CN106328907A - Preparation method of graphene composite film containing Si nanoparticles - Google Patents

Preparation method of graphene composite film containing Si nanoparticles Download PDF

Info

Publication number
CN106328907A
CN106328907A CN201610989120.8A CN201610989120A CN106328907A CN 106328907 A CN106328907 A CN 106328907A CN 201610989120 A CN201610989120 A CN 201610989120A CN 106328907 A CN106328907 A CN 106328907A
Authority
CN
China
Prior art keywords
nano
particle
graphene
graphene oxide
supporting
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
Application number
CN201610989120.8A
Other languages
Chinese (zh)
Inventor
张达明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuxi Mingsheng Strong Blower Co Ltd
Original Assignee
Wuxi Mingsheng Strong Blower Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wuxi Mingsheng Strong Blower Co Ltd filed Critical Wuxi Mingsheng Strong Blower Co Ltd
Priority to CN201610989120.8A priority Critical patent/CN106328907A/en
Publication of CN106328907A publication Critical patent/CN106328907A/en
Pending legal-status Critical Current

Links

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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Abstract

The invention prepares a self-supporting Si nanoparticle/graphene oxide composite film through a simple microporous vacuum filtration method, and successfully obtains a self-supporting Si nanoparticle/graphene composite film through reduction. The self-supporting Si nanoparticle/graphene composite film material provided by the invention shows excellent electrochemical performance, and obviously improves the defects of pure Si nanoparticles such as high capacity fading speed, poor cycle stability, short cycle life, severe volume expansion effect and the like.

