CN108987686A - Polyaniline-coated silicon based composite material and preparation method thereof - Google Patents
Polyaniline-coated silicon based composite material and preparation method thereof Download PDFInfo
- Publication number
- CN108987686A CN108987686A CN201810634124.3A CN201810634124A CN108987686A CN 108987686 A CN108987686 A CN 108987686A CN 201810634124 A CN201810634124 A CN 201810634124A CN 108987686 A CN108987686 A CN 108987686A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- silica
- base material
- eigenstate
- based composite
- 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
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 172
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010703 silicon Substances 0.000 title claims abstract description 64
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 124
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000013019 agitation Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 15
- 239000010405 anode material Substances 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000010410 dusting Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920000775 emeraldine polymer Polymers 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 inorganic acid anion Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, 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
- H01M4/628—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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of preparation methods of polyaniline-coated silicon based composite material, which comprises the following steps: provides the mixed solution of silica-base material, aniline monomer, inorganic acid aqueous solution；Ammonium persulfate solution is added dropwise under agitation, carries out home position polymerization reaction, is filtered processing after reaction, collects polyaniline and wraps up silica-base material powder, be washed with deionized water to neutrality, obtains polyaniline package silica-base material；It disperses neutral polyaniline package silica-base material in ammonia spirit, stir process, filtering is washed with deionized water to neutrality, obtains polyaniline in eigenstate package silica-base material.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of polyaniline-coated silicon based composite material and its systems
Preparation Method.
Background technique
With the higher requirement to secondary battery capacity, silicon is as a kind of high theoretical specific capacity (4200mAh g-1) start
It introduces in negative electrode of lithium ion battery.However, the silicon as ion cathode material lithium, in charge and discharge process, volume can occur huge
Variation, keep material powder phenomenon-tion serious.In charging process, due to breakage of particles generate new interface will continue to it is anti-with electrolyte
SEI film should be generated, causes SEI film thickness more and more thicker, the loss of negative electrode active material, constantly consumption electrolyte is caused, makes battery
Capacity sharply declines.In addition, in electrolyte the presence of HF not only can corroding electrode material, cause electrolyte to fail, also will affect
Cathode SEI film quality.Currently, generally solving the problems, such as material dusting with carbon-coated method.Then the carbon-coating actually coated
It is extremely difficult to the purpose of uniformly continuous, keeps internal silicon locally exposed.Polyaniline can be used as calcining carbon materials as a kind of macromolecule
The presoma of material, it is common practice to the doped polyaniline of oxidizing process synthesis be calcined, the carbon material rich in nitrogen-atoms is obtained.
Since calcined polyaniline loses high molecular characteristic, do not have oxidation/reduction invertibity and it is doped with go to adulterate
The problem of ability mutually converted between state, HF corroding electrode material causes electrolyte to fail, influences cathode SEI film quality, is still
So exist.
Summary of the invention
The purpose of the present invention is to provide a kind of polyaniline-coated silicon based composite materials and preparation method thereof, it is intended to solve existing
Some is negative by calcining the carbon coating silicon substrate for forming cladding carbon material in silicon substrate surface using polyaniline as cladding precursor material
Pole material, since calcined polyaniline loses high molecular characteristic, carbon coating silicon based anode material does not have oxidation/reduction
Invertibity and it is doped with go the ability mutually converted between doped, HF corroding electrode material causes electrolyte to fail, shadow
The problem of ringing cathode SEI film quality.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of preparation method of polyaniline-coated silicon based composite material, comprising the following steps:
The mixed solution of silica-base material, aniline monomer, inorganic acid aqueous solution is provided；Ammonium persulfate is added dropwise under agitation
Solution carries out home position polymerization reaction, is filtered processing after reaction, collects polyaniline and wraps up silica-base material powder, spends
Ion is washed to neutrality, obtains polyaniline package silica-base material；
It disperses neutral polyaniline package silica-base material in ammonia spirit, stir process, filtering is washed with deionized water
To neutrality, polyaniline in eigenstate package silica-base material is obtained.
