CN108963227A - Conducting polymer coated Si composite carbon nanometer tube negative electrode material and its preparation method and application - Google Patents
Conducting polymer coated Si composite carbon nanometer tube negative electrode material and its preparation method and application Download PDFInfo
- Publication number
- CN108963227A CN108963227A CN201810794569.8A CN201810794569A CN108963227A CN 108963227 A CN108963227 A CN 108963227A CN 201810794569 A CN201810794569 A CN 201810794569A CN 108963227 A CN108963227 A CN 108963227A
- Authority
- CN
- China
- Prior art keywords
- silicon
- carbon nanotube
- polyaniline
- coated
- negative electrode
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 31
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 28
- 239000002322 conducting polymer Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 101
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 101
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000010703 silicon Substances 0.000 claims abstract description 89
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 89
- 229920000767 polyaniline Polymers 0.000 claims abstract description 81
- 239000006185 dispersion Substances 0.000 claims abstract description 48
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 94
- 239000007788 liquid Substances 0.000 claims description 62
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000036961 partial effect Effects 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 26
- 239000003995 emulsifying agent Substances 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 17
- 239000004530 micro-emulsion Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 14
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 12
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical group CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229920001296 polysiloxane Polymers 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 238000005253 cladding Methods 0.000 abstract description 7
- 239000011856 silicon-based particle Substances 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 238000010410 dusting Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- -1 carbon nanotube compound Chemical class 0.000 abstract 1
- 239000002071 nanotube Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 102220043159 rs587780996 Human genes 0.000 description 20
- 239000000523 sample Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical group [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 150000004996 alkyl benzenes Chemical class 0.000 description 5
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910014913 LixSi Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation methods of conducting polymer coated Si composite carbon nanometer tube negative electrode material, in sub-micron or nano-silicon in situ Polymerization and synchronous doping conductive polymer polyanilinc under the conditions of not using organic solvent, the cladding of polyaniline effectively inhibits the volume expansion of silicon, and good conductive capability is provided for silicon, the pi-conjugated effect of π-of polyaniline and carbon nanotube is utilized later, pre-dispersed carbon nanotube is added, so that polyaniline-coated silicon particle is evenly dispersed and is firmly secured in nanotube dispersion system.Highly conductive, elastomeric carbon nanotube provides stable inflatable elastomeric space and conductive capability further for polyaniline-coated silicon particle, thoroughly solves the destruction of the volume expansion, dusting of silicon to cathode.The polyaniline-coated nano-silicon composite carbon nanotube being finally prepared, silicon, polyaniline, three kinds of materials of carbon nanotube compound synergistic effect under, for simple substance silicone content up to 50%, specific capacity can reach 1800mAh/g or more.
Description
Technical field
The invention belongs to lithium cell cathode material technical fields, and in particular to a kind of conducting polymer coated Si composite carbon is received
Mitron negative electrode material and its preparation method and application.
Background technique
Commercial Li-ion battery negative electrode material is mainly graphite-like carbon negative pole material at present, and theoretical specific capacity is only
372mAh/g(LiC6), seriously limit the further development of lithium ion battery.Silica-base material is theoretical in grinding negative electrode material
The highest research system of specific capacity, the alloy formed are LixSi (x=0~4.4), it is 4200mAh/ that theoretical specific capacity, which is up to,
G, because of its low intercalation potential, low atomic mass, high-energy density and the high Li molar fraction in Li-Si alloy, it is considered to be
The alternative product of carbon negative pole material.However, silicium cathode has serious volume expansion due to it in embedding de- lithium cyclic process
And contraction, the destruction and mechanical crushing of material structure are caused, poor cycle performance is shown so as to cause electrode.
Summary of the invention
In order to solve the above problems existing in the present technology, the present invention provides a kind of simple substance silicone content height, specific capacity are high
Conducting polymer coated Si composite carbon nanometer tube negative electrode material and its preparation method and application.
The technical scheme adopted by the invention is as follows:
A kind of preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material, includes the following steps:
(1) elemental silicon is dispersed in water, is crushed through being sanded, obtains nano-silicon dispersion liquid；
(2) emulsifier and emulsion dispersion agent and soluble in water are taken respectively, aniline monomer is added later, are thoroughly mixed
It is even, obtain aniline microemulsion；
(3) step (1) the nano-silicon dispersion liquid is added in step (2) the aniline microemulsion, initiator is added
Initiated polymerization obtains polyaniline-coated silicon liquid；
(4) multi-walled carbon nanotube is dispersed in water, is crushed through being sanded, obtains carbon nanotube dispersed paste；
(5) carbon nanotube dispersed paste is added in polyaniline-coated silicon liquid, through high speed shear decentralized processing, is obtained
Silicon-polyaniline-carbon nanotube three-layer composite structure slurry；Wherein, excessive polyaniline nanoparticles, to carbon nano tube surface
Effectively modification is formed, by compound Three-tider architecture specific surface area of carbon nanotube is declined to a great extent, from 260 original ㎡/g
It is down to 38 ㎡/g.The formation area of carbon nano tube surface SEI film in lithium battery cyclic process can be greatly reduced, to substantially subtract
The loss of lithium ion, is greatly decreased irreversible capacity for the first time in few SEI film forming process, enables the storage lithium of carbon nanotube itself
Power effectively plays；
(6) ammonium carbonate is added into step (5) described slurry to be neutralized, successively washed, dry, crushing, obtains later
To polyaniline-coated nano-silicon composite carbon nanotube.
It is 300-1000nm that silicon grain diameter, which is D50, in step (1), in the nano-silicon dispersion liquid, the nano-silicon dispersion liquid
Middle silicon mass concentration is 5-15wt% or other feasible concentration.The silicon of 300-1000nm, which is conducive to lithium ion, relatively to be held
Easy insertion and abjection, to realize the preferable high rate performance of lithium battery.
