CN107919469A - A kind of method of silicon-carbon nanotube graphene synthetic for manufacturing crinkled shape and the synthetic based on this method manufacture - Google Patents

A kind of method of silicon-carbon nanotube graphene synthetic for manufacturing crinkled shape and the synthetic based on this method manufacture Download PDF

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CN107919469A
CN107919469A CN201711173126.9A CN201711173126A CN107919469A CN 107919469 A CN107919469 A CN 107919469A CN 201711173126 A CN201711173126 A CN 201711173126A CN 107919469 A CN107919469 A CN 107919469A
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silicon
crinkled
graphene
silico
synthetic
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张喜栋
蒋韩权
吉大燮
金宣冏
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Korea Institute of Geoscience and Mineral Resources KIGAM
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Korea Institute of Geoscience and Mineral Resources KIGAM
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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
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/23—Oxidation
    • 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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

One embodiment of the invention provides a kind of method for the silicon-carbon nanotube graphene synthetic for manufacturing crinkled shape, its step includes：The step of manufacture contains silicon, carbon nanotubes, the mixture of graphene oxide and solvent (step 1)；And the spray drying mixture, and (step 2) the step of be heat-treated.Another embodiment of the present invention provides a kind of silicon-carbon nanotube graphene synthetic of crinkled shape, it includes：Agglomerate the silicon flocculating agent of multiple silicon particles；Around multiple crinkled graphenes of the silicon flocculating agent；And between the silicon particle, between the crinkled graphene and between the silicon particle and crinkled graphene bridging point multiple carbon nanotubes.

Description

A kind of method of silico-carbo nanotube-graphene alkene synthetic for manufacturing crinkled shape and it is based on The synthetic of this method manufacture
Technical field
The present invention relates to a kind of method for the silico-carbo nanotube-graphene alkene synthetic for manufacturing crinkled shape, based on this method The synthetic of manufacture and the storage battery including the synthetic, more specifically, being related to a kind of manufacture includes that silicon, carbon nanometer will be contained The method of the synthetic for the step of mixture of pipe and graphene oxide is spray-dried and is heat-treated, the system based on this method The synthetic made and the storage battery including the synthetic.
Background technology
In early period in technique of the silicon ingot for manufacturing semiconductor and solar energy battery adopted silicon chip, generation contains a large amount of silicon grains The slurries of son, wherein most are processed as discarded object.But if the silicon being separated and recovered from from discarded silicon mud is in order to high attached Value added recycling, is applied as lithium-ions battery cathode material, then in energy economy ＆ environment side, it is contemplated that can obtain huge Effect.
In addition, lithium-ions battery is due to its height output, the characteristic of high-energy, as the sub- instrument of Portable power, combined drive The main energy sources of electrical automobile etc., are attracted attention in energy field.At present, the carbon used as lithium-ions battery cathode material Although coulombic efficiency can reach 99.9% to series cathode material in a short time, there is the limitation of low-voltage capacity.Therefore, silicon Series cathode material has the theoretical capacity (3500mAh/g) of about 10 times of carbon series cathode materials, can be to overcome the limitation Strong candidate's cathode material.But silicon is in the charging and discharging of lithium-ions battery, the larger change meeting based on volume Cause cracking, due to being continuously generated unstable solid electrolyte on the decomposition reaction silicon face based on lithium ion and electrolyte Interface (Solid Electrolyte Interface, SEI), therefore with the progress of charging-discharging cycle, there are capacitance reduction The problem of.In order to solve this problem, researcher is researching and developing the synthetic technology of silicon and carbon system material.
The performance of lithium-ions battery is determined by cathode material, but needs sufficient high conductivity, wide specific surface area, high temperature Condition needed for stability, uniform pore structure, low cost etc..Mainly by including high purity graphite (graphite), activated carbon (Activated carbon；AC), carbon nanotubes (Carbon nanotubes；MWCNTs), graphene (Graphene；GR) Carbon-based material is widely used as lithium-ions battery cathode material.Wherein, there is wide specific surface area (theoretical value 2,600m2/ G), faster electron mobility and the graphene of excellent physical characteristic as the material for energy storage device by looking steadily Mesh.However, using cathode material made of graphene between the graphene film of two-dimensional structure with layer again constantly occurs Folded and coacervation, so as to cause electrolyte to be difficult the problem of being impregnated with synthetic electrode.
Korean granted patent is announced No. 10-1368474 and discloses the skill for being coated with carbon in silicon particle using core shell structure Art is to improve problem.Using impeller flour mill using silicon nano and petroleum pitch table or carbon black, graphene manufacture silicon- Carbon structure and the maximum charge capacity for obtaining 819mAh/g.The results show come out impeller flour mill be difficult be coated with carbon member The plating carbon of the problem of element, generation carbon or graphene are laminated again and simple silicon face is difficult silicon volume when solving discharge and recharge The problem of varying widely.
It is to be combined by silane based compound with carbon that Korean granted patent, which announces the technology disclosed in No. 10-1686331, Assembly carry out liquid reactions, manufacture silico-carbo synthetic, and be used for electric power storage pool cathode.As a result, obtained after 100 cycles Efficiency for charge-discharge is 95% high value.Carbon assembly it is mesoporous in the silicon systems material that has due to being subject to the mesoporous of carbon assembly Space limitation, the expansion of silicon volume, the mesoporous stacking that there are problems that solving carbon assembly can be limited.However, carbon combines Body cannot be fully coated in silicon face, make silicon exposure in the electrolytic solution, when for a long time in use, in the presence of cannot ensure electricity The problem of stability of pole.