Preferably, the concentration of the inorganic acid is 0.1-2.0mol/L.
Preferably, in the step of preparing polyaniline package silica-base material, the additive amount of the ammonium persulfate solution meets: institute
The molar ratio for stating ammonium persulfate and the aniline monomer is 2-3:1.
Preferably, the concentration of the ammonia spirit is 0.1-2.0mol/L.
Preferably, the reaction temperature of the home position polymerization reaction is 15-35 DEG C, and the reaction time is no less than half an hour.
Preferably, the inorganic acid is selected from least one of sulfuric acid, hydrochloric acid, nitric acid.
Preferably, the silica-base material in Si-C composite material, silicon O compoiste material, carbon coating silicon oxygen material extremely
Few one kind.
Preferably, the adding proportion of the silica-base material and the aniline monomer meets: with the polyaniline in eigenstate packet
The total weight for wrapping up in silica-base material is 100% meter, and the weight percentage of polyaniline in eigenstate is 0.1%-10%.
Another aspect of the present invention provides a kind of polyaniline-coated silicon based composite material, the polyaniline-coated silicon substrate composite wood
Material is that polyaniline in eigenstate wraps up silica-base material, including kernel and is coated on the clad of the core surface, the kernel
For silica-base material, the clad is polyaniline in eigenstate.
It preferably, is the eigenstate polyphenyl in terms of 100% by the total weight of polyaniline in eigenstate package silica-base material
The weight percentage of amine is 0.1%-10%.
Further aspect of the present invention provides a kind of lithium ion battery, and the polyaniline-coated silicon substrate including the method for the present invention preparation is multiple
Condensation material or the above-mentioned polyaniline-coated silicon based composite material of the present invention.
The preparation method of polyaniline-coated silicon based composite material provided by the invention, by the way that polyaniline is passed through in-situ polymerization
Mode be covered on silica-base material surface, then by doped polyaniline (Emeraldine Salt, ES) by way of reduction
It goes to adulterate, obtains polyaniline in eigenstate (Leucoemeradine Base, LB), thus obtain silica-base material surface and be coated with this
The polyaniline in eigenstate for levying state polyaniline wraps up silica-base material.On the one hand, the polyaniline in eigenstate is as a kind of macromolecule material
Material, short texture, continuous whole clad can be formed by being coated on silica-base material surface, can reduce the powder of negative electrode material
Change.Particularly, when silica-base material is carbon coating silica-base material, the polyaniline in eigenstate can repair carbon coating layer, make carbon
Clad is continuous whole.It on the other hand, can under acidic environment since the backbone segment of polyaniline in eigenstate is to contain quinoid structure
To obtain doped polyaniline by acid doping.Therefore, polyaniline in eigenstate package silica-base material of the present invention is used as lithium ion
When cell negative electrode material, HF in electrolyte is can be absorbed in the polyaniline in eigenstate, drops low HF concentration, reduces HF to electricity to reach
The destruction of pole material and electrolyte improves the purpose of battery performance.Polyaniline in eigenstate is converted into doped in acid condition
Shown in the reaction of polyaniline such as following formula (turning left from the right side), wherein HA represents inorganic acid, A-Represent inorganic acid anion, reaction equation
The left side is doped polyaniline, and the right is polyaniline in eigenstate.In addition, the polyaniline in eigenstate is reacted with acid is converted into doping
State polyaniline can also realize material from non-conductive to conductive variation.
Polyaniline-coated silicon based composite material provided by the invention, silica-base material surface are coated with the sheet of polyaniline in eigenstate
It levies state polyaniline and wraps up silica-base material.On the one hand, the polyaniline in eigenstate is as a kind of high molecular material, short texture, packet
Continuous whole clad can be formed by overlaying on silica-base material surface, can reduce the dusting of negative electrode material.Particularly, work as silicon substrate
When material is carbon coating silica-base material, the polyaniline in eigenstate can repair carbon coating layer, keep carbon coating layer continuous whole.Separately
On the one hand, since the backbone segment of polyaniline in eigenstate can be mixed by acid doping under acidic environment containing quinoid structure
Miscellaneous state polyaniline.Therefore, when polyaniline in eigenstate package silica-base material of the present invention is used as lithium ion battery negative material, institute
Stating polyaniline in eigenstate can be absorbed HF in electrolyte, drop low HF concentration, reduce HF to electrode material and electrolyte to reach
It destroys, improves the purpose of battery performance.In addition, the polyaniline in eigenstate is reacted with acid is converted into doped polyaniline, may be used also
To realize material from non-conductive to conductive variation.
