CN109244378A - Preparation method of porous nano silicon-carbon composite material - Google Patents
Preparation method of porous nano silicon-carbon composite material Download PDFInfo
- Publication number
- CN109244378A CN109244378A CN201710560159.2A CN201710560159A CN109244378A CN 109244378 A CN109244378 A CN 109244378A CN 201710560159 A CN201710560159 A CN 201710560159A CN 109244378 A CN109244378 A CN 109244378A
- Authority
- CN
- China
- Prior art keywords
- carbon
- composite material
- silicon
- porous nano
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000007740 vapor deposition Methods 0.000 claims description 10
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011856 silicon-based particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229910021382 natural graphite Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract 3
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 33
- 229910052710 silicon Inorganic materials 0.000 description 26
- 239000010703 silicon Substances 0.000 description 26
- 239000002002 slurry Substances 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000010907 mechanical stirring Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 12
- 239000011149 active material Substances 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- -1 polypropylene Polymers 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 239000011863 silicon-based powder Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 235000012907 honey Nutrition 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229910002058 ternary alloy Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a porous nano silicon-carbon composite material, which comprises the steps of firstly coating carbon on the surface of a nano silicon to form carbon-coated nano silicon, then mixing and sintering the carbon-coated nano silicon with a metal oxide and a carbon material to obtain a precursor of the porous nano silicon-carbon composite material, washing the precursor with an acid solution to remove the metal oxide in the precursor, and drying to obtain the porous nano silicon-carbon composite material.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery negative material.Specifically, the present invention provides one kind
The preparation method of porous nano Si-C composite material.
Background technique
Lithium ion battery is because it is high with operating voltage, specific energy is high, capacity is big, self discharge is small, cyclicity is good, uses the longevity
Order outstanding advantages of long, light-weight, small in size and the desired electrical as the portable electronic devices such as mobile phone, laptop
Source.In order to meet requirement, high capacity, extended-life lithium ion battery become an important research side of lithium ion battery development
To.Since the specific capacity of positive electrode is relatively low, the room for promotion of capacity is little, therefore the development work of high-capacity lithium ion cell
It is concentrated mainly on negative electrode material.The existing negative electrode material being commercially used is carbon material, and theoretical specific capacity only has 372mAh/
G, therefore the high-capacity cathode material for finding substitution carbon becomes an important research direction.
Si sill is a kind of common lithium ion battery negative material, is managed in people are studied up to now material
Highest by specific capacity, the theoretical specific capacity of pure silicon is 4200mAh/g, much larger than negative electrode material natural graphite commercial at this stage
With the theoretical capacity of artificial graphite, it is considered to be the lithium ion battery negative material of most promising high capacity.But pure simple substance
Silicon can not be used as electrode material, because its conductivity is low, silicon is semiconductor material, and conductivity only has 6.7*10-4S/cm, separately
On the one hand in battery charge and discharge process, the silicon as negative electrode material can generate huge volume expansion, cause negative electrode material with
Negative current collector is detached from, and cycle performance of battery is unable to satisfy commercial requirement.For the above two aspects problem, common practice in industry
It is to be mixed with Carbon materials using silicon, i.e. Si-C composite material utilizes the electricity of the good electric conductivity solution elemental silicon of Carbon materials
The problem of conductance, on the other hand the smaller ratio for reducing silicon in Si-C composite material, reduces the size of silicon, such as use nanometer
Silicon reduces the bulking effect of material entirety.
Patent CN103337612B discloses a kind of nanoporous Si-C composite material and preparation method thereof, utilizes aluminium base
Ternary alloy three-partalloy is as raw material, and using free etch, feature includes the following steps: that component is included silicon, carbon, aluminium by (1)
Ternary alloy three-partalloy piece is placed in sodium hydroxide solution or hydrochloric acid or sulfuric acid solution;(2) it at a temperature of 10~40 DEG C, places anti-
It answers 5~40 hours;(3) alloy after corrosion is collected, is washed with water to corrosion solution used and is washed away completely repeatedly, then 4
It is dried at a temperature of~100 DEG C, as nanoporous Si/C composite material.Had by the material agent of this method preparation three-dimensional continuous
Nano pore structure bulk structure, to alleviate the stress of traditional silicon nano material breathing, to inhibit structure breaking, this
Outside, continuous structure forms the huge network of electronics and ionic conduction, help to obtain high stability and conduction
Property.But since the silicon of nanoscale is unstable in aqueous solution, it is easy to happen vigorous reaction, or even generate as hydrogen
Flammable explosive gas, this method are directly placed in the ternary alloy three-partalloy piece of silicon, carbon, aluminium in solution, touch aqueous solution in silicon
Place will cause the loss of silicon, and cause danger.