Therefore, the task of top priority is a kind of battery terminal material of exploitation, it can solve to receive using two-dimensional graphene and carbon The problem of stacking again and cohesion for occurring during mitron, the expansion issues of silicon large volume can be housed, and utilize carbon double application Silicon face, to prevent silicon face and electrolyte from directly contacting.
【Look-ahead technique document Prior Art】
【Patent document】
(patent document 1) Korean granted patent announces No. 10-1368474
(patent document 2) Korean granted patent announces No. 10-1686331
The content of the invention
The present invention exists as the technical solution for solving the problems, such as foregoing background technology, the purpose of the present invention In, there is provided a kind of silico-carbo nanotube-graphene alkene synthetic of crinkled shape, it can solve to use two-dimensional graphene and carbon nanometer The problem of stacking again and cohesion for occurring during pipe, the collision of silicon large volume can be housed, can prevent silicon face and electrolyte Directly contact.
Another object of the present invention is to, there is provided a kind of silico-carbo nanotube-graphene alkene synthetic of crinkled shape, the synthesis When thing is applied to battery terminal material, excellent electrology characteristic, high-capacitance are shown.
A further object of the present invention is, by re-using discarded silicon mud, for excellent electrology characteristic Battery terminal material.
In order to realize the purpose, state as the present invention provides a kind of silico-carbo nanotube-graphene alkene for manufacturing crinkled shape The method of synthetic, its step include：The step of manufacturing the mixture containing silicon, carbon nanotubes, graphene oxide and solvent (step It is rapid 1)；And the spray drying mixture, and (step 2) the step of be heat-treated.
In one embodiment, the silicon of the step 1 can be by carrying out Ore Leaching to discarded silicon mud, and is optionally sequestered and returns Receive silicon and purchase.
In one embodiment, the step of being dried is additionally included in after the Ore Leaching, to containing having carried out the drying After the solution of the discarded silicon mud of step carries out ultrasonication, it is centrifuged, so as to be optionally sequestered and recycle silicon.
In one embodiment, the ultrasonication, carry out 1 hour to 10 it is small when, it is described centrifugation be with 100rpm extremely The rotary speed of 1000rpm performs 1 minute to 60 minutes.
In one embodiment, the carbon nanotubes of the step 1 can by by carbon nanotubes sour molten including sulfuric acid and nitric acid Decentralized processing is carried out in liquid and is prepared.
The carbon nanotube concentration of the mixture of step 1 described in one embodiment can be 0.05wt% to 0.2wt%.
In one embodiment, the silicon concentration of the mixture of the step 1 can be 0.3wt% to 1.3wt%.
In one embodiment, the graphene oxide concentration of the mixture of the step 1 is 0.1wt% to 0.5wt%.
In one embodiment, the step 2 is by second fluid nozzle, by the mixture of the step 1 with aerosol droplets The step of form is sprayed (step 2a)；And the drop of the spraying formation is set to pass through tubulose heating furnace by transferring gas Go forward side by side drying, the step of reductive heat treatment (step 2b) and carry out.
In one embodiment, the heat treatment temperature of step 2 or the step 2b can be 500 DEG C to 1000 DEG C.
In addition, in order to realize the purpose, another pattern of the invention provides a kind of silico-carbo nanometer for manufacturing crinkled shape The method of pipe-graphene synthetic, its step include：After discarded silicon mud is carried out Ore Leaching, optionally will from leachate Silicon separate and recycling, and to carbon nanotubes carry out acid treatment the step of (step 0)；Manufacture includes the silicon of the recycling, through at sour The step of mixture of the carbon nanotubes of reason, graphene oxide and solvent (step 1)；By second fluid nozzle, by the step 1 Mixture the step of being sprayed in the form of aerosol droplets (step 2a)；And by transferring gas, make the spraying The step of drop of formation is through tubulose heating furnace and is dried, reductive heat treatment (step 2b).
And then in order to realize the purpose, another pattern of the invention provide a kind of silico-carbo nanotube of crinkled shape- Graphene synthetic, it includes：Agglomerate the silicon flocculating agent of multiple silicon particles；Around multiple crinkled graphite of the silicon flocculating agent Alkene；And between the silicon particle, between the crinkled graphene and a structure of an essay for the silicon particle and crinkled graphene Multiple carbon nanotubes of bridge point.
And then in order to realize the purpose, another pattern of the invention provides a kind of storage battery, it includes：Anode；Contain There is the cathode of silico-carbo nanotube-graphene alkene synthetic as claimed in claim 12；The separation possessed between the anode and cathode Film；And electrolyte.
State as according to the present invention, using manufactured synthetic as during battery terminal materials'use, it is big to can remove silicon The problem of expanding to volume, can prevent that silicon is contacted with the direct of electrolyte in synthetic during discharge and recharge, shows that excellent electricity is special Property.
In addition, manufactured synthetic is connected with carbon nanotubes by making between multiple silicon particles, it is possible to increase conductivity, it is multiple Also carbon nanotubes is connected between crinkled graphene, can not only prevent stratification, but also with the excellent of conductivity can be improved Point.
The effect of the present invention it will be appreciated that be not limited to the effect, but including be based on detailed description of the invention or Invention described in patent claims form can the obtained institute of inference it is effective.