Lithium ion battery provided by the invention, due to including the polyaniline-coated silicon based composite material of the method for the present invention preparation
Or the above-mentioned polyaniline-coated silicon based composite material of the present invention, therefore HF can be effectively reduced, electrode material and electrolyte are broken
It is bad, improve battery performance.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
On the one hand the embodiment of the present invention provides a kind of polyaniline-coated silicon based composite material, the polyaniline-coated silicon substrate
Composite material is that polyaniline in eigenstate wraps up silica-base material, including kernel and is coated on the clad of the core surface, institute
Stating kernel is silica-base material, and the clad is polyaniline in eigenstate.
Polyaniline-coated silicon based composite material provided in an embodiment of the present invention, silica-base material surface are coated with eigenstate polyphenyl
The polyaniline in eigenstate of amine wraps up silica-base material.On the one hand, the polyaniline in eigenstate is dredged as a kind of high molecular material, structure
Pine, continuous whole clad can be formed by being coated on silica-base material surface, can reduce the dusting of negative electrode material.Particularly,
When silica-base material is carbon coating silica-base material, the polyaniline in eigenstate can repair carbon coating layer, keep carbon coating layer continuous
Completely.It on the other hand, can be by acid doping under acidic environment since the backbone segment of polyaniline in eigenstate is to contain quinoid structure
Obtain doped polyaniline.Therefore, polyaniline in eigenstate package silica-base material of the present invention is used as negative electrode of lithium ion battery material
When material, HF in electrolyte is can be absorbed in the polyaniline in eigenstate, drops low HF concentration, reduces HF to electrode material and electricity to reach
The destruction for solving liquid, improves the purpose of battery performance.In addition, the polyaniline in eigenstate is reacted with acid is converted into doped polyphenyl
Amine can also realize material from non-conductive to conductive variation.Polyaniline in eigenstate is converted into doped poly- in acid condition
Shown in the reaction of aniline such as following formula (turning left from the right side), wherein HA represents inorganic acid, A-Inorganic acid anion is represented, reaction equation is left
While being doped polyaniline, the right is polyaniline in eigenstate.In addition, the polyaniline in eigenstate with acid react be converted into it is doped
Polyaniline can also realize material from non-conductive to conductive variation.
In the embodiment of the present invention, it is preferred that with the total weight of polyaniline in eigenstate package silica-base material for 100%
The weight percentage of meter, the polyaniline in eigenstate is 0.1%-10%, thus obtains the polyaniline in eigenstate of suitable thickness
Clad closes to guarantee to have when the polyaniline in eigenstate package silica-base material is used as lithium ion battery negative material
Suitable gram volume.If the too high levels of the polyaniline in eigenstate, coating thickness is blocked up, then can reduce gram appearance of material
Amount, or even cannot function as the preferred negative electrode material use of lithium ion battery；It is difficult if the content of the polyaniline in eigenstate is too low
To realize complete continuous cladding, can not achieve the effect that HF is preferably avoided to influence.
In the embodiment of the present invention, the silica-base material is conventional silica-base material, including but not limited to Si-C composite material,
At least one of silicon O compoiste material, carbon coating silicon oxygen material.Particularly, when the silica-base material sheet is as core-shell structure,
And outer layer be carbon material layer when, the polyaniline in eigenstate can repair carbon coating layer, keep carbon coating layer continuous whole.
Polyaniline-coated silicon based composite material described in the embodiment of the present invention can be prepared by following methods.
