CN104993110B - A kind of preparation method of composite negative electrode material of lithium ion battery - Google Patents
A kind of preparation method of composite negative electrode material of lithium ion battery Download PDFInfo
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- CN104993110B CN104993110B CN201510315196.8A CN201510315196A CN104993110B CN 104993110 B CN104993110 B CN 104993110B CN 201510315196 A CN201510315196 A CN 201510315196A CN 104993110 B CN104993110 B CN 104993110B
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- composite negative
- ion battery
- lithium ion
- negative electrode
- electrode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 discloses a kind of preparation methods of composite negative electrode material of lithium ion battery, it is characterised in that：It is prepared using surface modification and hydrothermal reduction method jointmSi@G composite negative pole materials.Specifically include following steps：Nano-silicon is surface modified first；Then it is added to together with reducing agent in the dispersion liquid of graphite oxide, hydro-thermal reaction is carried out after being uniformly dispersed, is transferred to after suction filtration in aqueous solution and carries out ion exchange, after suction filtration, freeze-drying to obtain the final product.Prepared by the present inventionm‑Si@GComposite structure is stablized, and cycle performance and high rate performance are excellent.
Description
Technical field
The invention belongs to lithium ion battery material and preparation method thereof fields, are related to a kind of lithium ion battery and usem- Si@G are answered
Close the preparation method of negative material.
Background technology
Silicium cathode is because with highest theoretical specific capacity（4 200 mAh·g-1）, low removal lithium embedded current potential（0.02~0.6 V vs.
Li+/Li）, have received the extensive concern of domestic and foreign scholars；But the huge volume change of material in de-/process of intercalation itself
（~300%）Causing electrode material, gradually dusting crushes, and the electrical contact between silicon particle and its between collector is made to be deteriorated,
The specific capacity of material is caused to decay rapidly, and the adjoint poor high rate performance of relatively low electron conductivity also further hinders
Practical application of the silicon as lithium ion battery negative material；And graphene is because of its excellent physicochemical properties, such as splendid electricity
Sub- conductibility and high specific surface area, while the flexibility of its structure can help to buffer other materials in intercalation/deintercalation Li
There are larger volume variations in the process, it is even more important for preparing the presoma of graphene, such as graphene oxide, surface tool
There is a large amount of oxygen-containing functional group, can effectively combine other ions or functional group, graphene composite negative pole is in recent years in lithium
Huge potentiality are shown in ion battery field.
The methods of silicon and the composite material of graphene reported at present are mainly using mechanical mixture, suction filtration, freeze-drying
It prepares, silicon particle is dispersed between graphene sheet layer, and in two-dimentional sandwich, but bond strength is poor on the whole, and structure is not
Stablize, easily detached in charge and discharge process；In order to improve the chemical property of silicium cathode, a kind of stable structure is inventedmThe preparation method of-Si@G composite negative pole materials is of great significance.
Invention content
The technical problems to be solved by the invention are to provide a kind of preparemThe method of-Si@G composite negative pole materials, inhibits to receive
The volume expansion of rice silicon, so as to obtain the higher silicium cathode material of structural stability, improves the chemical property of material.
Technical scheme of the present invention includes the following steps：
Nano-silicon, reagent A, water and dispersant are added in absolute ethyl alcohol, magnetic agitation, controlling reaction temperature is in 20-
95 DEG C carry out 1 ~ 48 h of reaction, and obtained uniform suspension is filtered or centrifuged, the nano-silicon after being modified, gained
Product Labeling ism-Si。
Surface after modification is carried can be the same as the nano-silicon for the functional group that graphite oxide surface functional group is combined（m-Si）
Be added in the dispersion liquid of graphite oxide with together with reducing agent, be stirred by ultrasonic, and obtain uniform suspension, after to be transferred to hydro-thermal anti-
It answers and hydro-thermal reaction is carried out in kettle, products therefrom filtering is placed in aqueous solution after progress ion exchange, washing, drying to obtain the final productm-
Si@G composite negative pole materials.
The reagent A is one kind or several in triethanolamine, the concentrated sulfuric acid, hydrogen peroxide and vinyltrimethoxysilane
Kind.