In step (2), the emulsifier is dodecyl benzene sulfonic acid DBSA, and the emulsion dispersion agent is dodecyl sulphate
Ammonium ALS；The emulsifier and the molar ratio of the emulsion dispersion agent are 1:1, the quality of the emulsifier and the aniline monomer
Than for 1-1.7:1；
Emulsion droplet partial size in the aniline microemulsion is 20-120nm.
In step (3), the mass ratio of silicon and aniline monomer is 5:1-10:1 in the nano-silicon dispersion liquid；
The molar ratio of the initiator and aniline monomer is 0.6:1-0.7:1.
It in step (3), is added before initiator, also addition hydrochloric acid, hydrochloric acid additive amount is 0.5-1mol/L；
The initiator is ammonium sulfate, and the temperature for carrying out the polymerization reaction is 0-30 DEG C, carries out the polymerization reaction
Time is 8-20h.
In step (4), the partial size of carbon nanotube is D50≤1.5Dm in the carbon nanotube dispersed paste.
In step (5), carbon nanotube and silicon in the polyaniline-coated silicon liquid in the carbon nanotube dispersed paste
Mass ratio is 0.8:1-1.3:1.
In step (6), pH=7 is neutralized to described in progress；
The washing is carried out using deionized water；
The temperature for carrying out the drying is 80-120 DEG C.
The conducting polymer coated Si composite carbon nanometer tube negative electrode material that the method is prepared.
Application of the conducting polymer coated Si composite carbon nanometer tube negative electrode material in production lithium cell cathode material.
The invention has the benefit that
The preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material of the present invention, by first preparing
Nano-silicon dispersion liquid is obtained, then aniline microemulsion is prepared, later by sub-micro under conditions of not using organic solvent
Rice or nano-silicon in situ Polymerization and synchronous doping conductive polymer polyanilinc, the effective body for inhibiting silicon of the cladding of polyaniline
Product expansion, and good conductive capability is provided for silicon, the pi-conjugated effect of π-of polyaniline and carbon nanotube, addition are utilized later
By the pre-dispersed carbon nanotube of high-energy ball milling, so that polyaniline-coated silicon particle is evenly dispersed and is firmly secured to carbon nanotube
In dispersion.Highly conductive, elastomeric carbon nanotube provides stable expansion bullet further for polyaniline-coated silicon particle
Property space and conductive capability, to thoroughly solve the destruction of the volume expansion of silicon, dusting to cathode.In addition, polyaniline-coated
Silicon and appropriate excessive nanoscale polyaniline particles are adsorbed in carbon nanotube, all form effective physics to carbon nanotube and repair
Decorations, are greatly lowered the specific surface area of carbon nanotube, so that the reversible lithium storage capacity of carbon nanotube itself be enable to play；Finally
The polyaniline-coated nano-silicon composite carbon nanotube being prepared, in the compound collaboration of silicon, three kinds of polyaniline, carbon nanotube materials
Under effect, for simple substance silicone content up to 50%, specific capacity can reach 1800mAh/g or more, coulombic efficiency, high rate performance and follow for the first time
Ring stability greatly improves, and the polyaniline-coated nano-silicon composite carbon nanotube can be used alone as cathode, can also with it is existing
There is the addition of graphite cathode system arbitrary proportion compound, can be added according to the demand proper proportion of cathode specific capacity.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1
The present embodiment provides a kind of preparation methods of conducting polymer coated Si composite carbon nanometer tube negative electrode material, including such as
Lower step:
(1) elemental silicon (D50=7 microns, purity 99.95%, iron content < 120ppm) is dispersed in water, through powder is sanded
Broken 4h obtains nano-silicon dispersion liquid, and silicon grain diameter is D50=300nm in the nano-silicon dispersion liquid；
(2) emulsifier dodecyl benzene sulfonic acid DBSA (while being also the protonic acid doping agent of polyaniline) and lotion are taken respectively
Dispersing agent ammonium lauryl sulfate ALS is simultaneously soluble in water, and the molar ratio of the emulsifier and the emulsion dispersion agent is 1:1, it
After be added aniline monomer, the mass ratio of the aniline monomer and the emulsifier is 1:1.7, is thoroughly mixed uniformly, obtains
Emulsion droplet partial size is the aniline microemulsion of 20-30nm；
(3) step (1) the nano-silicon dispersion liquid is added in step (2) the aniline microemulsion, is received described in control
The mass ratio of silicon and aniline monomer is 5:1 in rice silicon dispersion liquid, acid medium needed for hydrochloric acid supplement polymerization reaction is first added,
Hydrochloric acid additive amount is 0.5mol/L；Initiator ammonium sulfate initiated polymerization is added, the initiator and aniline monomer are controlled
Molar ratio be 0.6:1, polymeric reaction temperature be 25 DEG C, polymerization reaction time 8h obtains polyaniline-coated silicon liquid；In
It is doped in polyaniline molecule chain with filtering, cleaning, dried product exhibited weight measurement dodecyl benzene sulfonic acid 95%, assigns silicon
The excellent electric conductivity in surface；Blackish green polyaniline-coated is in khaki nanometer silicon face, because polyaniline-coated layer is relatively thin about
50nm cannot block the color of silicon completely, therefore product polyaniline-coated silicon is the micro- green of the colour of loess；Polyphenyl through detecting, after cladding
The partial size of amine coated Si is 500nm, and four probe tabletting conductivity are 2.4S/cm；
(4) by multi-walled carbon nanotube, (CNTS, purity 99.5%, iron content are less than 100ppm, caliber 15-20nm, draw ratio
1:500, aggregated particle size D50 < 10Dm, four probe tabletting conductivity=11S/cm) it is dispersed in water, it is crushed through being sanded, obtains carbon
Nanotube dispersed paste, the partial size of carbon nanotube is D50=1.5Dm in the carbon nanotube dispersed paste；It is observed by Electronic Speculum,
It is dispersed preferable；
(5) carbon nanotube dispersed paste is added in polyaniline-coated silicon (PANSI) liquid, controls the carbon nanotube
Carbon nanotube and the mass ratio of silicon in the polyaniline-coated silicon liquid are 1.3:1 in dispersed paste, are dispersed through high speed shear
Emulsification treatment obtains silicon-polyaniline-carbon nanotube three-layer composite structure slurry；Polyaniline and carbon nanotube are in the pi-conjugated effect of π-
It should act on down, PANSI is attached together with CNTS rapidly, and mixing liquid becomes black, upper liquid after water intaking dilution precipitating completely
Body is colorless and transparent, and no PANSI suspends, and illustrates to be attached together with CNTS completely；Carbon nanotube is into one under high shear agitation
Step dispersion, PANSI is evenly dispersed and is embedded between carbon nanotube；Carbon nano-tube fibre shape elastic bunch is formed around PANSI
Space is tied up, stable and firm silicon-polyaniline-carbon nanotube three-layer composite structure is formed；It, D50=4 microns of partial size, should through detecting
The composite construction that the PANSI+CNTS of partial size not instead of single structure, multiple PANSI and CNTS are formed；Four probe tabletting conductances
Rate is 10S/cm, close to the conductivity of CNTS used 11S/cm itself；
(6) sal volatile is added into step (5) described slurry to hydrochloric acid and ammonium persulfate and undoped 12
Alkyl benzene sulphonate carries out being neutralized to pH=7, successively adopts later and is washed with deionized, 80 DEG C of dryings, crushes, obtains polyaniline packet
Cover nano-silicon composite carbon nanotube.Through detecting, in the polyaniline-coated nano-silicon composite carbon nanometer tube composite materials, elemental silicon
Content 35.7%.