Correspondingly, on the other hand the embodiment of the present invention provides a kind of preparation method of polyaniline-coated silicon based composite material,
The following steps are included:
S01., the mixed solution of silica-base material, aniline monomer, inorganic acid aqueous solution is provided；Over cure is added dropwise under agitation
Acid ammonium solution carries out home position polymerization reaction, is filtered processing after reaction, collects polyaniline and wraps up silica-base material powder,
It is washed with deionized water to neutrality, obtains polyaniline package silica-base material；
S02. it disperses neutral polyaniline package silica-base material in ammonia spirit, deionization is used in stir process, filtering
It is washed to neutrality, obtains polyaniline in eigenstate package silica-base material.
The preparation method of polyaniline-coated silicon based composite material provided in an embodiment of the present invention, by the way that polyaniline is passed through original
The mode of position polymerization is covered on silica-base material surface, then by doped polyaniline (Emeraldine by way of reduction
Salt, ES) it goes to adulterate, polyaniline in eigenstate (Leucoemeradine Base, LB) is obtained, silica-base material surface is thus obtained
It is coated with the polyaniline in eigenstate package silica-base material of polyaniline in eigenstate.On the one hand, the polyaniline in eigenstate is as a kind of
High molecular material, short texture, continuous whole clad can be formed by being coated on silica-base material surface, can reduce cathode material
The dusting of material.Particularly, when silica-base material is carbon coating silica-base material, the polyaniline in eigenstate can repair carbon coating
Layer, keeps carbon coating layer continuous whole.On the other hand, since the backbone segment of polyaniline in eigenstate is containing quinoid structure, in acidity
Doped polyaniline can be obtained by acid doping under environment.Therefore, polyaniline in eigenstate described in the embodiment of the present invention wraps up silicon substrate
When material is used as lithium ion battery negative material, HF in electrolyte is can be absorbed in the polyaniline in eigenstate, drops low HF concentration,
To reach the destruction for reducing HF to electrode material and electrolyte, the purpose of battery performance is improved.Polyaniline in eigenstate is in acid item
Shown in the reaction such as following formula (turning left from the right side) for being converted into doped polyaniline under part, wherein HA represents inorganic acid, A-It represents inorganic
Sour anion, the reaction equation left side are doped polyaniline, and the right is polyaniline in eigenstate.In addition, the polyaniline in eigenstate with
Acid reaction is converted into doped polyaniline, and material can also be realized from non-conductive to conductive variation.
Specifically, the mixed solution of silica-base material, aniline monomer, inorganic acid aqueous solution is provided in above-mentioned steps S01,
In, the silica-base material is selected from least one of Si-C composite material, silicon O compoiste material, carbon coating silicon oxygen material.It is described
Reaction monomers of the aniline monomer as polyaniline.Preferably, the adding proportion of the silica-base material and the aniline monomer meets:
Total weight by polyaniline in eigenstate package silica-base material is in terms of 100%, and the weight percentage of polyaniline in eigenstate is
0.1%-10%, thus obtains the polyaniline in eigenstate clad of suitable thickness, to guarantee the polyaniline in eigenstate package
There is suitable gram volume when silica-base material is used as lithium ion battery negative material.If the content mistake of the aniline monomer
Height, then the coating thickness formed is blocked up, then can reduce the gram volume of material, or even cannot function as the preferred negative of lithium ion battery
Pole materials'use；If the content of the aniline monomer is too low, it is difficult to realize complete continuous cladding, can not be reached preferable
The effect for avoiding HF from influencing.
It is anti-to be doped to aniline monomer in-situ polymerization on the one hand as doping molecule for inorganic acid in the inorganic acid aqueous solution
Ying Zhong is adulterated in polymerization, and formation contains doped polyaniline；Meanwhile the acidic environment that the inorganic acid provides, it can also promote
Into the generation of home position polymerization reaction, and improve its own doping rate.Herein, it should be appreciated that due to organic acid molecule
Amount is big, and corresponding steric hindrance is big, when its with the polyaniline that is formed in polymerization process close to when, the two is difficult to effectively combine,
Doping effect can be reduced, or even cannot be doped, therefore, the present invention uses inorganic acid to provide doped chemical simultaneously for the present invention
Acid reaction environment is provided.Preferably, the concentration of the inorganic acid be 0.1-2.0mol/L, so as to obtain suitable doping and
Adulterate effect.