Brief description of the drawings
Fig. 1 is the side of the silico-carbo nanotube-graphene alkene synthetic of manufacture crinkled shape of the diagram based on one embodiment of the invention The exemplary schematic diagram of method.
Fig. 2 is the side of the silico-carbo nanotube-graphene alkene synthetic of manufacture crinkled shape of the diagram based on one embodiment of the invention Another exemplary schematic diagram of method.
Fig. 3 is to illustrate silico-carbo-graphene synthetic (a), the exemplary signal of silico-carbo nanotube-graphene alkene (b) synthetic Figure.
Fig. 4 is the embodiment 1 (c, f), embodiment 2 (b, e) and embodiment 3 (a, d) by Scanning Electron microscope photographing In manufactured crinkled shape silico-carbo nanotube-graphene alkene synthetic shape high magnification (40000x) and low range (10000x) photo.
Fig. 5 is the X for illustrating the silico-carbo nanotube-graphene alkene synthetic of manufactured crinkled shape into embodiment 3 of embodiment 1 The curve map of ray diffraction analysis result.
Fig. 6 is the drawing for illustrating the silico-carbo nanotube-graphene alkene synthetic of manufactured crinkled shape into embodiment 3 of embodiment 1 The curve map of graceful analytic approach implementing result.
Fig. 7 is the diagram electrostatic of manufactured storage battery based on charging-discharging cycle into embodiment 6 and comparative example 1 of embodiment 4 The curve map of capacity (a) and coulombic efficiency (b).
Fig. 8 is the side of the silico-carbo nanotube-graphene alkene synthetic of manufacture crinkled shape of the diagram based on one embodiment of the invention Another exemplary schematic diagram of method.
Embodiment
Hereinafter, referring to the drawings, preferred embodiment of the present invention is described in detail.
By referring to accompanying drawing and its embodiment that describes in detail, advantages of the present invention and feature and realize that its method will It is gradually clear.
But the invention is not restricted to the embodiment of following record, but various forms that can be different are implemented, simply, this Embodiment be in order to the present invention it is easier to understand, and enable the technical field of the invention have usual knowledge technical staff Enough it is more fully understood by the category of invention and provides.Moreover, the present invention is only defined by the scope of claim.
And then when illustrating the present invention, when judge related known technology when explanation may obscure the present invention purport when, then By its detailed description is omitted.
Research (Application No. 10-2017-0018239, before the applying date of the invention before the present inventor It is undisclosed) in, as shown in Fig. 3 (a), it have developed silico-carbo-graphene synthetic.First, micron-sized silicon particle is dissolved in water In and carburet thing crushed together, by particle size drop to less than 1 micron size at the same time manufacture scribble carbon compound Silico-carbo suspension.Manufacture afterwards is internal silicon, and outside scribbles the spherical silico-carbo synthetic of carbon, by manufactured silico-carbo synthetic After being mixed with graphene oxide, it is incorporated into making graphene oxide surround silico-carbo synthetic by aerosol process, passes through Silico-carbo element-graphene synthetic is manufactured, develops high-capacity battery cathode material.At this time, manufactured silico-carbo-graphene closes It is more than 1500mAh/g to be shown in 50 cycle capacities in lithium-ions battery evaluating characteristics result into thing.In silico-carbo-graphite The inside of alkene synthetic is there are multiple silico-carbo synthetics, and graphene surrounds silico-carbo synthetic again in outside, so that dual multiple Close carbon material.
Simply, present inventors have developed silico-carbo nanotube-graphene alkene synthetic, it is compared to such as Fig. 3 (a) institutes The invention of silico-carbo-graphene synthetic of research and development before showing, whens lithium-ions battery evaluating characteristics, which can further improve, leads Electric rate, by controlling large volume to change, can improve electrochemical properties during discharge and recharge, and then complete the present invention.
State as the present invention provides a kind of method for the silico-carbo nanotube-graphene alkene synthetic for manufacturing crinkled shape, the party Method includes：The step of manufacturing the mixture containing silicon, carbon nanotubes, graphene oxide and solvent (step 1) S10；And to institute The step of stating mixture to be spray-dried, and being heat-treated (step 2) S20.
Hereinafter, the side of the silico-carbo nanotube-graphene alkene synthetic for the crinkled shape of manufacture being related to for state as the present invention Method, is described in detail respectively by step.
In the method for the silico-carbo nanotube-graphene alkene synthetic for the crinkled shape of manufacture that state as the present invention is related to, institute State the mixture that step 1 (S10) manufacture includes silicon, carbon nanotubes, graphene oxide and solvent.
The silicon of the step 1 can be by carrying out Ore Leaching to discarded silicon mud, and is optionally sequestered and recycles silicon and purchase 's.
The discarded silicon mud can produce in silicon chip manufacturing process, it is also possible in the cut-out or grinding of silicon chip Produced in technique.In the Cutting process, using metal scroll saw (wire saw) and using oily containing silicon carbide and cutting Deng cut-out slurries, the silicon mud containing substantial amounts of silicon particle and silicon carbide can be produced.
As the acid that can be used in the Ore Leaching, hydrochloric acid, sulfuric acid, nitric acid etc. can be used, salt preferably can be used Acid.During using mixed acid, silicon may be dissolved, therefore it is not recommended that be used.