Embodiment 2
The present embodiment provides a kind of preparation methods of conducting polymer coated Si composite carbon nanometer tube negative electrode material, including such as
Lower step:
(1) elemental silicon (D50=7 microns, purity 99.95%, iron content < 120ppm) is dispersed in water, through powder is sanded
Broken 2h obtains nano-silicon dispersion liquid, and silicon grain diameter is D50=1000nm in the nano-silicon dispersion liquid；
(2) emulsifier dodecyl benzene sulfonic acid DBSA (while being also the protonic acid doping agent of polyaniline) and lotion are taken respectively
Dispersing agent ammonium lauryl sulfate ALS is simultaneously soluble in water, and the molar ratio of the emulsifier and the emulsion dispersion agent is 1:1, it
After be added aniline monomer, the mass ratio of the aniline monomer and the emulsifier is 1:1, is thoroughly mixed uniformly, obtains cream
Liquid size droplet diameter is the aniline microemulsion of 110-120nm；
(3) step (1) the nano-silicon dispersion liquid is added in step (2) the aniline microemulsion, is received described in control
The mass ratio of silicon and aniline monomer is 10:1 in rice silicon dispersion liquid, and acidity needed for hydrochloric acid supplement polymerization reaction is first added is situated between
Matter, hydrochloric acid additive amount are 1mol/L；Initiator ammonium sulfate initiated polymerization is added, the initiator and aniline monomer are controlled
Molar ratio be 0.7:1, polymeric reaction temperature be 30 DEG C, polymerization reaction time 20h obtains polyaniline-coated silicon liquid；Through
It neutralizes, filtering, clean, dried product exhibited weight measurement dodecyl benzene sulfonic acid 88% is doped in polyaniline molecule chain, imparting
The excellent electric conductivity of silicon face；Blackish green polyaniline-coated is in khaki nanometer silicon face, because polyaniline-coated layer is relatively thin
About 200nm cannot block the color of silicon completely, therefore product polyaniline-coated silicon is the micro- green of the colour of loess；It is poly- after cladding through detecting
The partial size of aniline coated Si is 2Dm, and four probe tabletting conductivity are 1.7S/cm；
(4) by multi-walled carbon nanotube, (CNTS, purity 99.5%, iron content are less than 100ppm, caliber 15-20nm, draw ratio
1:500, aggregated particle size D50 < 10Dm, four probe tabletting conductivity=11S/cm) it is dispersed in water, it is crushed through being sanded, obtains carbon
Nanotube dispersed paste, the partial size of carbon nanotube is D50=1.5Dm in the carbon nanotube dispersed paste；It is observed by Electronic Speculum,
It is dispersed preferable；
(5) carbon nanotube dispersed paste is added in polyaniline-coated silicon (PANSI) liquid, controls the carbon nanotube
Carbon nanotube and the mass ratio of silicon in the polyaniline-coated silicon liquid are 0.8:1 in dispersed paste, are dispersed through high speed shear
Emulsification treatment obtains silicon-polyaniline-carbon nanotube three-layer composite structure slurry；Polyaniline and carbon nanotube are in the pi-conjugated effect of π-
It should act on down, PANSI is attached together with CNTS rapidly, and mixing liquid becomes black, upper liquid after water intaking dilution precipitating completely
Body is colorless and transparent, and no PANSI suspends, and illustrates to be attached together with CNTS completely；Carbon nanotube is into one under high shear agitation
Step dispersion, PANSI is evenly dispersed and is embedded between carbon nanotube；Carbon nano-tube fibre shape elastic bunch is formed around PANSI
Space is tied up, stable and firm silicon-polyaniline-carbon nanotube three-layer composite structure is formed；It, D50=6 microns of partial size, should through detecting
The composite construction that the PANSI+CNTS of partial size not instead of single structure, multiple PANSI and CNTS are formed；Four probe tabletting conductances
Rate is 8S/cm, close to the conductivity of CNTS used 11S/cm itself；
(6) sal volatile is added into step (5) described slurry to hydrochloric acid and ammonium persulfate and undoped 12
Alkyl benzene sulphonate carries out being neutralized to pH=7, successively adopts later and is washed with deionized, 120 DEG C of dryings, crushes, obtains polyaniline
Coat nano-silicon composite carbon nanotube.Through detecting, in the polyaniline-coated nano-silicon composite carbon nanometer tube composite materials, simple substance
Silicone content 50%.