The size of the nano-silicon is 30 ~ 300 nm.
The dispersant is in cetyl trimethylammonium bromide, sodium alginate, neopelex and acetone
One or more.
The nano-silicon:Water:Dispersant:Reagent A:Mass ratio=0.5-2 of absolute ethyl alcohol:1.5-3:0.05-0.3:
0.01-10:25。
The reducing agent be polyvinylpyrrolidone, polyethylene glycol, water soluble chitosan and ethylene glycol in one kind or
Several, dosage is 1 ~ 3 times of theoretical amount.
DescribedmThe mass ratio of-Si and graphite oxide is 0.2 ~ 1：1.
The hydrothermal reaction condition is：Reaction temperature is 120 ~ 250 DEG C, and the reaction time is 2 ~ 24 h；The hydro-thermal
Reaction times are 1 ~ 2 time.
The ion-exchange reaction temperature is room temperature, and the reaction time is 24 ~ 72 h；Drying mode is freeze-drying, is pressed
Power is 60 Mpa, and the time is 48 ~ 72 h.
The invention has the advantages that：
The present invention is prepared for using the method that surface modification-hydrothermal reduction-ion exchange is combinedm- Si@G composite negative poles
Material；Nano-silicon is surface modified, can not only nano-silicon be made preferably to disperse, but also can take nano-silicon surface
Active group promotes it to carry out chemical combination bond with graphite oxide and closes, enhances the structural stability of composite material, compound so as to be promoted
The cyclical stability of material, obtains electrochemical performancem- Si@G composite negative pole materials are prepared compound by the present invention
Li insertion extraction performance up to 1000 more than mAh/g, has very excellent chemical property to material for the first time.
Description of the drawings
Fig. 1 is in embodiment 1mThe SEM figures of-Si@G composite materials.
In 1 for Fig. 2mThe corresponding TEM figures of-Si@G composite materials.
Fig. 3 is in embodiment 1mThe XRD diagram of-Si@G composite materials.
Fig. 4 is in embodiment 1mThe first charge-discharge curve of-Si@G composite materials.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and detailed description.Following embodiment is intended to illustrate
Invention rather than limitation of the invention further.
Embodiment 1
Using nano-silicon as raw material, in the ethanol solution of water, cetyl trimethylammonium bromide is selected（CTAB）For dispersant,
Triethanolamine is reagent A, control m (nano-silicon):M (water):m(CTAB):M (reagent A):M (absolute ethyl alcohol)=2:2:0.2:5:
25, reaction temperature is 25 DEG C, and the reaction time is 24 h, after centrifugationm- Si powder.
It willm- Si is with graphite oxide according to 1:4 ratio is disperseed, and adds polyvinylpyrrolidone（Adding proportion is reason
1 times of stoichiometric）For reducing agent, ultrasonic agitation is transferred in hydrothermal reaction kettle after being uniformly dispersed and carries out hydro-thermal reaction, and reaction temperature is
160 DEG C, the reaction time is 20 h, and products therefrom filtering is placed on progress 24 h of ion exchange in aqueous solution, and washing, freezing are dry
After dry 48 h to obtain the final productm- Si@G composite negative pole materials.
Gained composite material SEM is schemed as shown in Figure 1, it can be seen from the figure that nano-silicon is wrapped in graphene well
In conductive network.
TEM schemes as shown in Fig. 2, result is consistent with sem analysis result, and graphene is in silk shape, and lamella is less, to receive
Rice silicon provides good cladding and conductive network.
For XRD diagram as shown in figure 3, nano silicon structure is apparent, the small peak at 26 is the characteristic peak of graphene.Chemical property
As shown in figure 4, it takes off lithium specific capacity for the first time is up to 1283.8 mAh/g, electro-chemical activity
It is higher.
Embodiment 2
Using nano-silicon as raw material, in the ethanol solution of water, neopelex is selected（SDBS）For dispersant, sulfuric acid
Mixed liquor with hydrogen peroxide is reagent A, controls m (nano-silicon):M (water):m(SDBS):M (reagent A):M (absolute ethyl alcohol)=1:
2:0.5:8:25, reaction temperature is 25 DEG C, and the reaction time is 24 h, after centrifugationm- Si powder.