Patent CN201510106478.7 disclose a kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof and
Using 1) by sanded treatment after silicon powder ball mill grinding, by treated, silicon powder is dispersed in macromolecule polymer solution or containing a source of aluminum
Solution or colloid containing silicon source in and be ultrasonically treated, so that silicon powder is suspended in the solution, prevent to reunite.2) by step 1)
It after resulting solution decompression rotary evaporation removes solvent, is sintered, is coated in silicon face amorphous under non-oxidizing atmosphere
Carbon or aluminum oxide.3) by the silicon powder coated obtained by step 2) and inorganic carbon source, hydroxy compounds dispersing agent, again divide equally
The polymeric additive that son amount is 50000-400000 carries out mechanical stirring, is uniformly mixed, the suitable weak solution of viscosity.4)
The resulting weak solution of step 3) is subjected to spray drying treatment, obtains Si-C composite material, and carry out under non-oxidizing atmosphere
Sintering, obtains porous Si-C composite material.5) it in the hole of the resulting Si-C composite material of step 4), fills inorganic or has
Machine carbon source configures the higher concentrated solution of viscosity, carries out spray drying treatment, obtains fine and close spherical composite material, and non-oxygen
It is sintered under the property changed atmosphere, finally obtains the Silicon-carbon composite material for lithium ion battery of high-tap density, stable circulation.It obtains
Si-C composite material the advantages of being integrated with Si-C composite material and porous material, by multi-buffering-layer, improve silicon substrate
Expect the problem poor as cyclicity existing for lithium ion battery negative material, coulombic efficiency is low, but also can be real by regulation
The ratio of silicon powder and carbon source during testing prepares composite material of the reversible capacity between 400-1200mAh/g.But this is specially
Silicon powder in the solution of macromolecule polymer solution or containing a source of aluminum or the colloid containing silicon source and is ultrasonically treated by benefit, keeps silicon powder outstanding
It floats in the solution, i.e., prepares material by the way of collosol and gel, can be brought in extensive industrialization technology scheme very big
Inconvenience handles the thing that large-scale colloid is a relative difficulty.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of preparation sides of porous nano Si-C composite material
Method.A carbon coating first is carried out in nanometer silicon face, carbon-coated nano-silicon is formed, then by carbon-coated nano-silicon and metal
Oxide and carbon material are mixed, are sintered, and the presoma of porous nano Si-C composite material is obtained, by presoma acid solution
It is washed, removes the metal oxide in presoma, obtain porous nano Si-C composite material after dry.Due to molten with acid
Before liquid is washed, for nanometer silicon face by carbon coating, carbon layer on surface has completely cut off contact of the nano-silicon with solution, leads to silicon
It can not be reacted with solution, avoid the loss of silicon, reduce danger.
The present invention is achieved by the following technical solutions:
The present invention provides a kind of preparation methods of negative electrode of lithium ion battery Si-C composite material, comprising the following steps:
(1) partial size is put into Equipment for Heating Processing in 50~1000g of silicon particle of 5~100nm, is warming up to vapor deposition
650~1650 DEG C of temperature;
(2) start to be passed through gaseous carbon source, the duration is 1~10h, flow 0.1-20L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, metal oxide and carbon material are mixed, wherein the weight of carbon-coated nano-silicon accounts for
Than being 2~35%, the weight accounting of metal oxide is 2~85%, remaining is carbon material.Three's mixture is placed into hot place
It is sintered in reason equipment, leads to nitrogen or inert gas shielding, sintering temperature is 500~1650 DEG C, and sintering time is 2~36h, natural
It cools to room temperature, obtains the presoma of porous nano Si-C composite material;
(5) presoma is washed with the acid solution of 0.5~10mol/L, is then washed with deionized water, it is dry
Porous nano Si-C composite material is obtained afterwards;
The gaseous carbon source is a combination of one or more object of alkane, alkene, alkynes, aromatic hydrocarbon, ethers, preferably
For acetylene;
The Equipment for Heating Processing are as follows: tube furnace, batch-type furnace, board-like furnace or high-temperature rotary furnace, preferably high-temperature rotary furnace;
The metal oxide are as follows: aluminum oxide, magnesia, calcium oxide, iron oxide, di-iron trioxide, zinc oxide, oxygen
Change a combination of one or more object of copper;
The carbon material are as follows: natural graphite, artificial graphite, carbonaceous mesophase spherules, carbon nanotube, graphene, in carbon fiber
A combination of one or more object;
The acid solution are as follows: sulfuric acid solution, hydrochloric acid solution, nitric acid solution, phosphoric acid solution, one kind of hydrofluoric acid solution or two
Kind or more composition;
Preferably, the vapor deposition temperature is 750~1400 DEG C, and sintering temperature is 500~1250 DEG C;
Preferably, acid solutions are 3~9mol/L.
Preferably, the weight accounting of carbon-coated nano-silicon is 5~20%, the weight accounting of metal oxide is 30~
60%, remaining is carbon material.