Embodiment 3
The present embodiment provides a kind of preparation methods of conducting polymer coated Si composite carbon nanometer tube negative electrode material, including such as
Lower step:
(1) elemental silicon (D50=7 microns, purity 99.95%, iron content < 120ppm) is dispersed in water, through powder is sanded
Broken 3h obtains nano-silicon dispersion liquid, and silicon grain diameter is D50=500nm in the nano-silicon dispersion liquid；
(2) emulsifier dodecyl benzene sulfonic acid DBSA (while being also the protonic acid doping agent of polyaniline) and lotion are taken respectively
Dispersing agent ammonium lauryl sulfate ALS is simultaneously soluble in water, and the molar ratio of the emulsifier and the emulsion dispersion agent is 1:1, it
After be added aniline monomer, the mass ratio of the aniline monomer and the emulsifier is 1:1.3, is thoroughly mixed uniformly, obtains
Emulsion droplet partial size is the aniline microemulsion of 50-60nm；
(3) step (1) the nano-silicon dispersion liquid is added in step (2) the aniline microemulsion, is received described in control
The mass ratio of silicon and aniline monomer is 7:1 in rice silicon dispersion liquid, acid medium needed for hydrochloric acid supplement polymerization reaction is first added,
Hydrochloric acid additive amount is 0.75mol/L；Initiator ammonium sulfate initiated polymerization 14h is added, the initiator and aniline are controlled
The molar ratio of monomer is 0.7:1, and polymeric reaction temperature is 0 DEG C, and polymerization reaction time 12h obtains polyaniline-coated silicon liquid；
Neutralized, filtering, cleaning, dried product exhibited weight measurement dodecyl benzene sulfonic acid 90% are doped in polyaniline molecule chain, are assigned
Give the excellent electric conductivity of silicon face；Blackish green polyaniline-coated in khaki nanometer silicon face because polyaniline-coated layer compared with
Thin about 100nm cannot block the color of silicon completely, therefore product polyaniline-coated silicon is the micro- green of the colour of loess；Through detecting, after cladding
The partial size of polyaniline-coated silicon is 800nm, and four probe tabletting conductivity are 2.1S/cm；
(4) by multi-walled carbon nanotube, (CNTS, purity 99.5%, iron content are less than 100ppm, caliber 15-20nm, draw ratio
1:500, aggregated particle size D50 < 10Dm, four probe tabletting conductivity=11S/cm) it is dispersed in water, it is crushed through being sanded, obtains carbon
Nanotube dispersed paste, the partial size of carbon nanotube is D50=1.5Dm in the carbon nanotube dispersed paste；It is observed by Electronic Speculum,
It is dispersed preferable；
(5) carbon nanotube dispersed paste is added in polyaniline-coated silicon (PANSI) liquid, controls the carbon nanotube
Carbon nanotube and the mass ratio of silicon in the polyaniline-coated silicon liquid are 1.1:1 in dispersed paste, are dispersed through high speed shear
Emulsification treatment obtains silicon-polyaniline-carbon nanotube three-layer composite structure slurry；Polyaniline and carbon nanotube are in the pi-conjugated effect of π-
It should act on down, PANSI is attached together with CNTS rapidly, and mixing liquid becomes black, upper liquid after water intaking dilution precipitating completely
Body is colorless and transparent, and no PANSI suspends, and illustrates to be attached together with CNTS completely；Carbon nanotube is into one under high shear agitation
Step dispersion, PANSI is evenly dispersed and is embedded between carbon nanotube；Carbon nano-tube fibre shape elastic bunch is formed around PANSI
Space is tied up, stable and firm silicon-polyaniline-carbon nanotube three-layer composite structure is formed；It, D50=5 microns of partial size, should through detecting
The composite construction that the PANSI+CNTS of partial size not instead of single structure, multiple PANSI and CNTS are formed；Four probe tabletting conductances
Rate is 9S/cm, close to the conductivity of CNTS used 11S/cm itself；
(6) sal volatile is added into step (5) described slurry to hydrochloric acid and ammonium persulfate and undoped 12
Alkyl benzene sulphonate carries out being neutralized to pH=7, successively adopts later and is washed with deionized, 100 DEG C of dryings, crushes, obtains polyaniline
Coat nano-silicon composite carbon nanotube.Through detecting, in the polyaniline-coated nano-silicon composite carbon nanometer tube composite materials, simple substance
Silicone content 42%.