The embodiment of the present invention provide silica-base material, aniline monomer, inorganic acid aqueous solution the mode of mixed solution be preferably,
First silicon based anode material is dispersed in inorganic acid aqueous solution, aniline monomer is then added, obtains mixed solution after mixing.
In the embodiment of the present invention, ammonium persulfate solution is added dropwise under agitation, carries out home position polymerization reaction.The over cure
Ammonium persulfate in acid ammonium solution for aoxidizing aniline monomer, and then causes home position polymerization reaction as oxidant.Preferably,
The additive amount of the ammonium persulfate solution meets: the molar ratio of the ammonium persulfate and the aniline monomer is 2-3:1, such as benzene
Amine additive amount is 1mol, and the additive amount of ammonium persulfate is 2-3mol, to send out with being conducive to home position polymerization reaction steady ordered
It is raw.
In the embodiment of the present invention, the reaction temperature of the home position polymerization reaction is at 60 DEG C or less, it is preferred that the original
The reaction temperature of position polymerization reaction is 15-35 DEG C, and the reaction time is not less than half an hour.If reaction temperature is too low, such as it is lower than 5 DEG C
When, it is unfavorable for promoting the progress of home position polymerization reaction；The room temperature condition of 35 DEG C of control, on the one hand, reaction can be normally carried out, separately
On the one hand, can be energy saving, while heating operation is avoided, simplify reaction process.
It is filtered processing after the home position polymerization reaction, collects polyaniline and wrap up silica-base material powder, using going
Ionized water washes polyaniline package silica-base material powder, is washed to neutrality, removes remaining inorganic acid, to avoid
The residual of inorganic acid influences the progress that following step goes doping by ammonium hydroxide.After being washed to neutrality, polyaniline package silicon substrate is obtained
Material.
In above-mentioned steps S02, disperses neutral polyaniline package silica-base material in ammonia spirit, polyaniline is wrapped up
Doped polyaniline carries out doping treatment in silica-base material, to obtain backbone segment as the eigenstate polyphenyl containing quinoid structure
Amine, and then polyaniline in eigenstate package silica-base material is being used as lithium ion battery negative material in use, polyaniline in eigenstate
Low HF concentration can be dropped by the HF in Electolyte-absorptive, to reach the destruction for reducing HF to electrode material and electrolyte, improved
The purpose of battery performance.
Preferably, the concentration of the ammonia spirit is 0.1-2.0mol/L, thus provides suitable pH environment, passes through reduction
Originally the inorganic anion being doped in polyaniline molecule is gone to adulterate by reaction, obtains polyaniline in eigenstate package silica-base material；
Obtained polyaniline in eigenstate is protected simultaneously, prevents it from miscellaneous side reaction occurs.If the concentration of the ammonia spirit is too low, it is difficult to
It effectively realizes and goes doping effect；If the excessive concentration of ammonia spirit, since ammonium hydroxide itself has reproducibility, over reduction can be led
It causes polyaniline in eigenstate not adulterate again, loses the ability combined with acid, and then polyaniline in eigenstate is being wrapped up into silicon substrate
Material is used as lithium ion battery negative material in use, the polyaniline of over reduction is unable to the HF in Electolyte-absorptive, thus cannot
It solves to influence caused by HF.
Reduction reaction of the embodiment of the present invention is realized by stir process.Reaction time should be not less than half an hour, preferably 2-
16 hours, more preferably 12 hours, to avoid ammonium hydroxide over reduction caused by obtained polyaniline in eigenstate.
And another further aspect of the embodiment of the present invention provides a kind of lithium ion battery, including the poly- of the method for the present invention preparation
Aniline coats silicon based composite material or the above-mentioned polyaniline-coated silicon based composite material of the present invention.