The present invention has the advantages that compared with prior art
(1) preparation method of porous nano Si-C composite material of the present invention, before being washed with acid solution, nanometer
For silicon face by carbon coating, carbon layer on surface has completely cut off contact of the nano-silicon with solution, causes silicon that can not react with solution, avoids
The loss of silicon, reduces danger;
(2) present invention has coated one layer of carbon in Si particle surface deposition using the method for vapor deposition, and the material of acquisition is led
Electrical property is more preferable;
(3) present invention uses the presoma of acid elution porous nano Si-C composite material, can reduce that final product is porous to be received
The pH value of rice Si-C composite material, in lithium ion battery production, high ph-values normally result in negative electrode slurry condensation, mobility
Difference can not be coated, and the porous nano Si-C composite material of low ph value of the present invention will avoid after being made into battery cathode slurry
Condense phenomenon.
(4) when selecting acetylene as gaseous carbon source, the efficiency highest for the carbon that is vapor-deposited.
(5) present invention process is simple, is easy to carry out large-scale production.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments be only used for the present invention without
For limiting the scope of the invention.Externally it should be understood that after reading the contents of the present invention, those skilled in the art are to this hair
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Embodiment 1
(1) partial size is put into high-temperature rotary furnace in the silicon particle 200g of 50nm, is warming up to vapor deposition temperature 1200
℃;
(2) start to be passed through acetylene, duration 3h, flow 1L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, magnesia and natural graphite are mixed, wherein the weight accounting of carbon-coated nano-silicon
It is 5%, the weight accounting of magnesia is 35%, remaining is natural graphite.Three's mixture is placed into batch-type furnace and is sintered, is led to
The nitrogen of 1L/min, sintering temperature are 700 DEG C, and sintering time is for 24 hours that natural cooling is cooled to room temperature, obtains porous nano silicon
The presoma of carbon composite;
(5) presoma is washed with the sulfuric acid solution of 8mol/L, is then washed with deionized water, be after dry
Obtain porous nano Si-C composite material.
Performance evaluation uses simulated battery, the production method is as follows:
The porous nano Si-C composite material for using embodiment to prepare respectively makes simulated battery, production as active material
Steps are as follows:
1, ingredient and mechanical stirring, according to active material 3.4g, conductive agent 0.2g (is not needed then) with the presence of carbon black situation,
It is living that the ratio of 5% Kynoar PVDF 8g and N-Methyl pyrrolidone NMP 0.8g weigh porous nano Si-C composite material
Property substance, conductive agent, 5% PVDF and NMP, then mechanical stirring mode is used to be configured to solid content as 32.26% slurry, stirred
About 15min is mixed, slurry preferably, measures slurry pH value in honey paste.
2, slurry is coated on copper foil, makes pole piece.
3, pole piece dries drying, is placed directly in air dry oven, and 95~100 DEG C are toasted 2 hours, and it is dry to be then placed in vacuum
Dry case, 95~100 DEG C vacuum drying 10 hours.
4, assembled battery, makees cathode with lithium piece, makees diaphragm with polypropylene or polyethylene, with 1mol/L LiPF6 (volume ratio
Ethylene carbonate and dimethyl carbonate mixed liquor for 1: 1) it is used as electrolyte, it is assembled into simulated battery.
5, simulation electricity is measured using the blue electric battery test system of the LAND type of the CT2001C of Wuhan Jin Nuo Electronics Co., Ltd.
The data in pond, voltage range are 0.005~2.0V, and charging and discharging currents are the chemical property that 0.2C evaluates material, negative electrode slurry
PH value is 8, reversible capacity 510mAh/g, efficiency for charge-discharge 89%, and circulation is after 15 weeks, capacity retention ratio 97%.
Embodiment 2
(1) partial size is put into high-temperature rotary furnace in the silicon particle 50g of 10nm, is warming up to 750 DEG C of temperature of vapor deposition;
(2) start to be passed through propane, duration 10h, flow 0.5L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, aluminum oxide and carbonaceous mesophase spherules are mixed, wherein carbon-coated nano-silicon
Weight accounting is 20%, and the weight accounting of aluminum oxide is 60%, remaining is carbonaceous mesophase spherules.Three's mixture is placed
It is sintered into batch-type furnace, leads to the nitrogen of 1L/min, sintering temperature is 1100 DEG C, and sintering time 2h, natural cooling is cooled to room
Temperature obtains the presoma of porous nano Si-C composite material;
(5) presoma is washed with the nitric acid solution of 1mol/L, is then washed with deionized water, be after dry
Obtain porous nano Si-C composite material.
Performance evaluation uses simulated battery, the production method is as follows:
The porous nano Si-C composite material for using embodiment to prepare respectively makes simulated battery, production as active material
Steps are as follows:
1, ingredient and mechanical stirring, according to active material 3.4g, conductive agent 0.2g (is not needed then) with the presence of carbon black situation,
It is living that the ratio of 5% Kynoar PVDF 8g and N-Methyl pyrrolidone NMP 0.8g weigh porous nano Si-C composite material
Property substance, conductive agent, 5% PVDF and NMP, then mechanical stirring mode is used to be configured to solid content as 32.26% slurry, stirred
About 15min is mixed, slurry preferably, measures slurry pH value in honey paste.