Embodiment 4
The present embodiment provides a kind of preparation methods of conducting polymer coated Si composite carbon nanometer tube negative electrode material, including such as
Lower step:
(1) elemental silicon (D50=7 microns, purity 99.95%, iron content < 120ppm) is dispersed in water, through powder is sanded
Broken 3h obtains nano-silicon dispersion liquid, and silicon grain diameter is D50=500nm in the nano-silicon dispersion liquid；
(2) emulsifier dodecyl benzene sulfonic acid DBSA (while being also the protonic acid doping agent of polyaniline) and lotion are taken respectively
Dispersing agent ammonium lauryl sulfate ALS is simultaneously soluble in water, and the molar ratio of the emulsifier and the emulsion dispersion agent is 1:1, it
After be added aniline monomer, the mass ratio of the aniline monomer and the emulsifier is 1:1.2, is thoroughly mixed uniformly, obtains
Emulsion droplet partial size is the aniline microemulsion of 60-70nm；
(3) step (1) the nano-silicon dispersion liquid is added in step (2) the aniline microemulsion, is received described in control
The mass ratio of silicon and aniline monomer is 8:1 in rice silicon dispersion liquid, acid medium needed for hydrochloric acid supplement polymerization reaction is first added,
Hydrochloric acid additive amount is 0.8mol/L；Initiator ammonium sulfate initiated polymerization 15h is added, the initiator and aniline list are controlled
The molar ratio of body is 0.7:1, and polymeric reaction temperature is 20 DEG C, and polymerization reaction time 15h obtains polyaniline-coated silicon liquid；
Neutralized, filtering, cleaning, dried product exhibited weight measurement dodecyl benzene sulfonic acid 92% are doped in polyaniline molecule chain, are assigned
Give the excellent electric conductivity of silicon face；Blackish green polyaniline-coated in khaki nanometer silicon face because polyaniline-coated layer compared with
Thin about 90nm cannot block the color of silicon completely, therefore product polyaniline-coated silicon is the micro- green of the colour of loess；Through detecting, after cladding
The partial size of polyaniline-coated silicon is 780nm, and four probe tabletting conductivity are 2.2S/cm；
(4) by multi-walled carbon nanotube, (CNTS, purity 99.5%, iron content are less than 100ppm, caliber 15-20nm, draw ratio
1:500, aggregated particle size D50 < 10Dm, four probe tabletting conductivity=11S/cm) it is dispersed in water, it is crushed through being sanded, obtains carbon
Nanotube dispersed paste, the partial size of carbon nanotube is D50=1.5Dm in the carbon nanotube dispersed paste；It is observed by Electronic Speculum,
It is dispersed preferable；
(5) carbon nanotube dispersed paste is added in polyaniline-coated silicon (PANSI) liquid, controls the carbon nanotube
Carbon nanotube and the mass ratio of silicon in the polyaniline-coated silicon liquid are 1.2:1 in dispersed paste, are dispersed through high speed shear
Emulsification treatment obtains silicon-polyaniline-carbon nanotube three-layer composite structure slurry；Polyaniline and carbon nanotube are in the pi-conjugated effect of π-
It should act on down, PANSI is attached together with CNTS rapidly, and mixing liquid becomes black, upper liquid after water intaking dilution precipitating completely
Body is colorless and transparent, and no PANSI suspends, and illustrates to be attached together with CNTS completely；Carbon nanotube is into one under high shear agitation
Step dispersion, PANSI is evenly dispersed and is embedded between carbon nanotube；Carbon nano-tube fibre shape elastic bunch is formed around PANSI
Space is tied up, stable and firm silicon-polyaniline-carbon nanotube three-layer composite structure is formed；Through detecting, D50=5.1 microns of partial size,
The composite construction that the PANSI+CNTS of the partial size not instead of single structure, multiple PANSI and CNTS are formed；Four probe tabletting electricity
Conductance is 9.5S/cm, close to the conductivity of CNTS used 11S/cm itself；
(6) sal volatile is added into step (5) described slurry to hydrochloric acid and ammonium persulfate and undoped 12
Alkyl benzene sulphonate carries out being neutralized to pH=7, successively adopts later and is washed with deionized, 110 DEG C of dryings, crushes, obtains polyaniline
Coat nano-silicon composite carbon nanotube.Through detecting, in the polyaniline-coated nano-silicon composite carbon nanometer tube composite materials, simple substance
Silicone content 41%.
Embodiment 5
The present embodiment provides a kind of preparation methods of conducting polymer coated Si composite carbon nanometer tube negative electrode material, including such as
Lower step:
(1) elemental silicon (D50=7 microns, purity 99.95%, iron content < 120ppm) is dispersed in water, through powder is sanded
Broken 3.5h obtains nano-silicon dispersion liquid, and silicon grain diameter is D50=400nm in the nano-silicon dispersion liquid；
(2) emulsifier dodecyl benzene sulfonic acid DBSA (while being also the protonic acid doping agent of polyaniline) and lotion are taken respectively
Dispersing agent ammonium lauryl sulfate ALS is simultaneously soluble in water, and the molar ratio of the emulsifier and the emulsion dispersion agent is 1:1, it
After be added aniline monomer, the mass ratio of the aniline monomer and the emulsifier is 1:1.5, is thoroughly mixed uniformly, obtains
Emulsion droplet partial size is the aniline microemulsion of 35-45nm；
(3) step (1) the nano-silicon dispersion liquid is added in step (2) the aniline microemulsion, is received described in control
The mass ratio of silicon and aniline monomer is 6:1 in rice silicon dispersion liquid, acid medium needed for hydrochloric acid supplement polymerization reaction is first added,
Hydrochloric acid additive amount is 0.6mol/L；Initiator ammonium sulfate initiated polymerization 18h is added, the initiator and aniline list are controlled
The molar ratio of body is 0.7:1, and polymeric reaction temperature is 22 DEG C, and polymerization reaction time 15h obtains polyaniline-coated silicon liquid；
Neutralized, filtering, cleaning, dried product exhibited weight measurement dodecyl benzene sulfonic acid 93% are doped in polyaniline molecule chain, are assigned
Give the excellent electric conductivity of silicon face；Blackish green polyaniline-coated in khaki nanometer silicon face because polyaniline-coated layer compared with
Thin about 80nm cannot block the color of silicon completely, therefore product polyaniline-coated silicon is the micro- green of the colour of loess；Through detecting, after cladding
The partial size of polyaniline-coated silicon is 700nm, and four probe tabletting conductivity are 2.3S/cm；
(4) by multi-walled carbon nanotube, (CNTS, purity 99.5%, iron content are less than 100ppm, caliber 15-20nm, draw ratio
1:500, aggregated particle size D50 < 10Dm, four probe tabletting conductivity=11S/cm) it is dispersed in water, it is crushed through being sanded, obtains carbon
Nanotube dispersed paste, the partial size of carbon nanotube is D50=1.5Dm in the carbon nanotube dispersed paste；It is observed by Electronic Speculum,
It is dispersed preferable；
(5) carbon nanotube dispersed paste is added in polyaniline-coated silicon (PANSI) liquid, controls the carbon nanotube
Carbon nanotube and the mass ratio of silicon in the polyaniline-coated silicon liquid are 1.2:1 in dispersed paste, are dispersed through high speed shear
Emulsification treatment obtains silicon-polyaniline-carbon nanotube three-layer composite structure slurry；Polyaniline and carbon nanotube are in the pi-conjugated effect of π-
It should act on down, PANSI is attached together with CNTS rapidly, and mixing liquid becomes black, upper liquid after water intaking dilution precipitating completely
Body is colorless and transparent, and no PANSI suspends, and illustrates to be attached together with CNTS completely；Carbon nanotube is into one under high shear agitation
Step dispersion, PANSI is evenly dispersed and is embedded between carbon nanotube；Carbon nano-tube fibre shape elastic bunch is formed around PANSI
Space is tied up, stable and firm silicon-polyaniline-carbon nanotube three-layer composite structure is formed；Through detecting, D50=4.8 microns of partial size,
The composite construction that the PANSI+CNTS of the partial size not instead of single structure, multiple PANSI and CNTS are formed；Four probe tabletting electricity
Conductance is 9.2S/cm, close to the conductivity of CNTS used 11S/cm itself；
(6) sal volatile is added into step (5) described slurry to hydrochloric acid and ammonium persulfate and undoped 12
Alkyl benzene sulphonate carries out being neutralized to pH=7, successively adopts later and is washed with deionized, 110 DEG C of dryings, crushes, obtains polyaniline
Coat nano-silicon composite carbon nanotube；Through detecting, in the polyaniline-coated nano-silicon composite carbon nanometer tube composite materials, simple substance
Silicone content 39.5%.