The Ore Leaching can be by adding the discarded silicon mud and carrying out in acid solution, and the concentration of the acid solution is preferred For 1M to 5M, the discarded silicon mud concentration of acid solution is preferably 0.5g/ml to 2g/ml.The Ore Leaching concentration and discarded silicon mud are dense The metal impurities of silicon mud are discarded in degree to be readily removable, and can minimize the wasting of resources.
The Ore Leaching preferably at a temperature of 50 DEG C to 150 DEG C, carry out 1 hour to 10 it is small when.In the Ore Leaching temperature Degree and time range, the metal impurities of discarded silicon mud can be easily removed, and can minimize the wasting of resources.
Room temperature cooling is carried out to the solution through the Ore Leaching, can be in remaining discarded silicon mud after separating and filtering liquid Addition distilled water is washed.
Drying steps are may also include after the Ore Leaching, by through the execution drying steps, comprising discarded silicon mud After solution carries out ultrasonication, it is centrifuged and optionally separates and recycle silicon.
In solution comprising the discarded silicon mud, the discarded silicon mud：Solid-to-liquid ratio (the g of distilled water：ML it is preferably) 1：50 To 200.In the range of the solid-to-liquid ratio, after chat the ultrasound of step and involve centrifuging treatment and can easily carry out, money can be made Source, which wastes, to be minimized.
The ultrasonication preferably be carried out 1 hour to 10 it is small when.It is described molten in the range of the ultrasonic treatment time The silicon of silicon mud and silicon carbide (SiC) are discarded in liquid to be easily separated, and can minimize the wasting of resources.
Preferably, it is described centrifuge by centrifugal apparatus by the solution of the ultrasonication with 100rpm extremely The rotary speed of 1000rpm, carries out 1 minute to 60 minutes., can in the centrifugation rotary speed and in the range of the time Silicon is easily recycled, the wasting of resources can be minimized.
The silicon particle size of the recycling can be 1 μm to 5 μm.
The carbon nanotubes of the step 1 can be by individual layer wall carbon nano tube (Single-walled Carbon Nanotube), double-wall carbon nanotubes (Double-Walled Carbon Nanotube), multi-walled carbon nanotube (Multi- Walled Carbon Nanotube), select in the group of cord-like carbon nanotubes (Rope Carbon Nanotube) composition More than one, are preferably multi-walled carbon nanotube, can improve the electrology characteristic of manufactured synthetic.
The carbon nanotubes of the step 1 can be carried out by by carbon nanotubes in the acid solution including sulfuric acid and nitric acid Decentralized processing and purchase.Specifically, in sulfuric acid：The volume ratio of nitric acid is 2 to 4：Disperse in the acid solution of 1 form mixing Carbon nanotubes, when stirring 1 hour small to 10 at a temperature of 50 DEG C to 80 DEG C and can carry out.
When carrying out acid treatment to the carbon nanotubes, carbon nanotubes：The solid-to-liquid ratio (g/mL) of acid solution is 1：150 to 250。
Further include the step that the carbon nanotubes of the acid treatment is washed and dried using hydrochloric acid solution.
Before acid treatment, dispersiveness of the carbon nanotubes through acid treatment to solvent can be improved.
To respectively reach it fixed dense by the way that silicon, carbon nanotubes and graphene oxide are mixed with flux for the step 1 Degree, the spray drying of step is chatted after, can easily form the synthetic as subject matter.
The carbon nanotube concentration of the mixture of the step 1 is preferably 0.05wt% to 0.2wt%.When the mixture When carbon nanotube concentration is less than 0.05wt%, after chat in the silico-carbo nanotube-graphene alkene synthetic of manufactured crinkled shape in step Carbon nanotubes may not fulfil fully between silicon-silicon, between graphene-graphene the bridge formation of physics effect, comprising being made Synthetic storage battery in, there will be electrology characteristic it is low the problem of.When the carbon nanotube concentration of the mixture exceedes During 0.2wt%, carbon nanotubes is agglomerated in the silico-carbo nanotube-graphene alkene synthetic of manufactured crinkled shape, is including synthetic There may be the increased problem of interface resistance between electrolyte-synthetic in storage battery.
The silicon concentration of the mixture of the step 1 can be 0.3wt% to 1.3wt%, it is preferable that can be for 0.5wt% extremely 1.1wt%.When meeting the silicon concentration scope, can prevent from chatting after the silico-carbo nanotube of crinkled shape made of step- Excessive cohesion between the silicon particle of graphene synthetic, and during the progress discharge and recharge of the electrode comprising synthetic, can prevent from being cracked.
The graphene oxide concentration of the mixture of the step 1 finishes watching 0.1wt% to 0.5wt%, it is preferable that can be 0.1wt% to 0.3wt%.When the graphene oxide concentration of the mixture is less than 0.1wt%, chatted after made of step In the silico-carbo nanotube-graphene alkene synthetic of crinkled shape, the problem of cannot fully wrapping silicon there are crinkled graphene, Thus, when synthetic is applied to storage battery, it is possible to create the increased problem of interface resistance between electrolyte-synthetic.Work as institute When stating the graphene oxide concentration of mixture more than 0.5wt%, it may not be possible to be readily formed the synthetic of crinkled shape.
The solvent of the step 1 can be by distilled water, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, butanol, Ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethylacetylamide, n-methyl-2-pyrrolidone, hexane, ring Hexanone, toluene, chloroform, dichloro-benzenes, dimethylbenzene, trimethylbenzene, pyridine, methyl naphthalene, nitromethane, acrylonitrile, stearylamine, aniline and Dimethyl sulfoxide composition group in select more than one, it is preferable that can be used distilled water.