Lithium ion battery provided in an embodiment of the present invention, since the polyaniline-coated silicon substrate for including the method for the present invention preparation is multiple
Condensation material or the above-mentioned polyaniline-coated silicon based composite material of the present invention, therefore HF can be effectively reduced to electrode material and electrolysis
The destruction of liquid improves battery performance.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of polyaniline-coated silicon based composite material, comprising the following steps:
5g silicon carbon material is well dispersed in the aqueous sulfuric acid of the 1mol/L of 500mL, adds 0.1g aniline list
Body, continuing stirring 2h keeps aniline fully dispersed.The ammonium persulfate aqueous solution that 200ml contains 11.4g is added dropwise with vigorous stirring,
6h is persistently stirred to fully reacting.Polyaniline package silicon based anode material powder is obtained by filtration, is washed with deionized water to neutrality.It will
In the ammonia spirit for the 0.5mol/L that obtained neutral polyaniline package silicon based anode material powder is scattered in 500mL again,
Stir 12h.Filtering is washed with deionized water to neutrality and obtains polyaniline in eigenstate package silicon based anode material.
Embodiment 2
A kind of preparation method of polyaniline-coated silicon based composite material, comprising the following steps:
In the aqueous hydrochloric acid solution for the 0.8mol/L that 2g carbon package silicon oxygen anode material is well dispersed in 300mL, then
0.01g aniline monomer is added, continuing stirring 2h keeps aniline fully dispersed.100ml is added dropwise with vigorous stirring and contains 4.564g's
Ammonium persulfate aqueous solution persistently stirs 6h to fully reacting.Be obtained by filtration polyaniline package silicon based anode material powder, spend from
Son is washed to neutrality.Again disperse obtained neutral polyaniline package silicon based anode material powder in the 1.0mol/ of 100mL
In the ammonia spirit of L, 12h is stirred.Filtering is washed with deionized water to neutrality and obtains polyaniline in eigenstate package silicon-based anode material
Material.
Embodiment 3
A kind of preparation method of polyaniline-coated silicon based composite material, comprising the following steps:
In the aqueous solution of nitric acid for the 0.8mol/L that 4g carbon package silicon oxygen anode material is well dispersed in 500mL, then
0.02g aniline monomer is added, continuing stirring 2h keeps aniline fully dispersed.250ml is added dropwise with vigorous stirring and contains 9.128g's
Ammonium persulfate aqueous solution persistently stirs 6h to fully reacting.Be obtained by filtration polyaniline package silicon based anode material powder, spend from
Son is washed to neutrality.Again disperse obtained neutral polyaniline package silicon based anode material powder in the 0.8mol/ of 300mL
In the ammonia spirit of L, 12h is stirred.Filtering is washed with deionized water to neutrality and obtains polyaniline in eigenstate package silicon-based anode material
Material.
By above-described embodiment 1, gained sample is respectively designated as S1, S2 and S3 in embodiment 2 and embodiment 3, in embodiment
Using to the silica-base material for not wrapping up polyaniline be respectively designated as D1, D2 and D3.2g is taken to be scattered in all samples
100mL contains in ethylene carbonate (EC) solution of 0.01mol/L HF, stirs 1h, filtering.Filter cake after filtering is dispersed again
It in 100mL ethylene carbonate (EC), filters after stirring 1h, with ethylene carbonate (EC) repeated flushing 10 times when filtering, obtains
Product dried in 60 DEG C of baking ovens.Sample tests wherein fluorine element content with scanning electron microscope energy disperse spectroscopy sxemiquantitative after drying, and obtains
To S1, the fluorine atom percentage in S2 and S3 is 1.84%, 1.39%, 1.27%, and fluorine atom percentage in D1, D2 and D3
It is 0.01%, 0.02%, 0.01%.The result shows that wrapping up in the composite material of polyaniline fluorine content much higher than uncoated
Silica-base material, the cladding of polyaniline can effectively absorb HF acid.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of polyaniline-coated silicon based composite material, which comprises the following steps:
The mixed solution of silica-base material, aniline monomer, inorganic acid aqueous solution is provided；It is molten that ammonium persulfate is added dropwise under agitation
Liquid carries out home position polymerization reaction, is filtered processing after reaction, collects polyaniline package silica-base material powder, spend from
Son is washed to neutrality, obtains polyaniline package silica-base material；
It disperses neutral polyaniline package silica-base material in ammonia spirit, stir process, filtering is washed with deionized water into
Property, obtain polyaniline in eigenstate package silica-base material.