Experimental example
Electrochemical property test:
Conducting polymer coated Si composite carbon nanometer tube negative electrode material obtained in embodiment 1-3 is assembled into button respectively
Battery A1, A2, A3；Preparation method are as follows: add binder and distilled water in negative electrode material, be stirred slurrying, be coated in
It is obtained by drying, rolling on copper foil.Binder used is SBR binder, and negative electrode material is prepared negative for embodiment 1-3
Pole material, solvent are secondary distilled water, its ratio be: negative electrode material: SBR: distilled water=55g:2g:220ml；Chemical property
It is carried out on the blue electricity CT2001A type cell tester in Wuhan, charging/discharging voltage range is 0.005V to 3.0V, and charge-discharge velocity is
0.1C。
Comparative example: the graphite purchased in the market+silicium cathode system is negative electrode material, silicone content 8%, other operations and implementation
Example is identical, and test result is shown in Table 1.
Table 1- embodiment and comparative example buckle electrical test results comparison
As it can be seen from table 1 the electric discharge of the conducting polymer coated Si composite carbon nanometer tube negative electrode material of embodiment preparation
Capacity and its efficiency are apparently higher than comparative example.
The cycle performance contrast table of table 2- embodiment and comparative example
From table 2 it can be seen that the cycle performance for the material that embodiment is prepared is obviously excellent in the cycle performance in each stage
In comparative example, the good cycle of material.
The high rate performance of table 3- material
From table 3 it can be seen that material of the present invention still is able to keep very high capacity when being large current discharge,
Show good high rate performance.
The present invention is not limited to above-mentioned preferred forms, anyone can show that other are various under the inspiration of the present invention
The product of form, however, make any variation in its shape or structure, it is all that there is skill identical or similar to the present application
Art scheme, is within the scope of the present invention.
Claims (10)
1. a kind of preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material, which is characterized in that including as follows
Step:
(1) elemental silicon is dispersed in water, is crushed through being sanded, obtains nano-silicon dispersion liquid；
(2) emulsifier and emulsion dispersion agent and soluble in water are taken respectively, aniline monomer is added later, are thoroughly mixed uniformly,
Obtain aniline microemulsion；
(3) step (1) the nano-silicon dispersion liquid is added in step (2) the aniline microemulsion, initiator is added and causes
Polymerization reaction obtains polyaniline-coated silicon liquid；
(4) multi-walled carbon nanotube is dispersed in water, is crushed through being sanded, obtains carbon nanotube dispersed paste；
(5) carbon nanotube dispersed paste is added in polyaniline-coated silicon liquid, through high speed shear decentralized processing, obtains silicon-
Polyaniline-carbon nanotube three-layer composite structure slurry；
(6) ammonium carbonate is added into step (5) described slurry to be neutralized, successively washed, dry, crushing, is gathered later
Aniline coats nano-silicon composite carbon nanotube.
2. the preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material according to claim 1, special
Sign is, it is 300-1000nm that silicon grain diameter, which is D50, in step (1), in the nano-silicon dispersion liquid.
3. the preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material according to claim 1, special
Sign is, in step (2), the emulsifier is dodecyl benzene sulfonic acid DBSA, and the emulsion dispersion agent is dodecyl sulphate
The molar ratio of ammonium ALS, the emulsifier and the emulsion dispersion agent is 1:1, the quality of the emulsifier and the aniline monomer
Than for 1-1.7:1；
Emulsion droplet partial size in the aniline microemulsion is 20-120nm.
4. the preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material according to claim 1, special
Sign is, in step (3), the mass ratio of silicon and aniline monomer is 5:1-10:1 in the nano-silicon dispersion liquid；
The molar ratio of the initiator and aniline monomer is 0.6:1-0.7:1.
5. the preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material according to claim 1, special
Sign is, in step (3), is added before initiator, also addition hydrochloric acid, and hydrochloric acid additive amount is 0.5-1mol/L；
The initiator is ammonium sulfate, and the temperature for carrying out the polymerization reaction is 0-30 DEG C, carries out the time of the polymerization reaction
For 8-20h.
6. the preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material according to claim 1, special
Sign is, in step (4), the partial size of carbon nanotube is D50≤1.5Dm in the carbon nanotube dispersed paste.
7. the preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material according to claim 1, special
Sign is, in step (5), the matter of carbon nanotube and silicon in the polyaniline-coated silicon liquid in the carbon nanotube dispersed paste
The ratio between amount is 0.8:1-1.3:1.