2, slurry is coated on copper foil, makes pole piece.
3, pole piece dries drying, is placed directly in air dry oven, and 95~100 DEG C are toasted 2 hours, and it is dry to be then placed in vacuum
Dry case, 95~100 DEG C vacuum drying 10 hours.
4, assembled battery, makees cathode with lithium piece, makees diaphragm with polypropylene or polyethylene, with 1mol/L LiPF6 (volume ratio
Ethylene carbonate and dimethyl carbonate mixed liquor for 1: 1) it is used as electrolyte, it is assembled into simulated battery.
5, simulation electricity is measured using the blue electric battery test system of the LAND type of the CT2001C of Wuhan Jin Nuo Electronics Co., Ltd.
The data in pond, voltage range are 0.005~2.0V, and charging and discharging currents are the chemical property that 0.2C evaluates material.Negative electrode slurry
PH value is 8.6, reversible capacity 570mAh/g, efficiency for charge-discharge 85%, and circulation is after 15 weeks, capacity retention ratio 95%.
Embodiment 3
(1) partial size is put into high-temperature rotary furnace in the silicon particle 1000g of 100nm, is warming up to vapor deposition temperature 1400
℃;
(2) start to be passed through ethylene, duration 2h, flow 15L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, zinc oxide and artificial graphite are mixed, wherein the weight accounting of carbon-coated nano-silicon
It is 15%, the weight accounting of zinc oxide is 10%, remaining is artificial graphite.Three's mixture is placed into batch-type furnace and is sintered,
The nitrogen of logical 1L/min, sintering temperature are 1300 DEG C, and sintering time 5h, natural cooling is cooled to room temperature, obtains porous nano
The presoma of Si-C composite material;
(5) presoma is washed with the hydrochloric acid solution of 5mol/L, is then washed with deionized water, be after dry
Obtain porous nano Si-C composite material.
Performance evaluation uses simulated battery, the production method is as follows:
The porous nano Si-C composite material for using embodiment to prepare respectively makes simulated battery, production as active material
Steps are as follows:
1, ingredient and mechanical stirring, according to active material 3.4g, conductive agent 0.2g (is not needed then) with the presence of carbon black situation,
It is living that the ratio of 5% Kynoar PVDF 8g and N-Methyl pyrrolidone NMP 0.8g weigh porous nano Si-C composite material
Property substance, conductive agent, 5% PVDF and NMP, then mechanical stirring mode is used to be configured to solid content as 32.26% slurry, stirred
About 15min is mixed, slurry preferably, measures slurry pH value in honey paste.
2, slurry is coated on copper foil, makes pole piece.
3, pole piece dries drying, is placed directly in air dry oven, and 95~100 DEG C are toasted 2 hours, and it is dry to be then placed in vacuum
Dry case, 95~100 DEG C vacuum drying 10 hours.
4, assembled battery, makees cathode with lithium piece, makees diaphragm with polypropylene or polyethylene, with 1mol/L LiPF6 (volume ratio
Ethylene carbonate and dimethyl carbonate mixed liquor for 1: 1) it is used as electrolyte, it is assembled into simulated battery.
5, simulation electricity is measured using the blue electric battery test system of the LAND type of the CT2001C of Wuhan Jin Nuo Electronics Co., Ltd.
The data in pond, voltage range are 0.005~2.0V, and charging and discharging currents are the chemical property that 0.2C evaluates material.Negative electrode slurry
PH value is 8.1, reversible capacity 533mAh/g, efficiency for charge-discharge 87%, and circulation is after 15 weeks, capacity retention ratio 92%.
Embodiment 4
(1) partial size is put into tube furnace in the silicon particle 50g of 30nm, is warming up to 1100 DEG C of temperature of vapor deposition;
(2) start to be passed through propane, duration 5h, flow 1L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, copper oxide and natural graphite are mixed, wherein the weight accounting of carbon-coated nano-silicon
It is 15%, the weight accounting of copper oxide is 30%, remaining is natural graphite.Three's mixture is placed into batch-type furnace and is sintered,
The nitrogen of logical 1L/min, sintering temperature are 600 DEG C, and sintering time 12h, natural cooling is cooled to room temperature, obtains porous nano
The presoma of Si-C composite material;
(5) presoma is washed with the phosphoric acid solution of 2mol/L, is then washed with deionized water, be after dry
Obtain porous nano Si-C composite material.
Performance evaluation uses simulated battery, the production method is as follows:
The porous nano Si-C composite material for using embodiment to prepare respectively makes simulated battery, production as active material
Steps are as follows:
1, ingredient and mechanical stirring, according to active material 3.4g, conductive agent 0.2g (is not needed then) with the presence of carbon black situation,
It is living that the ratio of 5% Kynoar PVDF 8g and N-Methyl pyrrolidone NMP 0.8g weigh porous nano Si-C composite material
Property substance, conductive agent, 5% PVDF and NMP, then mechanical stirring mode is used to be configured to solid content as 32.26% slurry, stirred
About 15min is mixed, slurry preferably, measures slurry pH value in honey paste.