The step 1 may also include the step of ultrasonication and scattered manufactured mixture.
In the method for the manufacture silico-carbo nanotube-graphene alkene synthetic that one pattern of the present invention is related to, the step 2 (S20) the manufactured mixture is spray-dried, and is heat-treated.
What the step 2 can be carried out by step 2 and step 2b, the step 2a is by the step by second fluid nozzle The step of rapid 1 mixture is sprayed in the form of aerosol droplets；Step 2b is by transferring gas by the spraying shape Into drop pass through tubulose heating furnace, and be dried, the step of reductive heat treatment.
The second fluid nozzle of the step 2a can by based on the collision of liquids and gases and mixed and disperse so as to Can be purchased liquid.The second fluid nozzle is different from the nozzle of existing direct weighting formula, has under low voltage situations, can also tie up The advantages of holding ultra tiny spraying.
The transfer to heating furnace of the drop of the step 2b can be by selecting in the group that is made of argon gas, helium and nitrogen More than one gases transfer selected, it is preferable that can be transferred by argon gas.
The flow velocity of the gas for transferring drop to heating furnace of the step 2b can be 5L/min to 15L/min, it is preferable that Can be 5L/min to 10L/min.In the step 2b drop to heating furnace transfer when, flow velocity can be 2ml/min to 10ml/min, Preferably, it can be 2ml/min to 8ml/min.In the transfer gas flow rate and drop flow rates, the drying of drop and Self assembly can be carried out easily, can minimize the wasting of resources.
The drying temperature of step 2 or the step 2b can be 150 DEG C to 250 DEG C, it is preferable that can be 180 DEG C to 220 ℃.When the drying temperature is less than 150 DEG C, the problem of dividing solvent to evaporate there are drop internal and remain, cause crinkled The graphene cohesion of shape, so as to produce the problem of silicon cannot be easily wrapped by, the temperature of the heating furnace exceeds 250 DEG C When, when forming the synthetic comprising crinkled graphene oxide, excessive energy waste may be caused.
Transferring and being dried to heating furnace by the step 2b, so that existing solvent is evaporated in drop, Graphene oxide piece is molded (capillary molding) phenomenon by capillary and is mutually molded, and thus can make crinkled shape Graphene oxide is around silicon and agglomerates.
Synthetic by the drying of the step 2b can be trapped in the filter by cyclone separator, perform use afterwards It is heat-treated in reduced graphene oxide serving.
The heat treatment of step 2 or the step 2b can carry out at a temperature of 500 DEG C to 1000 DEG C, it is preferable that can be Carried out at a temperature of 600 DEG C to 900 DEG C.When the heat treatment temperature is less than 600 DEG C, it is understood that there may be the reduction of graphene oxide The worry of inefficiency, when the heat treatment temperature exceeds 1000 DEG C, it is understood that there may be the worry that silicon particle is damaged, and in stone In the reduction process of black olefinic oxide, there is a possibility that to consume the energy excessively.
The heat treatment of the step 2b can carry out in electric furnace, can be selected in the group being made of argon gas, helium and nitrogen Carried out in more than one the gaseous environment selected, it is preferable that carried out in ar gas environment.
When carrying out the heat treatment of the step 2b, gas can show predetermined flow rate, can be 0.5l/min to 2l/min, For the gas that can easily promote reductive heat treatment to carry out, its flow velocity not limited to this.
The heat treatment of step 2 or the step 2b can carry out 10 minutes to 100 minutes, it is preferable that can carry out 15 minutes To 80 minutes.When the heat treatment time was less than 10 minutes, it can cause graphene oxide that reduction cannot be effectively performed Problem, when the heat treatment time exceeds 100 minutes, in the reduction process of graphene oxide, exists and consumes the energy excessively Possibility.
Pass through method (the silico-carbo nanotube-graphene alkene synthetic made of step 1 to step 2), such as Fig. 3 (b) institutes Show, carbon nanotubes is connected between silicon-silicon particle, improve its conductivity, and equally have between crinkled graphene film Carbon nanotubes, can not only prevent stratification, and can improve conductivity.
And then manufactured silico-carbo nanotube-graphene alkene synthetic can buffer lithium storage battery discharge and recharge by carbon nanotubes When silicon large volume change and make its reduction, simultaneously as graphene covers all silicon, prevent silicon face with electrolyte from straight Contact, can prevent electrode damage, show excellent electrode characteristic.
Another pattern of the present invention provides a kind of method for the silico-carbo nanotube-graphene alkene synthetic for manufacturing crinkled shape, its Step includes：
After discarded silicon mud is carried out Ore Leaching, silicon is optionally sequestered and recycled from leachate, and to carbon nanotubes The step of carrying out acid treatment (step 0) S00；
Manufacture includes the step of mixture of the silicon of the recycling, the carbon nanotubes of acid treatment, graphene oxide and solvent (step 1) S10；
By second fluid nozzle, the step of mixture of the step 1 is sprayed in the form of aerosol droplets (step Rapid 2a) S21；And
The drop for forming the spraying by transferring gas passes through tubulose heating furnace and is dried, reductive heat treatment Step (step 2b) S22.
The Ore Leaching condition of discarded silicon mud of the step 0, the separation and recovery method of silicon, carbon nanotubes acid treatment, carbon are received The species of mitron can be same as described above.