2. the preparation method of polyaniline-coated silicon based composite material as described in claim 1, which is characterized in that the inorganic acid
Concentration be 0.1-2.0mol/L.
3. the preparation method of polyaniline-coated silicon based composite material as described in claim 1, which is characterized in that prepare polyaniline
In the step of wrapping up silica-base material, the additive amount of the ammonium persulfate solution meets: the ammonium persulfate and the aniline monomer
Molar ratio be 2-3:1.
4. the preparation method of polyaniline-coated silicon based composite material as described in claim 1, which is characterized in that the ammonium hydroxide is molten
The concentration of liquid is 0.1-2.0mol/L.
5. the preparation method of polyaniline-coated silicon based composite material according to any one of claims 1-4, which is characterized in that institute
The reaction temperature for stating home position polymerization reaction is 15-35 DEG C, and the reaction time is not less than half an hour.
6. the preparation method of polyaniline-coated silicon based composite material according to any one of claims 1-4, which is characterized in that institute
It states inorganic acid and is selected from least one of sulfuric acid, hydrochloric acid, nitric acid；And/or
The silica-base material is selected from least one of Si-C composite material, silicon O compoiste material, carbon coating silicon oxygen material.
7. the preparation method of polyaniline-coated silicon based composite material according to any one of claims 1-4, which is characterized in that institute
The adding proportion for stating silica-base material and the aniline monomer meets: with the total weight of polyaniline in eigenstate package silica-base material
For 100% meter, the weight percentage of polyaniline in eigenstate is 0.1%-10%.
8. a kind of polyaniline-coated silicon based composite material, which is characterized in that the polyaniline-coated silicon based composite material is intrinsic
State polyaniline wraps up silica-base material, including kernel and is coated on the clad of the core surface, the kernel is silicon substrate
Material, the clad are polyaniline in eigenstate.
9. polyaniline-coated silicon based composite material as claimed in claim 8, which is characterized in that with the polyaniline in eigenstate packet
The total weight for wrapping up in silica-base material is 100% meter, and the weight percentage of the polyaniline in eigenstate is 0.1%-10%.
10. a kind of lithium ion battery, which is characterized in that the polyaniline including the preparation of any one of such as claim 1-7 the method
Coat silicon based composite material or the polyaniline-coated silicon based composite material of claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810634124.3A CN108987686A (en) | 2018-06-20 | 2018-06-20 | Polyaniline-coated silicon based composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810634124.3A CN108987686A (en) | 2018-06-20 | 2018-06-20 | Polyaniline-coated silicon based composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108987686A true CN108987686A (en) | 2018-12-11 |
Family
ID=64540761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810634124.3A Pending CN108987686A (en) | 2018-06-20 | 2018-06-20 | Polyaniline-coated silicon based composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108987686A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112467114A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Silica composite material, preparation method thereof and lithium ion battery |
| CN112531150A (en) * | 2020-12-09 | 2021-03-19 | 合肥国轩高科动力能源有限公司 | Conductive polyaniline modified nitrogen-doped C/SiOx lithium ion battery negative electrode material and preparation method thereof |
| CN112751031A (en) * | 2019-10-30 | 2021-05-04 | 华为技术有限公司 | Cathode material, preparation method thereof, lithium ion battery and terminal |
| CN113277518A (en) * | 2021-04-27 | 2021-08-20 | 郑州市博卓科技有限公司 | Silica raw material and preparation method thereof |
| CN114420910A (en) * | 2022-01-19 | 2022-04-29 | 山东能源集团有限公司 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
| 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 |
| WO2023163011A1 (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 and negative electrode active material for secondary batteries, and secondary battery |
-
2018
