vacuum (<10 Pa).Using metal lithium sheet as to electrode, adopt Celgard 2400 barrier film, 1 mol × L
-1liPF
6+ EC+DMC+DEC (EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at German M.Braun company Unlab type dry argon gas glove box (H
2o < 1 ppm, O
2< 1 ppm) in be assembled into experimental cell, adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test, discharge and recharge cut-ff voltage scope is 0.01 V ~ 1.5 V (vs. Li
+/ Li), probe temperature is 25
oc, as shown in Figure 5 and Figure 6, the specific capacity head of porous Si/C complex microsphere can reach 2280.5 mAh × g in week to test result
-1, efficiency is 67% first, at 200 mA × g
-1current density under circulation 100 weeks afterwards specific capacity still can reach 1100 mAh × g
-1, and coulombic efficiency remains on more than 98% always; This material also has excellent high rate performance, at 2 A × g
-1current density under, specific capacity still can reach 650 mAh × g
-1.
Embodiment 2: take 0.3 g sodium alginate and 0.2 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, take 2.4 g sorbester p17s is dissolved in 60 mL isooctane solutions simultaneously, take 0.17 g Tween 80 to be dissolved in the 3 mL aqueous solution, take 0.269 gCuCl
2be dissolved in 2.5 mL water.Proceed in there-necked flask by sorbester p17 isooctane solution, under the mechanical agitation of 800 revs/min, instillation is dispersed with the sodium alginate soln of silicon, emulsification 20 minutes, then instills the Tween 80 aqueous solution, then continues emulsification 8 minutes, then instill CuCl
2the aqueous solution, makes its gel solidification 20 minutes.By cured product centrifugation, cured product, to remove isooctane, is placed in liquid nitrogen flash freezing by absolute ethanol washing 4 times, then to move in freeze drier dry 20 hours.
Above-mentioned dried compound powder is laid in aluminium oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5
othe heating rate of C/ minute is raised to 900
oc, is incubated and carries out carbonization in 3 hours.
It is the hydrofluoric acid solution of 10% that the silicon-carbon compound powder obtained after the above-mentioned carbonization of 0.24 g is placed in 30 mL mass fractions, soaks 1 hour, centrifugation, and absolute ethanol washing 4 times, to remove hydrofluoric acid, is placed in 70
odry 18 hours of the vacuum drying oven of C, namely obtains porous Si/C complex microsphere.
Embodiment 3: take 0.4 g sodium alginate and 0.2 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, take 2.4 g sorbester p17s is dissolved in 60 mL isooctane solutions simultaneously, take 0.17 g Tween 80 to be dissolved in the 3 mL aqueous solution, take 0.538 gCuCl
2be dissolved in 3 mL water.Proceed in there-necked flask by sorbester p17 isooctane solution, under the mechanical agitation of 1000 revs/min, instillation is dispersed with the sodium alginate soln of silicon, emulsification 20 minutes, then instills the Tween 80 aqueous solution, then continues emulsification 8 minutes, then instill CuCl
2the aqueous solution, makes its gel solidification 20 minutes.By cured product centrifugation, cured product, to remove isooctane, is placed in liquid nitrogen flash freezing by absolute ethanol washing 5 times, then to move in freeze drier dry 28 hours.
Above-mentioned dried compound powder is laid in aluminium oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5
othe heating rate of C/ minute is raised to 800
oc, is incubated and carries out carbonization in 3 hours.
It is the hydrofluoric acid solution of 8% that the silicon-carbon compound powder obtained after the above-mentioned carbonization of 0.255 g is placed in 30 mL mass fractions, soaks 1.5 hours, centrifugation, and absolute ethanol washing 5 times, to remove hydrofluoric acid, is placed in 80
odry 15 hours of the vacuum drying oven of C, namely obtains porous Si/C complex microsphere.