The silicon of the step 1, the concentration of carbon nanotubes and graphene oxide and solvent can be same as described above.
The heat treatment condition of the spray condition of the step 2a and the step 2b can be same as described above.
The another pattern of the present invention provides a kind of silico-carbo nanotube-graphene alkene synthetic of crinkled shape, it includes：
Agglomerate the silicon flocculating agent of multiple silicon particles；Around multiple crinkled graphenes of the silicon flocculating agent；And institute State between silicon particle, between the crinkled graphene and between the silicon particle and crinkled graphene bridging point multiple carbon Nanotube.
In the silico-carbo nanotube-graphene alkene synthetic for the crinkled shape that state as the present invention is related to, the synthetic Internal such as Fig. 3 (b) is shown, and can include makes the silicon flocculating agent that carbon nanotubes is connected between silicon and silicon.The outside of the synthetic Same such as Fig. 3 (b) is shown, can be crinkled between crinkled graphene and crinkled graphene formed with carbon nanotubes is connected to Graphene flocculating agent.
The silico-carbo nanotube-graphene alkene synthetic for the crinkled shape that state as the present invention is related to, its particle size can be 1 μ M to 10 μm.
The silico-carbo nanotube-graphene alkene synthetic for the crinkled shape that state as the present invention is related to, its silicon：Carbon nanotubes weight It can be 100 to measure ratio：6.25 to 25.
The silico-carbo nanotube-graphene alkene synthetic for the crinkled shape that state as the present invention is related to, its silicon：Crinkled graphite Alkene weight ratio can be 100：6.25 to 62.5.
The another pattern of the present invention provides a kind of storage battery, it includes：Anode；Containing silicon as claimed in claim 12- The cathode of carbon nanotubes-graphene synthetic；The separation membrane possessed between the anode and cathode；And electrolyte.
The storage battery can be lithium storage battery, and the synthetic can make as the active material of the cathode of lithium storage battery With.At this time, the silico-carbo nanotube-graphene alkene synthetic is agglomerated based on the silicon that the portion that is contained within is connected by carbon nanotubes Agent and the distinctive structure of crinkled graphene around the silicon flocculating agent, can show that height is led when using lithium-ions battery Electric rate, can improve the electrochemical properties of discharge and recharge.That is, discharge and recharge when, can since silicon face with electrolyte does not occur directly to contact Prevent generation solid electrolyte interface layer, show the effect that can house larger volumetric expansion.
Hereinafter, according to embodiment and experimental example, more specific description is carried out to the present invention.But following embodiments and experiment Example is only intended to illustrate the present invention, not for limiting the scope of the invention.
<Embodiment 1>Si-CNT-Gr synthetics 1
Step 0：First, Ore Leaching is carried out, to remove the metal impurities contained of discarded silicon mud.Using hydrochloric acid (HCl, 36%, Sigma Aldrich) carry out Ore Leaching.After discarded silicon mud 5g and hydrochloric acid 2M is mixed in the conical flask of 500ml, Abundant reaction when progress 5 is small at a temperature of 100 DEG C.After the temperature of mixed solution is down to room temperature after reaction, using true Air filter is dried after being taken second place using 5L distillations water washing 2.
Discarded silicon mud by Ore Leaching process utilizes ultrasonication and centrifugal separation process, separation and recycling silicon.It is first First, the discarded silicon mud 5g of purification is evenly dispersed in 500ml distilled water and is prepared into colloidal substance.In the colloidal solution of preparation Ultrasonication during for divided silicon and small silicon carbide progress 5.By by super ripple processing processing colloidal solution using from Centrifugal separator (VS-5500N, Vision Science), recycles silicon particle, in the rotary speed of 500rpm (27g-force), Rotation 12 minutes, and obtain the silicon that average particle size is 1 μm to 5 μm.
In order to by the surface characteristic of multi-walled carbon nanotube (Multi-Walled Carbon Nanotube, MWCNT) from dredge Aqueous conversion is hydrophily, carries out acid treatment.The multi-walled carbon nanotube of 1g is dispersed in the sulfuric acid (99.5%) and 50mL of 150mL Nitric acid mixed solution in after, stirring 70 to 2 it is small when.Then, washed with 5% hydrochloric acid solution and done in an atmosphere It is dry.
Graphene oxide be by by graphite using the manufacture of improved Hummer methods after, and disperseed in distilled water And prepare.
Step 1：The silicon, the multi-walled carbon nanotube of acid treatment and the graphene oxide that are separated and recovered in the step 0 and distillation Water mixes, and it is respectively 0.8wt%, 0.2wt% and 0.2wt% to make its concentration.
Step 2a：Mixture made of the step 1 is utilized into nozzle type drying process with atomizing, manufactures silico-carbo nanometer Pipe-graphene oxide (Si-CNT-GO) synthetic.Nozzle type spray dryerPass through second fluid nozzle under a certain pressure Spray mixture, solvent evaporation process carry out in the drying chamber (chamber) of preheating temperature to 200 DEG C.At this time, gas is disperseed The flow of body and the transfer flow of mixture are respectively argon gas 10l/min, 4.5ml/min, and are returned in cyclone separator is trapped Receive the silico-carbo nanotube-graphene olefinic oxide synthetic of three-dimensional crinkled shape.