2, slurry is coated on copper foil, makes pole piece.
3, pole piece dries drying, is placed directly in air dry oven, and 95~100 DEG C are toasted 2 hours, and it is dry to be then placed in vacuum
Dry case, 95~100 DEG C vacuum drying 10 hours.
4, assembled battery, makees cathode with lithium piece, makees diaphragm with polypropylene or polyethylene, with 1mol/L LiPF6 (volume ratio
Ethylene carbonate and dimethyl carbonate mixed liquor for 1: 1) it is used as electrolyte, it is assembled into simulated battery.
5, simulation electricity is measured using the blue electric battery test system of the LAND type of the CT2001C of Wuhan Jin Nuo Electronics Co., Ltd.
The data in pond, voltage range are 0.005~2.0V, and charging and discharging currents are the chemical property that 0.2C evaluates material, negative electrode slurry
PH value is 8.2, reversible capacity 536mAh/g, efficiency for charge-discharge 86%, and circulation is after 15 weeks, capacity retention ratio 93%.
Embodiment 5
(1) partial size is put into high-temperature rotary furnace in the silicon particle 200g of 100nm, is warming up to vapor deposition temperature 900
℃;
(2) start to be passed through ethylene, duration 8h, flow 0.5L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, iron oxide and artificial graphite are mixed, wherein the weight accounting of carbon-coated nano-silicon
It is 12%, the weight accounting of iron oxide is 60%, remaining is artificial graphite.Three's mixture is placed into batch-type furnace and is sintered,
The nitrogen of logical 1L/min, sintering temperature are 550 DEG C, and sintering time 12h, natural cooling is cooled to room temperature, obtains porous nano
The presoma of Si-C composite material;
(5) presoma is washed with the nitric acid solution of 4mol/L, is then washed with deionized water, be after dry
Obtain porous nano Si-C composite material.
Performance evaluation uses simulated battery, the production method is as follows:
The porous nano Si-C composite material for using embodiment to prepare respectively makes simulated battery, production as active material
Steps are as follows:
1, ingredient and mechanical stirring, according to active material 3.4g, conductive agent 0.2g (is not needed then) with the presence of carbon black situation,
It is living that the ratio of 5% Kynoar PVDF 8g and N-Methyl pyrrolidone NMP 0.8g weigh porous nano Si-C composite material
Property substance, conductive agent, 5% PVDF and NMP, then mechanical stirring mode is used to be configured to solid content as 32.26% slurry, stirred
About 15min is mixed, slurry preferably, measures slurry pH value in honey paste.
2, slurry is coated on copper foil, makes pole piece.
3, pole piece dries drying, is placed directly in air dry oven, and 95~100 DEG C are toasted 2 hours, and it is dry to be then placed in vacuum
Dry case, 95~100 DEG C vacuum drying 10 hours.
4, assembled battery, makees cathode with lithium piece, makees diaphragm with polypropylene or polyethylene, with 1mol/L LiPF6 (volume ratio
Ethylene carbonate and dimethyl carbonate mixed liquor for 1: 1) it is used as electrolyte, it is assembled into simulated battery.
5, simulation electricity is measured using the blue electric battery test system of the LAND type of the CT2001C of Wuhan Jin Nuo Electronics Co., Ltd.
The data in pond, voltage range are 0.005~2.0V, and charging and discharging currents are the chemical property that 0.2C evaluates material, negative electrode slurry
PH value is 8.4, reversible capacity 425mAh/g, efficiency for charge-discharge 87%, and circulation is after 15 weeks, capacity retention ratio 96%.
Embodiment 6
(1) partial size is put into high-temperature rotary furnace in the silicon particle 200g of 80nm, is warming up to vapor deposition temperature 1600
℃;
(2) start to be passed through ethylene, duration 5h, flow 2L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, iron oxide and artificial graphite are mixed, wherein the weight accounting of carbon-coated nano-silicon
It is 5%, the weight accounting of iron oxide is 30%, remaining is artificial graphite.Three's mixture is placed into batch-type furnace and is sintered, is led to
The nitrogen of 1L/min, sintering temperature are 500 DEG C, and sintering time is for 24 hours that natural cooling is cooled to room temperature, obtains porous nano silicon
The presoma of carbon composite;
(5) presoma is washed with the hydrochloric acid solution of 3mol/L, is then washed with deionized water, be after dry
Obtain porous nano Si-C composite material.
Performance evaluation uses simulated battery, the production method is as follows:
The porous nano Si-C composite material for using embodiment to prepare respectively makes simulated battery, production as active material
Steps are as follows:
1, ingredient and mechanical stirring, according to active material 3.4g, conductive agent 0.2g (is not needed then) with the presence of carbon black situation,
It is living that the ratio of 5% Kynoar PVDF 8g and N-Methyl pyrrolidone NMP 0.8g weigh porous nano Si-C composite material
Property substance, conductive agent, 5% PVDF and NMP, then mechanical stirring mode is used to be configured to solid content as 32.26% slurry, stirred
About 15min is mixed, slurry preferably, measures slurry pH value in honey paste.