Description

A kind of preparation method of the graphene composite film containing Si nano-particle
Technical field
The present invention relates to technical field of new energies, particularly relate to the preparation of a kind of graphene composite film containing Si nano-particle Method.
Background technology
Lithium ion battery, as a kind of novel energy storage device, has been obtained above at portable type electronic product and widely should With.Along with the development in the field such as electric automobile and flexible electronic, lithium ion battery is had higher requirement, including higher Power density, higher output voltage, higher operating temperature and more preferable security performance and possess more preferable mechanical property And pliability.
For high performance lithium ion battery, the improvement of electrode active material and innovation are the core improving its combination property The heart and key.In terms of lithium ion battery negative material, business-like graphite cathode theoretical specific capacity low (372mAh/g), it is impossible to Meeting the requirement of a new generation's high performance lithium ion battery, researching and developing its alternative material is a kind of preferably selection, oxo transition metal Compound negative pole and silicium cathode material just have higher specific capacity, are the most promising negative materials, but because it is in circulation During Volumetric expansion, and then cause the too fast defect of capacity attenuation, be the Main Bottleneck limiting its application.
Graphene, as a kind of novel two-dimensional material, has extremely strong electric conductivity and fabulous mechanical strength, Ke Yizuo For transition metal oxide negative pole and the carrier of silicium cathode, suppress bulk effect in its charge and discharge process, reach to improve its performance Purpose.
Summary of the invention
It is an object of the invention to propose the preparation method of a kind of graphene composite film containing Si nano-particle, it is significantly It is scarce to improve that pure Si nano-particle capacity attenuation is too fast, cyclical stability is poor, cycle life is short, Volumetric expansion is serious etc. Fall into.
For reaching this purpose, the present invention by the following technical solutions:
A kind of preparation method of the graphene composite film containing Si nano-particle, including:
(1), under condition of ice bath, under mechanical agitation, 98% concentrated sulphuric acid adds crystalline graphite powder, adds and account for The sodium nitrate of graphite powder 50-80wt%, and account for the potassium permanganate of 2-4 times of weight of Graphene, react 30-120min under ice bath；
(2) it is heated to 30-40 DEG C of constant temperature 4-5h, adds deionized water and hydrogen peroxide, stir 1-3h, add 5% concentration HCl centrifuge washing, until sulfate radical-free ion, obtains graphene oxide powder；
(3) Si nano-particle is added with volume ratio 3:(0.5-2) in the mixed solution of the concentrated sulphuric acid that mixes and hydrogen peroxide, At 75-90 DEG C, constant temperature stirs 1-5 hour, obtains the Si nano-particle containing hydroxyl in surface；
(4) the Si nano-particle that hydroxyl is contained on described surface is washed and is vacuum dried, join mass fraction 0.5-3% Aminopropyl triethoxysilane in, under room temperature stir 12-36 hour, obtain the surface Si nano-particle with amino；
(5) by described graphene oxide ultrasonic disperse in water, after being completely dissolved, according to graphene oxide: MnO2Nanometer Line powder quality ratio is for 1:(0.5-2) ratio add the described surface Si nano-particle with amino, ultrasonic disperse also stirs 48-80h；
(6) vacuum filtration film forming, is dried at 75-90 DEG C, obtains self-supporting Si nano-particle/graphene oxide composite membrane；
(7) described composite membrane is put in hydrazine hydrate solution and reduce, vacuum drying, obtain self-supporting Si nano-particle/stone Ink alkene composite membrane.
The present invention a kind of simple ultrasonic disperse and the mode of physical agitation, and effectively utilize surface-functionalized Sl Condensation reaction between nano-particle and the oxygen-containing functional group of surface of graphene oxide, is uniformly adhered to oxygen by Si nano-particle Above functionalized graphene sheet, obtain highly homogeneous mixed solution on microcosmic.
It is prepared for self-supporting Si nano-particle/graphene oxide composite membrane by the method for simple micropore vacuum filtration, and Successfully being reduced to self-supporting Si nano-particle/graphene composite film, this is that one has good mechanical performance and pliability Self-supported membrane.
After the present invention is by being successfully combined Graphene and Si nano-particle, do not change respective characteristic；This compound Film is the perforated membrane of kind of layer structure, and Si nano-particle is supported on uniformly above graphene film and is mixed between lamella many In the middle of pore structure, constitute a kind of orderly structure.
The self-supporting Si nano-particle/graphene composite film material list of the present invention reveals the most excellent chemical property, Significantly improve that pure Si nano-particle capacity attenuation is too fast, cyclical stability is poor, cycle life is short, Volumetric expansion is serious Etc. defect.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.
Embodiment 1
A kind of preparation method of the graphene composite film containing Si nano-particle, including:
(1), under condition of ice bath, under mechanical agitation, 98% concentrated sulphuric acid adds crystalline graphite powder, adds and account for The sodium nitrate of graphite powder 50wt%, and account for the potassium permanganate of 2 times of weight of Graphene, react 30min under ice bath；
(2) being heated to 30 DEG C of constant temperature 4h, add deionized water and hydrogen peroxide, stir 1h, the HCl adding 5% concentration is centrifuged Washing, until sulfate radical-free ion, obtains graphene oxide powder；
(3) Si nano-particle is added in the mixed solution of the concentrated sulphuric acid with the mixing of volume ratio 3:0.5 and hydrogen peroxide, in 75 At DEG C, constant temperature stirs 1 hour, obtains the Si nano-particle containing hydroxyl in surface；
(4) the Si nano-particle that hydroxyl is contained on described surface is washed and is vacuum dried, join mass fraction 0.5% In aminopropyl triethoxysilane, stir 12 hours under room temperature, obtain the surface Si nano-particle with amino；
(5) by described graphene oxide ultrasonic disperse in water, after being completely dissolved, according to graphene oxide: MnO2Nanometer Line powder quality adds the described surface Si nano-particle with amino than the ratio for 1:0.5, and ultrasonic disperse also stirs 48h；
(6) vacuum filtration film forming, is dried at 75 DEG C, obtains self-supporting Si nano-particle/graphene oxide composite membrane；
(7) described composite membrane is put in hydrazine hydrate solution and reduce, vacuum drying, obtain self-supporting Si nano-particle/stone Ink alkene composite membrane.
Embodiment 2
A kind of preparation method of the graphene composite film containing Si nano-particle, including:
(1), under condition of ice bath, under mechanical agitation, 98% concentrated sulphuric acid adds crystalline graphite powder, adds and account for The sodium nitrate of graphite powder 80wt%, and account for the potassium permanganate of 4 times of weight of Graphene, react 120min under ice bath；
(2) being heated to 40 DEG C of constant temperature 5h, add deionized water and hydrogen peroxide, stir 3h, the HCl adding 5% concentration is centrifuged Washing, until sulfate radical-free ion, obtains graphene oxide powder；
(3) Si nano-particle is added in the mixed solution of the concentrated sulphuric acid with the mixing of volume ratio 3:2 and hydrogen peroxide, in 90 DEG C Lower constant temperature stirs 5 hours, obtains the Si nano-particle containing hydroxyl in surface；
(4) the Si nano-particle that hydroxyl is contained on described surface is washed and is vacuum dried, join the ammonia of mass fraction 3% In propyl-triethoxysilicane, stir 36 hours under room temperature, obtain the surface Si nano-particle with amino；
(5) by described graphene oxide ultrasonic disperse in water, after being completely dissolved, according to graphene oxide: MnO2Nanometer Line powder quality adds the described surface Si nano-particle with amino than the ratio for 1:2, and ultrasonic disperse also stirs 80h；
(6) vacuum filtration film forming, is dried at 90 DEG C, obtains self-supporting Si nano-particle/graphene oxide composite membrane；
(7) described composite membrane is put in hydrazine hydrate solution and reduce, vacuum drying, obtain self-supporting Si nano-particle/stone Ink alkene composite membrane.
Embodiment 3
A kind of preparation method of the graphene composite film containing Si nano-particle, including:
(1), under condition of ice bath, under mechanical agitation, 98% concentrated sulphuric acid adds crystalline graphite powder, adds and account for The sodium nitrate of graphite powder 70wt%, and account for the potassium permanganate of 3 times of weight of Graphene, react 30-120min under ice bath；
(2) be heated to 35 DEG C of constant temperature 4.5h, add deionized water and hydrogen peroxide, stir 2h, add the HCl of 5% concentration from The heart washs until sulfate radical-free ion, obtains graphene oxide powder；
(3) Si nano-particle is added in the mixed solution of the concentrated sulphuric acid with the mixing of volume ratio 3:1 and hydrogen peroxide, in 80 DEG C Lower constant temperature stirs 3 hours, obtains the Si nano-particle containing hydroxyl in surface；
(4) the Si nano-particle that hydroxyl is contained on described surface is washed and is vacuum dried, join the ammonia of mass fraction 2% In propyl-triethoxysilicane, stir 24 hours under room temperature, obtain the surface Si nano-particle with amino；
(5) by described graphene oxide ultrasonic disperse in water, after being completely dissolved, according to graphene oxide: MnO2Nanometer Line powder quality adds the described surface Si nano-particle with amino than the ratio for 1:1, and ultrasonic disperse also stirs 60h；
(6) vacuum filtration film forming, is dried at 80 DEG C, obtains self-supporting Si nano-particle/graphene oxide composite membrane；
(7) described composite membrane is put in hydrazine hydrate solution and reduce, vacuum drying, obtain self-supporting Si nano-particle/stone Ink alkene composite membrane.
The self-supporting Si nano-particle/graphene composite film material list of embodiment 1-3 reveals the most excellent electrochemistry Can, significantly improve that pure Si nano-particle capacity attenuation is too fast, cyclical stability is poor, cycle life is short, Volumetric expansion The defect such as serious.