Step 2b：The silico-carbo nanotube-graphene olefinic oxide synthetic of the crinkled shape of the recycling of the step 2a is in Ar rings In border, i.e. Ar flows are with 800 DEG C of progress, 30 minutes heat treatment processes in 1L/min, by the graphene oxide in synthetic Graphene is reduced to completely, is finally made silico-carbo nanotube-graphene alkene (Si-CNT-Gr) synthetic of the crinkled shape of three-dimensional.
<Embodiment 2>Si-CNT-Gr synthetics 2
In the step 1 of the embodiment 1, in addition to the concentration of carbon nanotubes is arranged to 0.1wt%, remainder Perform silico-carbo nanotube-graphene alkene (Si-CNT-Gr) synthesis identical with the embodiment 1, and that the crinkled shape of three-dimensional is made Thing.
<Embodiment 3>Si-CNT-Gr synthetics 3
In the step 1 of the embodiment 1, in addition to the concentration of carbon nanotubes is arranged to 0.05wt%, its remaining part The execution divided is identical with the embodiment 1, and the silico-carbo nanotube-graphene alkene (Si-CNT-Gr) that the crinkled shape of three-dimensional is made closes Into thing.
<Experimental example 1>The shape of synthetic, X-ray diffraction and Raman analysis
The shape of the manufactured synthetic of the embodiment 1 to 3 is shot by Scanning Electron microscope (SEM), and carries out X X ray diffraction analysis x, and Raman spectroscopy has been carried out, its results show is in Fig. 4 to Fig. 6 and table 1.
With reference to Fig. 4, substantially spherical according to synthetic made of the condition of embodiment 1 to 3, surface is due to capillary Compression forms a large amount of wrinkles, can confirm the graphene of crinkled shape, almost without exposing silicon on surface.The averaged particles ruler of synthetic It is very little when carbon nanotube concentration is respectively 0.05wt%, 0.1wt% and 0.2wt%, be respectively 1.5 μm, 2 μm and 3 μm.Therefore, It can confirm to be made with the spherical of 1 μm to 5 μm of various sizes by using the spray dryer for being provided with second fluid nozzle Synthetic.
As shown in figure 5, by the crystallinity analysis result based on X-ray, the position near about 28 ° can be confirmed, heat There is silicon in silico-carbo nanotube-graphene alkene synthetic after processing.About 25 ° to 30 ° of position, it is contemplated that graphene wave crest Slowly occur with carbon nanotubes wave crest, still, since the wave crest of silicon occurs suddenly, it is contemplated that it is difficult to distinguish the wave crest of carbon material.
By Raman (Raman) analysis result of Fig. 6, the silico-carbo nanotube-graphene alkene synthetic after heat treatment can be confirmed Silicon and carbon nanotubes and graphene.Silicon is shown as 518cm-1, carbon nanotubes and graphene are shown as 1340cm-1And 1600cm-1。
【Table 1】
<Embodiment 4>The lithium storage battery 1 of Si-CNT-Gr synthetics comprising crinkled shape
By manufactured synthetic in the embodiment 1, carbon black conductive material, polyvinylidene fluoride (PVdF) adhesive with 80：10：10 weight ratio mixing, after mixing and be sufficiently stirred with 1-methyl-2-pyrrolidinone solvent, is coated on copper shell, At a temperature of 120 DEG C, it is dried and removes 1-methyl-2-pyrrolidinone.After dry electrode is rolled using roll press, with institute The size needed is cut, 120 DEG C of vacuum bake and bank up with earth case carry out 12 it is small when more than drying to remove moisture removal.
The button cell of CR2032 specifications is manufactured inside the glove box of ar gas environment using the manufactured electrode.This When, use lithium metal foil as to electrode.Polyolefin separation membrane is accompanied between two electrodes, 1 molar concentration is used as electrolyte LiPF6/ ethyl cellulose (EC)：Dimethyl carbonate (DMC) (volume ratio 1：2), and it is made storage battery.
<Embodiment 5>The lithium storage battery 2 of Si-CNT-Gr synthetics comprising crinkled shape
In the embodiment 4, in addition to synthetic synthetic made of the embodiment 2 is replaced, remaining Partial execution is identical with the embodiment 4, and storage battery is made.
<Embodiment 6>The lithium storage battery 3 of Si-CNT-Gr synthetics comprising crinkled shape
The embodiment 4 it, in addition to synthetic synthetic made of the embodiment 3 is replaced, remaining Partial execution is identical with the embodiment 4, and storage battery is made.
<Comparative example 1>The storage battery of bag silicon-containing active substance
In the embodiment 4, in addition to using the silicon of the separation and recovery of the step 0 substitution synthetic and application, The execution of remainder is identical with the embodiment 4, and storage battery is made.
<Experimental example 2>Accumulator cell charging and discharging evaluating characteristics
The charging-discharging cycle of the manufactured storage battery of the embodiment 4 to 6 and comparative example 1 is tested to static capacity and storehouse Logical sequence is imitated, its results show is in Fig. 7 (a) and figure (b).
With reference to Fig. 7 (a), based on silicon mud by separating and recovering and purifying the evaluating characteristics knot of comparative example 1 made of silicon particle Fruit shows that initial capacity is the high value of 2800mAh/g, with the progress for writing the cycle, shows the trend strongly reduced, 15 cycles 500mAh/g is shown as afterwards.It is expected that this is because when discharge and recharge, cannot house the large volume change of silicon and silicon particle is exposed to electricity Xie Zhizhong is simultaneously contacted, so that in low cycle exhibit stabilization.On the contrary, include the silico-carbo nanotube-graphene alkene of crinkled shape in manufacture During the storage battery of synthetic, when comprising silicon, the carbon nanotube concentration of the mixture of carbon nanotubes and graphene oxide is When 0.2wt%, 0.1wt%, 0.05wt%, initial capacity is respectively indicated as 2100mAh/g, 1750mAh/g, 2000mAh/g, phase Than in silicon, though initial capacity is low, in 50 cycles, all capacity all rise to more than 1500mAh/g, show high charge and discharge Capacitance.