8. the preparation method of conducting polymer coated Si composite carbon nanometer tube negative electrode material according to claim 1, special
Sign is, in step (6), is neutralized to pH=7 described in progress；
The washing is carried out using deionized water；
The temperature for carrying out the drying is 80-120 DEG C.
9. the conducting polymer coated Si composite carbon nanometer tube cathode material that any one of claim 1-8 the method is prepared
Material.
10. conducting polymer coated Si composite carbon nanometer tube negative electrode material described in claim 9 is in production lithium cell cathode material
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810794569.8A CN108963227B (en) | 2018-07-19 | 2018-07-19 | Conductive polymer coated silicon composite carbon nanotube negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810794569.8A CN108963227B (en) | 2018-07-19 | 2018-07-19 | Conductive polymer coated silicon composite carbon nanotube negative electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108963227A true CN108963227A (en) | 2018-12-07 |
| CN108963227B CN108963227B (en) | 2021-02-19 |
Family
ID=64481900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810794569.8A Active CN108963227B (en) | 2018-07-19 | 2018-07-19 | Conductive polymer coated silicon composite carbon nanotube negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108963227B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109728281A (en) * | 2018-12-31 | 2019-05-07 | 青岛农业大学 | A kind of preparation method of the modified SiOx electrode material in surface |
| CN109755553A (en) * | 2019-03-20 | 2019-05-14 | 北京航空航天大学 | A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system |
| CN110931790A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Conjugated trapezoidal polymer-carbon nanotube composite material and preparation method and application thereof |
| CN111769266A (en) * | 2020-06-23 | 2020-10-13 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode material and lithium ion battery containing same |
| CN111816852A (en) * | 2020-06-29 | 2020-10-23 | 瑞声科技（南京）有限公司 | Preparation method of silicon-based composite negative electrode material |
| CN112500563A (en) * | 2020-11-13 | 2021-03-16 | 四川普利司德高分子新材料有限公司 | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as lithium ion battery cathode binder |
| WO2022078881A1 (en) * | 2020-10-13 | 2022-04-21 | Aixtron Se | Method for manufacturing an electrode for a lithium-ion battery, and electrode manufactured according to the method |
| TWI810978B (en) * | 2022-06-10 | 2023-08-01 | 鴻海精密工業股份有限公司 | Method of making lithium-ion battery anode |
| WO2023163012A1 (en) * | 2022-02-28 | 2023-08-31 | パナソニックＩｐマネジメント株式会社 | Negative electrode active material for secondary batteries, method for producing same, negative electrode and secondary battery |
| WO2023184098A1 (en) * | 2022-03-28 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Silicon-containing negative electrode active material, and negative electrode plate, secondary battery and electric device comprising same |
| TWI832294B (en) * | 2022-06-10 | 2024-02-11 | 鴻海精密工業股份有限公司 | Lithium-ion battery anode |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789307A (en) * | 2004-12-15 | 2006-06-21 | 同济大学 | Method for preparing high-contented polyaniline micro-emulsion |
| CN101210119A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Silicon-containing composite material and its preparation method and application |
| CN102134317A (en) * | 2010-01-27 | 2011-07-27 | 中国科学院合肥物质科学研究院 | Preparation method of carbon nano tube/polyaniline nano composite conductive powder |
| CN103227318A (en) * | 2013-04-02 | 2013-07-31 | 东莞新能源科技有限公司 | Silicon-based composite material, preparation method and application thereof |
| CN104332597A (en) * | 2014-10-20 | 2015-02-04 | 北京化工大学 | Polyacid/polyaniline/carbon nano tube electrode material as well as preparation method and application thereof |
| CN104409709A (en) * | 2014-11-27 | 2015-03-11 | 中航锂电（洛阳）有限公司 | Lithium-ion battery negative electrode material, preparation method and lithium ion battery |
| CN104518209A (en) * | 2014-12-09 | 2015-04-15 | 江西正拓新能源科技股份有限公司 | Lithium ion battery silicon composite material and preparation method thereof |
| CN106229495A (en) * | 2016-09-30 | 2016-12-14 | 深圳大学 | A kind of silicon based anode material of conducting polymer cladding and preparation method thereof |
| KR20180027745A (en) * | 2016-09-07 | 2018-03-15 | 한양대학교 산학협력단 | Amorphous Silicon Oxide-Conducting polymer Complex and Lithium Secondary Battery using the same |
-
2018
- 2018-07-19 CN CN201810794569.8A patent/CN108963227B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789307A (en) * | 2004-12-15 | 2006-06-21 | 同济大学 | Method for preparing high-contented polyaniline micro-emulsion |
| CN101210119A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Silicon-containing composite material and its preparation method and application |
| CN102134317A (en) * | 2010-01-27 | 2011-07-27 | 中国科学院合肥物质科学研究院 | Preparation method of carbon nano tube/polyaniline nano composite conductive powder |
| CN103227318A (en) * | 2013-04-02 | 2013-07-31 | 东莞新能源科技有限公司 | Silicon-based composite material, preparation method and application thereof |
| CN104332597A (en) * | 2014-10-20 | 2015-02-04 | 北京化工大学 | Polyacid/polyaniline/carbon nano tube electrode material as well as preparation method and application thereof |
| CN104409709A (en) * | 2014-11-27 | 2015-03-11 | 中航锂电（洛阳）有限公司 | Lithium-ion battery negative electrode material, preparation method and lithium ion battery |
| CN104518209A (en) * | 2014-12-09 | 2015-04-15 | 江西正拓新能源科技股份有限公司 | Lithium ion battery silicon composite material and preparation method thereof |
| KR20180027745A (en) * | 2016-09-07 | 2018-03-15 | 한양대학교 산학협력단 | Amorphous Silicon Oxide-Conducting polymer Complex and Lithium Secondary Battery using the same |