2, slurry is coated on copper foil, makes pole piece.
3, pole piece dries drying, is placed directly in air dry oven, and 95~100 DEG C are toasted 2 hours, and it is dry to be then placed in vacuum
Dry case, 95~100 DEG C vacuum drying 10 hours.
4, assembled battery, makees cathode with lithium piece, makees diaphragm with polypropylene or polyethylene, with 1mol/L LiPF6 (volume ratio
Ethylene carbonate and dimethyl carbonate mixed liquor for 1: 1) it is used as electrolyte, it is assembled into simulated battery.
5, simulation electricity is measured using the blue electric battery test system of the LAND type of the CT2001C of Wuhan Jin Nuo Electronics Co., Ltd.
The data in pond, voltage range are 0.005~2.0V, and charging and discharging currents are the chemical property that 0.2C evaluates material, negative electrode slurry
PH value is 8.5, reversible capacity 401mAh/g, efficiency for charge-discharge 72%, and circulation is after 15 weeks, capacity retention ratio 95%.
Claims (7)
1. a kind of preparation method of porous nano Si-C composite material, comprising the following steps:
(1) partial size is put into Equipment for Heating Processing in 50~1000g of silicon particle of 5~100nm, is warming up to vapor deposition temperature
650~1650 DEG C;
(2) start to be passed through gaseous carbon source, the duration is 1~10h, flow 0.1-20L/min;
(3) reaction stops, and natural cooling is cooled to room temperature to get carbon-coated nano-silicon is arrived;
(4) carbon-coated nano-silicon, metal oxide and carbon material are mixed, wherein the weight accounting of carbon-coated nano-silicon is
2~35%, the weight accounting of metal oxide is 2~85%, remaining is carbon material.Three's mixture is placed into heat treatment to set
Nitrogen or inert gas shielding are led in standby middle sintering, and sintering temperature is 500~1650 DEG C, and sintering time is 2~36h, natural cooling
It is cooled to room temperature, obtains the presoma of porous nano Si-C composite material;
(5) presoma is washed with the acid solution of 0.5~10mol/L, is then washed with deionized water, be after dry
Obtain porous nano Si-C composite material;
The gaseous carbon source is a combination of one or more object of alkane, alkene, alkynes, aromatic hydrocarbon, ethers;
The metal oxide are as follows: aluminum oxide, magnesia, calcium oxide, iron oxide, di-iron trioxide, zinc oxide, copper oxide
A combination of one or more object;
The carbon material are as follows: natural graphite, artificial graphite, carbonaceous mesophase spherules, carbon nanotube, graphene, one in carbon fiber
Kind or two or more compositions;
The acid solution are as follows: sulfuric acid solution, hydrochloric acid solution, nitric acid solution, phosphoric acid solution, hydrofluoric acid solution it is one or two kinds of with
On composition.
2. according to the preparation method of porous nano Si-C composite material described in claims 1, which is characterized in that the heat
Processing equipment are as follows: tube furnace, batch-type furnace, board-like furnace or high-temperature rotary furnace.
3. according to the preparation method of porous nano Si-C composite material described in claims 1, which is characterized in that the gas phase is heavy
Accumulated temperature degree is 750~1400 DEG C.
4. according to the preparation method of porous nano Si-C composite material described in claims 1, which is characterized in that the gaseous carbon
Source is acetylene.
5. according to the preparation method of porous nano Si-C composite material described in claims 1, which is characterized in that the acid solution
Concentration is 3~9mol/L.
6. according to the preparation method of porous nano Si-C composite material described in claims 1, which is characterized in that the carbon coating
The weight accounting of nano-silicon be 5~20%, the weight accounting of metal oxide is 30~60%, remaining is carbon material.