Embodiment 4: take 0.5 g sodium alginate and 0.35 g silica flour joins in beaker, add 60 mL deionized waters, magnetic agitation makes it be uniformly dispersed, take 4 g sorbester p17s is dissolved in 80 mL isooctane solutions simultaneously, take 0.27 g Tween 80 to be dissolved in the 4 mL aqueous solution, take 0.897 gCuCl
2be dissolved in 5 mL water.Proceed in there-necked flask by sorbester p17 isooctane solution, under the mechanical agitation of 1500 revs/min, instillation is dispersed with the sodium alginate soln of silicon, emulsification 30 minutes, then instills the Tween 80 aqueous solution, then continues emulsification 10 minutes, then instill CuCl
2the aqueous solution, makes its gel solidification 30 minutes.By cured product centrifugation, cured product, to remove isooctane, is placed in liquid nitrogen flash freezing by absolute ethanol washing 5 times, moves to freeze drier dry 30 hours.
Above-mentioned dried compound powder is laid in aluminium oxide porcelain boat, is placed in the thermal treatment zone of tube furnace, in a nitrogen atmosphere, according to 5
othe heating rate of C/ minute is raised to 1000
oc, is incubated and carries out carbonization in 2 hours.
It is the hydrofluoric acid solution of 5% that the silicon-carbon compound powder obtained after the above-mentioned carbonization of 0.36 g is placed in 40 mL mass fractions, soaks 1.5 hours, centrifugation, and absolute ethanol washing 5 times, to remove hydrofluoric acid, is placed in 90
odry 10 hours of the vacuum drying oven of C, namely obtains porous Si/C complex microsphere.
Claims (3)
1. a preparation method for porous Si/C complex microsphere, is characterized in that, comprises following processing step:
(1) prepare mass concentration be the sodium alginate aqueous solution of 5 ~ 10 g/L as aqueous phase, the ratio being 1:2 ~ 4:5 according to the mass ratio of silica flour and sodium alginate takes silica flour, joins in sodium alginate aqueous solution, and stirring makes it be uniformly dispersed; Preparation mass concentration be the sorbester p17 isooctane solution of 30 ~ 50 g/L as oil phase, the volume ratio of aqueous phase and oil phase is 1:2 ~ 2:1; Under the mixing speed of 500 ~ 1500 revs/min, in sorbester p17 isooctane solution, instillation is dispersed with the sodium alginate soln of silicon, emulsification 10 ~ 30 minutes; Then instillation accounts for the Tween 80 aqueous solution that the mass concentration of aqueous phase and oil phase cumulative volume 1% ~ 3% is 40 ~ 70 g/L, continues emulsification 5 ~ 10 minutes; Then instillation accounts for the coagulant aqueous solution that the mass concentration of aqueous phase and oil phase cumulative volume 1% ~ 5% is 100 ~ 180 g/L, makes its gel solidification 10 ~ 30 minutes; Centrifugation, absolute ethanol washing 3 ~ 5 times, to remove isooctane, washed product is placed in liquid nitrogen flash freezing, then freeze drying obtains compound powder in 20 ~ 30 hours;
(2) compound powder step (1) obtained under an inert atmosphere, with 5 ~ 10
othe ramp of C/ minute is to 800 ~ 1000
oc carburizing reagent 2 ~ 4 hours, then cools to room temperature with the furnace;
(3) be the hydrofluoric acid solution that 1:200 ~ 1:100 is placed in that mass fraction is 5 ~ 10% by the carbonized product of step (2) according to solid-to-liquid ratio, soak 0.5 ~ 1.5 hour, obtain suspension, centrifugation, absolute ethanol washing 3 ~ 5 times is to remove hydrofluoric acid, 50 ~ 100
oc vacuumize 10 ~ 20 hours, namely obtains porous Si/C complex microsphere.
2. preparation method according to claim 1, is characterized in that, in step (1), described coagulant is copper chloride.
3. preparation method according to claim 1, is characterized in that, in step (2), described inert gas is the one in nitrogen or argon gas.
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