- 2018-06-20 CN CN201810634124.3A patent/CN108987686A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112751031A (en) * | 2019-10-30 | 2021-05-04 | 华为技术有限公司 | Cathode material, preparation method thereof, lithium ion battery and terminal |
| CN112751031B (en) * | 2019-10-30 | 2023-10-20 | 华为技术有限公司 | Negative electrode material, preparation method thereof, lithium ion battery and terminal |
| CN112467114A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Silica composite material, preparation method thereof and lithium ion battery |
| CN112531150A (en) * | 2020-12-09 | 2021-03-19 | 合肥国轩高科动力能源有限公司 | Conductive polyaniline modified nitrogen-doped C/SiOx lithium ion battery negative electrode material and preparation method thereof |
| CN113277518A (en) * | 2021-04-27 | 2021-08-20 | 郑州市博卓科技有限公司 | Silica raw material and preparation method thereof |
| CN114420910A (en) * | 2022-01-19 | 2022-04-29 | 山东能源集团有限公司 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
| CN114420910B (en) * | 2022-01-19 | 2023-12-01 | 山东能源集团有限公司 | Nitrogen-doped silicon-carbon composite material with core-shell structure and preparation method thereof |
| 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 |
| WO2023163011A1 (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 and negative electrode active material for secondary batteries, and secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108987686A (en) | Polyaniline-coated silicon based composite material and preparation method thereof | |
| CN105185962B (en) | A kind of nickelic positive electrode and preparation method thereof and lithium ion battery | |
| CN105118967B (en) | A kind of doping tertiary cathode material of metal oxide coating modification and preparation method thereof | |
| CN110870113B (en) | Battery with novel composition | |
| JP3860542B2 (en) | Positive electrode active material for lithium secondary battery and method for producing the same | |
| CN108807950B (en) | Fluoride-modified nickel-rich ternary composite electrode material and preparation method thereof | |
| CN110945689B (en) | Battery cell having novel composition | |
| CN106960955B (en) | The ternary cathode material of lithium ion battery and preparation method thereof of vanadium sulfide cladding | |
| US11469417B2 (en) | Surface-functionalized, acidified metal oxide material in an acidified electrolyte system or an acidified electrode system | |
| CN108400291A (en) | A kind of lithium ion battery composite cathode material and preparation method thereof | |
| CN106257718B (en) | A kind of BN cladding is without cobalt Ni-Mn solid solution nickel hydroxide base anode materials | |
| Zhang et al. | Stabilization of Lattice Oxygen in Li‐Rich Mn‐Based Oxides via Swing‐like Non‐Isothermal Sintering | |
| CN103833088A (en) | Method for preparing doped spherical cobaltosic oxide | |
| CN108878877A (en) | A kind of water system zinc ion cathode active material for secondary battery and a kind of water system zinc ion secondary cell | |
| CN1966410A (en) | Preparation method of nickel magnesium cobalt hydroxide | |
| CN105428621B (en) | A kind of lithium ion conductor cladding nanometer LiMnPO4The method of modifying of/C positive electrode material | |
| CN108598379A (en) | A kind of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material and its preparation method and application | |
| CN108807920A (en) | LASO coats octahedral structure nickel ion doped composite material and preparation method | |
| CN107528060A (en) | A kind of nickelic positive electrode of gradient and preparation method thereof and lithium ion battery | |
| CN109920991A (en) | Tertiary cathode material and preparation method thereof and lithium ion battery comprising the material | |
| CN110121801A (en) | Positive electrode active materials and preparation method thereof and lithium secondary battery comprising it | |
| CN106450194B (en) | A kind of manganese base shape richness lithium material and its preparation method with uniform lithium phosphate clad | |
| CN110137464A (en) | Molybdic acid vanadium lithium coats rich lithium nickel cobalt manganese oxide positive electrode, anode pole piece and preparation method thereof and lithium battery | |
| CN1269240C (en) | Method for preparing positive electrode active material of rechargeable lithium cell | |
| CN115215379A (en) | Lithium composite oxide and method for producing same |
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 |