7. according to the preparation method of porous nano Si-C composite material described in claims 1, which is characterized in that the sintering temperature
Degree is 500~1250 DEG C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710560159.2A CN109244378A (en) | 2017-07-10 | 2017-07-10 | Preparation method of porous nano silicon-carbon composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710560159.2A CN109244378A (en) | 2017-07-10 | 2017-07-10 | Preparation method of porous nano silicon-carbon composite material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109244378A true CN109244378A (en) | 2019-01-18 |
Family
ID=65083856
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710560159.2A Pending CN109244378A (en) | 2017-07-10 | 2017-07-10 | Preparation method of porous nano silicon-carbon composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109244378A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109647298A (en) * | 2019-01-31 | 2019-04-19 | 济南大学 | Polyethylene-zinc oxide micrometer nanometer hierarchical structure composite micro-sphere material and application |
CN109860579A (en) * | 2019-04-02 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | Cathode material with core-shell structure and preparation method thereof |
CN111261856A (en) * | 2020-01-20 | 2020-06-09 | 广东工业大学 | Carbon sheet cage coated porous silicon material and preparation method and application thereof |
CN111584838A (en) * | 2020-05-06 | 2020-08-25 | 厦门大学 | Porous silicon/silicon-carbon composite material and preparation method and application thereof |
CN111785945A (en) * | 2020-07-21 | 2020-10-16 | 湖南中科星城石墨有限公司 | Graphene-coated nano silicon and preparation method thereof, silicon-carbon negative electrode material and preparation method thereof |
CN112467140A (en) * | 2020-08-14 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | High-safety graphite silicon carbon composite material and preparation method thereof |
CN113036109A (en) * | 2021-03-12 | 2021-06-25 | 广州巨湾技研有限公司 | Preparation method of high-rate silicon-carbon negative electrode microspheres and high-rate silicon-carbon negative electrode microspheres |
CN113130870A (en) * | 2021-04-09 | 2021-07-16 | 珠海冠宇电池股份有限公司 | Composite silicon material and lithium ion battery |
CN113479947A (en) * | 2021-06-29 | 2021-10-08 | 清华大学深圳国际研究生院 | Porous nano material surface modification method, filtering type disinfection device and method |
CN114744172A (en) * | 2022-04-06 | 2022-07-12 | 广东海洋大学 | Silicon-carbon composite negative electrode material and preparation method and application thereof |
CN116454256A (en) * | 2023-06-16 | 2023-07-18 | 北京壹金新能源科技有限公司 | Preparation method of silicon-carbon composite material, silicon-carbon composite material and battery |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105226241A (en) * | 2014-08-27 | 2016-01-06 | 深圳市国创新能源研究院 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
KR20160001481A (en) * | 2014-06-27 | 2016-01-06 | 주식회사 엘지화학 | Surface coated porous silicon based anode active material and preparation method thereof |
WO2016159663A1 (en) * | 2015-03-31 | 2016-10-06 | 주식회사 엘지화학 | Porous silicon-silicon oxide-carbon composite, and method for preparing same |
CN106159229A (en) * | 2016-07-28 | 2016-11-23 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon based composite material, preparation method and comprise the lithium ion battery of this composite |
CN106328898A (en) * | 2016-10-10 | 2017-01-11 | 东莞市凯金新能源科技股份有限公司 | Method for preparing lithium ion battery anode composite material through template method |
CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
US20170117539A1 (en) * | 2015-10-22 | 2017-04-27 | Samsung Electronics Co., Ltd. | Electrode active material, electrode and secondary battery including the same, and method of preparing the electrode active material |
CN106784707A (en) * | 2016-12-28 | 2017-05-31 | 江西正拓新能源科技股份有限公司 | A kind of preparation method of nano-silicone wire/carbon composite lithium ion battery cathode material |
CN106848257A (en) * | 2017-03-26 | 2017-06-13 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon-coated silicon negative electrode material with hollow structure |
-
2017
- 2017-07-10 CN CN201710560159.2A patent/CN109244378A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160001481A (en) * | 2014-06-27 | 2016-01-06 | 주식회사 엘지화학 | Surface coated porous silicon based anode active material and preparation method thereof |
CN105226241A (en) * | 2014-08-27 | 2016-01-06 | 深圳市国创新能源研究院 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
WO2016159663A1 (en) * | 2015-03-31 | 2016-10-06 | 주식회사 엘지화학 | Porous silicon-silicon oxide-carbon composite, and method for preparing same |
US20170117539A1 (en) * | 2015-10-22 | 2017-04-27 | Samsung Electronics Co., Ltd. | Electrode active material, electrode and secondary battery including the same, and method of preparing the electrode active material |
CN106159229A (en) * | 2016-07-28 | 2016-11-23 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon based composite material, preparation method and comprise the lithium ion battery of this composite |
CN106328898A (en) * | 2016-10-10 | 2017-01-11 | 东莞市凯金新能源科技股份有限公司 | Method for preparing lithium ion battery anode composite material through template method |
CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
CN106784707A (en) * | 2016-12-28 | 2017-05-31 | 江西正拓新能源科技股份有限公司 | A kind of preparation method of nano-silicone wire/carbon composite lithium ion battery cathode material |
CN106848257A (en) * | 2017-03-26 | 2017-06-13 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon-coated silicon negative electrode material with hollow structure |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109647298B (en) * | 2019-01-31 | 2021-04-06 | 济南大学 | Polyethylene-zinc oxide micron nano multilevel structure composite microsphere material and application |