As shown in Fig. 7 (b), all coulombic efficiencies of embodiment are all stably maintained at more than 95% on 50 cycles.Should The result is that since there is high conductivity around the synthetic of silicon particle by carbon nanotubes and graphene, by avoiding being subject to electrolyte Directly contact, can prevent the generation of unstable solid electrolyte interface layer, the large volume that when discharge and recharge can house silicon becomes Change and occur.
So far, the side of the silico-carbo nanotube-graphene alkene synthetic for the crinkled shape of manufacture being related to state as the present invention Method, the related specific embodiment of the storage battery of synthetic and the application synthetic is illustrated according to made of this method, but It is, it is obvious that in without departing from the scope of the present invention, various modifications implementation may be present.
Therefore, the definition of the scope of the present invention should not necessarily be limited by embodiment, but by rear narration claims and and its Equivalents and determine.
That is, foregoing embodiment, it should be understood that be all to be used for for example, non-be used to limit in all respects, although The scope of the present invention is compared to detailed description, depending on the claims chatted after being based more on, the implication based on the claims With scope and its equivalent concepts derived from the forms of all deformations be all understood to be within the scope of the present invention.

Claims (13)

1. a kind of method for the silico-carbo nanotube-graphene alkene synthetic for manufacturing crinkled shape, its step include：
The step of manufacturing the mixture containing silicon, carbon nanotubes, graphene oxide and solvent (step 1)；And
The step of being spray-dried the mixture, and being heat-treated (step 2).
2. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 1, it is characterised in that
The silicon of the step 1 is by carrying out Ore Leaching to discarded silicon mud, and is optionally sequestered and recycles silicon and purchase.
3. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 2, it is characterised in that
The step of being dried is additionally included in after the Ore Leaching, to containing the discarded silicon mud for having carried out the drying steps After solution carries out ultrasonication, it is centrifuged, so as to be optionally sequestered and recycle silicon.
4. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 3, it is characterised in that
The ultrasonication, carry out 1 hour to 10 it is small when, the centrifugation is with the rotation of 100rpm to 1000rpm speed Degree performs 1 minute to 60 minutes.
5. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 1, it is characterised in that
The carbon nanotubes of the step 1 is by the way that carbon nanotubes is carried out decentralized processing in the acid solution including sulfuric acid and nitric acid And prepare.
6. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 1, it is characterised in that
The carbon nanotube concentration of the mixture of the step 1 is 0.05wt% to 0.2wt%.
7. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 1, it is characterised in that
The silicon concentration of the mixture of the step 1 is 0.3wt% to 1.3wt%.
8. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 1, it is characterised in that
The graphene oxide concentration of the mixture of the step 1 is 0.1wt% to 0.5wt%.
9. the method for crinkled silico-carbo nanotube-graphene alkene synthetic is manufactured as claimed in claim 1, it is characterised in that
The step 2 is by second fluid nozzle, the step that the mixture of the step 1 is sprayed in the form of aerosol droplets Suddenly (step 2a)；And
The step of drop for forming the spraying by transferring gas is gone forward side by side drying through tubulose heating furnace, reductive heat treatment (step 2b) and carry out.
10. the side for manufacturing crinkled silico-carbo nanotube-graphene alkene synthetic as described in claim 1 or claim 9 Method, it is characterised in that
The heat treatment temperature of step 2 or the step 2b is 500 DEG C to 1000 DEG C.
11. a kind of method for the silico-carbo nanotube-graphene alkene synthetic for manufacturing crinkled shape, its step include：
After discarded silicon mud is carried out Ore Leaching, optionally silicon is separated and recycled from leachate, and carbon nanotubes is carried out The step of acid treatment (step 0)；
The step of manufacturing the mixture of the silicon for including the recycling, the carbon nanotubes through acid treatment, graphene oxide and solvent (step It is rapid 1)；
By second fluid nozzle, the step of mixture of the step 1 is sprayed in the form of aerosol droplets (step 2a)；And
By transferring gas, make the drop that the spraying is formed through tubulose heating furnace and be dried, the step of reductive heat treatment Suddenly (step 2b).
12. a kind of silico-carbo nanotube-graphene alkene synthetic of crinkled shape, it includes：
Agglomerate the silicon flocculating agent of multiple silicon particles；
Around multiple crinkled graphenes of the silicon flocculating agent；And
Between the silicon particle, bridging point between the crinkled graphene and between the silicon particle and crinkled graphene Multiple carbon nanotubes.
13. a kind of storage battery, it includes：
Anode；
Cathode containing silico-carbo nanotube-graphene alkene synthetic as claimed in claim 12；
The separation membrane possessed between the anode and cathode；And electrolyte.
CN201711173126.9A 2017-07-12 2017-11-22 A kind of method of silicon-carbon nanotube graphene synthetic for manufacturing crinkled shape and the synthetic based on this method manufacture Pending CN107919469A (en)

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