| CN106229495A (en) * | 2016-09-30 | 2016-12-14 | 深圳大学 | A kind of silicon based anode material of conducting polymer cladding and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| JIGUO TU等: "In-situ synthesis of silicon/polyaniline core/shell and its electrochemical performance for lithium-ion batteries", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| LISONG XIAO等: "Novel Si-CNT/polyaniline nanocomposites as lithium-ion battery anodes for improved cycling performance", 《MATERIALS TODAY: PROCEEDINGS》 * |
| XIAOMING ZHOU等: "Polyaniline-encapsulated silicon on three-dimensional carbon nanotubes foam with enhanced electrochemical performance for lithium-ion batteries", 《JOURNAL OF POWER SOURCES》 * |
| 冯明燕: "锂离子电池硅基负极材料的制备及电化学性能", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109728281B (en) * | 2018-12-31 | 2021-10-12 | 青岛农业大学 | Preparation method of surface modified SiOx electrode material |
| CN109728281A (en) * | 2018-12-31 | 2019-05-07 | 青岛农业大学 | A kind of preparation method of the modified SiOx electrode material in surface |
| CN109755553A (en) * | 2019-03-20 | 2019-05-14 | 北京航空航天大学 | A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system |
| CN110931790A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Conjugated trapezoidal polymer-carbon nanotube composite material and preparation method and application thereof |
| CN110931790B (en) * | 2019-10-25 | 2022-05-06 | 合肥国轩高科动力能源有限公司 | Conjugated trapezoidal polymer-carbon nanotube composite material and preparation method and application thereof |
| CN111769266A (en) * | 2020-06-23 | 2020-10-13 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode material and lithium ion battery containing same |
| CN111816852A (en) * | 2020-06-29 | 2020-10-23 | 瑞声科技（南京）有限公司 | Preparation method of silicon-based composite negative electrode material |
| WO2022078881A1 (en) * | 2020-10-13 | 2022-04-21 | Aixtron Se | Method for manufacturing an electrode for a lithium-ion battery, and electrode manufactured according to the method |
| CN112500563A (en) * | 2020-11-13 | 2021-03-16 | 四川普利司德高分子新材料有限公司 | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as lithium ion battery cathode binder |
| CN112500563B (en) * | 2020-11-13 | 2023-10-31 | 四川普利司德高分子新材料有限公司 | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery |
| WO2023163012A1 (en) * | 2022-02-28 | 2023-08-31 | パナソニックＩｐマネジメント株式会社 | Negative electrode active material for secondary batteries, method for producing same, negative electrode and secondary battery |
| WO2023184098A1 (en) * | 2022-03-28 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Silicon-containing negative electrode active material, and negative electrode plate, secondary battery and electric device comprising same |
| TWI810978B (en) * | 2022-06-10 | 2023-08-01 | 鴻海精密工業股份有限公司 | Method of making lithium-ion battery anode |
| TWI832294B (en) * | 2022-06-10 | 2024-02-11 | 鴻海精密工業股份有限公司 | Lithium-ion battery anode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108963227B (en) | 2021-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108963227A (en) | Conducting polymer coated Si composite carbon nanometer tube negative electrode material and its preparation method and application | |
| CN102544502B (en) | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery | |
| CN104638252B (en) | Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery | |
| CN105098151B (en) | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof | |
| CN103633295B (en) | A kind of Si-C composite material, lithium ion battery and its preparation method and application | |
| JP7030119B2 (en) | Microcapsule type silicon-carbon composite negative electrode material, its manufacturing method and its use | |
| CN101210119B (en) | Silicon-containing composite material and its preparation method and application | |
| CN106784714B (en) | A kind of silicon-based composite anode material for Li-ion battery and preparation method thereof | |
| CN105742599B (en) | Si-C composite material and preparation method thereof and negative electrode material and battery | |
| CN105355877B (en) | A kind of graphene metal oxide composite cathode material and preparation method thereof | |
| CN107565112A (en) | A kind of preparation method of graphene coated lithium ion secondary battery anode material | |
| CN111384373B (en) | Silicon-carbon composite material for lithium ion battery and preparation method thereof | |
| CN105047419B (en) | Manganese dioxide/carbon combination electrode material and preparation method thereof and ultracapacitor | |
| CN108281634A (en) | A kind of method and its application of graphene coated graphite negative material of lithium ion battery | |
| CN104103807A (en) | Silicon-carbon composite anode material, preparation method thereof and lithium ion battery | |
| CN103193263A (en) | Preparation method and application of hollow SnO2@C nanosphere in lithium ion battery | |
| CN107403920A (en) | A kind of silicon-carbon combination electrode and preparation method thereof | |
| CN106558729B (en) | A kind of lithium ion battery of graphene as anode sizing agent conductive agent | |
| CN100383037C (en) | Carbon material and nano silicon composite materials and method for preparing same and use thereof | |
| CN105702958B (en) | Preparation method and application of tin dioxide quantum dot solution and composite material thereof | |
| CN105161675A (en) | Preparation method for lithium titanate negative electrode slurry of lithium battery | |
| CN108470899A (en) | Nano-silicon/carbon composite, preparation method and include its lithium ion battery as negative material | |
| CN108807835A (en) | The preparation method and battery of one type of metal graphene negative material | |
| CN109546120A (en) | A kind of graphene-based Si-C composite material and preparation method thereof | |
| CN110247038A (en) | A kind of Bi2S3-MoS2/ graphene composite nano 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210825 Address after: 255000 1-11-3, floor 1, plant 3, entrepreneurship Park, Zibo science and Technology Industrial Park, No. 69, Sanying Road, Fangzhen Town, Zhangdian District, Zibo City, Shandong Province Patentee after: Zibo JuLang New Energy Technology Co.,Ltd. Address before: 255000 Room 501, unit 3, building 10, Chaoyang residential area, Chaoyang Street, Zhoucun District, Zibo City, Shandong Province Patentee before: Zhou Luzhong |