Claims (1)

1. a preparation method for the graphene composite film containing Si nano-particle, including:
(1), under condition of ice bath, under mechanical agitation, 98% concentrated sulphuric acid adds crystalline graphite powder, adds and account for graphite The sodium nitrate of powder 50-80wt%, and account for the potassium permanganate of 2-4 times of weight of Graphene, react 30-120min under ice bath；
(2) be heated to 30-40 DEG C of constant temperature 4-5h, add deionized water and hydrogen peroxide, stir 1-3h, add the HCl of 5% concentration from The heart washs until sulfate radical-free ion, obtains graphene oxide powder；
(3) Si nano-particle is added with volume ratio 3:(0.5-2) in the mixed solution of the concentrated sulphuric acid that mixes and hydrogen peroxide, in At 75-90 DEG C, constant temperature stirs 1-5 hour, obtains the Si nano-particle containing hydroxyl in surface；
(4) the Si nano-particle that hydroxyl is contained on described surface is washed and is vacuum dried, join the ammonia of mass fraction 0.5-3% In propyl-triethoxysilicane, stir 12-36 hour under room temperature, obtain the surface Si nano-particle with amino；
(5) by described graphene oxide ultrasonic disperse in water, after being completely dissolved, according to graphene oxide: MnO2Nano wire powder Mass ratio is 1:(0.5-2) ratio add described surface with the Si nano-particle of amino, ultrasonic disperse also stirs 48-80h；
(6) vacuum filtration film forming, is dried at 75-90 DEG C, obtains self-supporting Si nano-particle/graphene oxide composite membrane；
(7) described composite membrane is put in hydrazine hydrate solution and reduce, vacuum drying, obtain self-supporting Si nano-particle/Graphene Composite membrane.
CN201610989120.8A 2016-11-10 2016-11-10 Preparation method of graphene composite film containing Si nanoparticles Pending CN106328907A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610989120.8A CN106328907A (en) 2016-11-10 2016-11-10 Preparation method of graphene composite film containing Si nanoparticles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610989120.8A CN106328907A (en) 2016-11-10 2016-11-10 Preparation method of graphene composite film containing Si nanoparticles

Publications (1)

Publication Number Publication Date
CN106328907A true CN106328907A (en) 2017-01-11

Family

ID=57816815

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610989120.8A Pending CN106328907A (en) 2016-11-10 2016-11-10 Preparation method of graphene composite film containing Si nanoparticles

Country Status (1)