CN109647298A (en) * | 2019-01-31 | 2019-04-19 | 济南大学 | Polyethylene-zinc oxide micrometer nanometer hierarchical structure composite micro-sphere material and application |
CN109860579A (en) * | 2019-04-02 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | Cathode material with core-shell structure and preparation method thereof |
CN111261856A (en) * | 2020-01-20 | 2020-06-09 | 广东工业大学 | Carbon sheet cage coated porous silicon material and preparation method and application thereof |
CN111584838A (en) * | 2020-05-06 | 2020-08-25 | 厦门大学 | Porous silicon/silicon-carbon composite material and preparation method and application thereof |
CN111584838B (en) * | 2020-05-06 | 2021-03-16 | 厦门大学 | Porous silicon/silicon-carbon composite material and preparation method and application thereof |
CN111785945A (en) * | 2020-07-21 | 2020-10-16 | 湖南中科星城石墨有限公司 | Graphene-coated nano silicon and preparation method thereof, silicon-carbon negative electrode material and preparation method thereof |
CN112467140B (en) * | 2020-08-14 | 2022-07-01 | 珠海中科兆盈丰新材料科技有限公司 | High-safety graphite silicon carbon composite material and preparation method thereof |
CN112467140A (en) * | 2020-08-14 | 2021-03-09 | 珠海中科兆盈丰新材料科技有限公司 | High-safety graphite silicon carbon composite material and preparation method thereof |
CN113036109A (en) * | 2021-03-12 | 2021-06-25 | 广州巨湾技研有限公司 | Preparation method of high-rate silicon-carbon negative electrode microspheres and high-rate silicon-carbon negative electrode microspheres |
CN113130870A (en) * | 2021-04-09 | 2021-07-16 | 珠海冠宇电池股份有限公司 | Composite silicon material and lithium ion battery |
CN113479947A (en) * | 2021-06-29 | 2021-10-08 | 清华大学深圳国际研究生院 | Porous nano material surface modification method, filtering type disinfection device and method |
CN114744172A (en) * | 2022-04-06 | 2022-07-12 | 广东海洋大学 | Silicon-carbon composite negative electrode material and preparation method and application thereof |
CN114744172B (en) * | 2022-04-06 | 2024-03-22 | 广东海洋大学 | Silicon-carbon composite anode material and preparation method and application thereof |
CN116454256A (en) * | 2023-06-16 | 2023-07-18 | 北京壹金新能源科技有限公司 | Preparation method of silicon-carbon composite material, silicon-carbon composite material and battery |
CN116454256B (en) * | 2023-06-16 | 2023-10-03 | 北京壹金新能源科技有限公司 | Preparation method of silicon-carbon composite material, silicon-carbon composite material and battery |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109244378A (en) | Preparation method of porous nano silicon-carbon composite material | |
CN105810914B (en) | A kind of sodium-ion battery sulfur doping porous carbon materials and preparation method thereof | |
CN109256535B (en) | Silicon @ carbon composite material with yolk shell structure and preparation and application thereof | |
WO2015188726A1 (en) | Nitrogen-doped graphene coated nano-sulfur anode composite material, and preparation method and application thereof | |
CN105810915B (en) | A kind of preparation of order mesoporous carbon ball composite material of the embedding sulphur of graphene coated and the application as lithium sulfur battery anode material | |
CN105460917B (en) | A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy | |
Geng et al. | Improved electrochemical performance of biomass-derived nanoporous carbon/sulfur composites cathode for lithium-sulfur batteries by nitrogen doping | |
CN105336940B (en) | A kind of sodium titanate nano wire/graphene composite negative pole material and preparation method thereof | |
CN108394884A (en) | A kind of preparation method of chitosan-based high-specific surface area nitrogen/phosphor codoping carbon nanosheet | |
CN105762360A (en) | Graphene-silicon-coated composite negative electrode material and preparing method and application thereof | |
CN103078087B (en) | A kind of preparation method of lithium titanate/carbon nano tube composite cathode material | |
WO2022021933A1 (en) | Negative electrode material for nonaqueous electrolyte secondary battery, and preparation method therefor | |
CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
CN111063872A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
Xie et al. | Fabrication of a novel TiO 2/S composite cathode for high performance lithium–sulfur batteries | |
CN110323443A (en) | A kind of spherical N doping redox graphene material and its application | |
CN108199014A (en) | A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications | |
CN108615854A (en) | A kind of silicon substrate lithium ion battery anode active material and its preparation and application | |
CN105702956A (en) | Negative material for sodium-ion battery and preparation method of negative material | |
CN110767901A (en) | Preserved plum-shaped iron diselenide electrode material and preparation method and application thereof | |
CN109244458A (en) | Three-dimensional netted porous graphene/iron phosphate compound anode material of lithium and preparation method | |
CN110416501B (en) | Electrostatic self-assembly three-dimensional flower-shaped cobalt disulfide/rGO composite material and preparation method and application thereof | |
CN102299334A (en) | Carbon coated LiFePO4 porous anode and preparation method thereof | |
CN113690420B (en) | Nitrogen-sulfur doped silicon-carbon composite material and preparation method and application thereof | |
CN105047870A (en) | Nitrogen-doped carbon-coated silicon composite material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190118 |
|
WD01 | Invention patent application deemed withdrawn after publication |