Country Link
CN (1) CN106328907A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107039646A (en) * 2017-04-18 2017-08-11 合肥工业大学 Flexible negative material of a kind of lithium ion battery and preparation method thereof
CN109107557A (en) * 2018-07-10 2019-01-01 杭州高烯科技有限公司 A kind of photocatalysis graphene/silicon composite membrane and its preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101924211A (en) * 2010-08-19 2010-12-22 北京科技大学 Graphene/silicon lithium ion battery cathode material and preparation method thereof
CN103482620A (en) * 2013-09-11 2014-01-01 黄镇东 Graphene oxide or reduced graphene base mesh material and preparation method thereof
CN104916826A (en) * 2015-07-03 2015-09-16 东莞市迈科科技有限公司 Silicon cathode material coated with graphene and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101924211A (en) * 2010-08-19 2010-12-22 北京科技大学 Graphene/silicon lithium ion battery cathode material and preparation method thereof
CN103482620A (en) * 2013-09-11 2014-01-01 黄镇东 Graphene oxide or reduced graphene base mesh material and preparation method thereof
CN104916826A (en) * 2015-07-03 2015-09-16 东莞市迈科科技有限公司 Silicon cathode material coated with graphene and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JEONG K.LEE等: ""Silicon nanoparticles-graphene paper composites for Li ion battery anodes"", 《CHEMCOMM》 *
JIA-ZHAO WANG等: ""Flexible free-standing graphene-silicon composite film for lithium-ion batteries"", 《ELECTROCHEMISTRY COMMUNICATIONS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107039646A (en) * 2017-04-18 2017-08-11 合肥工业大学 Flexible negative material of a kind of lithium ion battery and preparation method thereof
CN109107557A (en) * 2018-07-10 2019-01-01 杭州高烯科技有限公司 A kind of photocatalysis graphene/silicon composite membrane and its preparation method and application
CN109107557B (en) * 2018-07-10 2021-08-03 杭州高烯科技有限公司 Photocatalytic graphene/silicon composite membrane and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN105742611B (en) A kind of lithium ion battery negative material, preparation method and lithium ion battery
CN106410181A (en) Preparation method of graphene composite containing MnO2 nanowires
CN102299326B (en) Graphene modified lithium iron phosphate/carbon composite material and its application
CN105428614B (en) A kind of nitrogen-doping porous composite negative pole material and preparation method thereof
CN105140469B (en) A kind of egg yolk structure transition metal oxide/graphene composite material and preparation method and application
WO2016107564A1 (en) Composite positive material for lithium-sulphur battery with high rate performance and preparation method
CN105390687B (en) A kind of high performance three-dimensional CNT composite negative pole material and its preparation method and application
CN102867963B (en) Anode active material of lithium sulfur battery and preparation method of anode active material
CN107452947B (en) Lead paste for positive plate of lead storage battery, preparation method of lead paste and lead storage battery
Gao et al. Solvothermal synthesis of α-PbO from lead dioxide and its electrochemical performance as a positive electrode material
CN104282918B (en) Lithium-air battery negative electrode, lithium-air battery and the method for preparing lithium-air battery electrode
Wang et al. Rational design of yolk–shell silicon dioxide@ hollow carbon spheres as advanced Li–S cathode hosts
CN105489898A (en) Conductive waterborne binder and preparation method therefor, and lithium ion battery
CN107579219A (en) For graphene/zinc oxide negative material of secondary zinc base battery and its preparation
CN107887591A (en) Improve lead plaster and cream of process for positive slab lattice of lead-acid accumulator and lead plaster adhesion and preparation method thereof
KR101406371B1 (en) Metal or Metal oxide/Graphene self-assembly Nanocomposite of Three-dimensional structure and Method of preparing the same
CN103515611B (en) A kind of lithium ion anode material of nano oxidized aluminium film cladding and preparation method thereof
CN103000887A (en) Preparation method of graphite-molybdenum sulfide nano-composite negative electrode material of ion battery
CN104916823A (en) Silicon/graphene oxide anode material for lithium battery and preparation method thereof
Jia et al. Sea urchin-like CuCo 2 S 4 microspheres with a controllable interior structure as advanced electrode materials for high-performance supercapacitors
Zheng et al. Facile synthesis of porous Co 3 O 4 nanoflakes as an interlayer for high performance lithium–sulfur batteries
CN104638248B (en) A kind of preparation method of graphene/lead compound composite
CN106328907A (en) Preparation method of graphene composite film containing Si nanoparticles
CN109103436A (en) A kind of lithium sulfur battery anode material and preparation method thereof
CN114678496A (en) Preparation of magnesium fluoride nanocrystalline @ nitrogen-doped graphene hollow nanospheres and application of magnesium fluoride nanocrystalline @ nitrogen-doped graphene hollow nanospheres in lithium metal batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170111

WD01 Invention patent application deemed withdrawn after publication