It willm- Si is with graphite oxide according to 1:2 ratio is disperseed, and adds ethylene glycol（Adding proportion is theoretical amount
1.5 again）For reducing agent, ultrasonic agitation is transferred in hydrothermal reaction kettle after being uniformly dispersed and carries out hydro-thermal reaction, reaction temperature 180
DEG C, the reaction time is 8 h, and products therefrom filtering is placed on progress 48 h of ion exchange in aqueous solution, washing, freeze-drying 60
H takes off lithium specific capacity and is up to 1103.9 mAh/g for the first time.
Embodiment 3
Using nano-silicon as raw material, in the ethanol solution of water, cetyl trimethylammonium bromide is selected（CTAB）For dispersant,
Triethanolamine is reagent A, control m (nano-silicon):M (water):m(CTAB):m(A):M (absolute ethyl alcohol)=2:2:0.2:5:25, instead
It is 25 DEG C to answer temperature, and the reaction time is 24 h, after centrifugationm- Si powder.
It willm- Si is with graphite oxide according to 1:1 ratio is disperseed, and adds polyethylene glycol（Adding proportion is theoretical amount
3 times）For reducing agent, ultrasonic agitation is transferred in hydrothermal reaction kettle after being uniformly dispersed and carries out hydro-thermal reaction, and reaction temperature is 250 DEG C,
Reaction time is 4h, and products therefrom filtering is placed on progress 72 h of ion exchange in aqueous solution, washing, 72 h of freeze-drying,
Lithium specific capacity is taken off for the first time is up to 1476.8 mAh/g.
Claims (8)
1. a kind of preparation method of composite negative electrode material of lithium ion battery, it is characterised in that：Surface after modification is carried into energy
The nano-silicon m-Si for the functional group being combined with graphite oxide surface functional group is added to point of graphite oxide together with reducing agent
In dispersion liquid, ultrasonic agitation and obtains uniform suspension, after be transferred in hydrothermal reaction kettle and carry out hydro-thermal reaction, products therefrom mistake
Filter is placed in aqueous solution after progress ion exchange, washing, drying up to m-Si@G composite negative pole materials, and G is the contracting of graphene
It writes；The reducing agent one or more of for polyvinylpyrrolidone, polyethylene glycol, water soluble chitosan and ethylene glycol,
Its dosage is 1~3 times of theoretical amount.
2. a kind of preparation method of composite negative electrode material of lithium ion battery as described in claim 1, it is characterised in that：It will receive
Rice silicon, reagent A, water and dispersant are added in absolute ethyl alcohol, and magnetic agitation, controlling reaction temperature carries out reaction 1 at 20-95 DEG C
Obtained uniform suspension is filtered or centrifuged, the nano-silicon after being modified by~48h, and products therefrom is labeled as m-Si；
The reagent A is one or more of triethanolamine, the concentrated sulfuric acid, hydrogen peroxide and vinyltrimethoxysilane.
3. a kind of preparation method of composite negative electrode material of lithium ion battery as claimed in claim 2, it is characterised in that：It is described
The size of nano-silicon is 30~300nm.
4. a kind of preparation method of composite negative electrode material of lithium ion battery as claimed in claim 2, it is characterised in that：It is described
Dispersant one or more of for cetyl trimethylammonium bromide, sodium alginate, neopelex and acetone.
5. a kind of preparation method of composite negative electrode material of lithium ion battery as claimed in claim 2, it is characterised in that：It is described
Nano-silicon:Water:Dispersant:Reagent A:Mass ratio=0.5-2 of absolute ethyl alcohol:1.5-3:0.05-0.3:0.01-10:25.
6. a kind of preparation method of composite negative electrode material of lithium ion battery as described in claim 1, it is characterised in that：It is described
M-Si and graphite oxide mass ratio be 0.2~1：1.
7. a kind of preparation method of composite negative electrode material of lithium ion battery as described in claim 1, it is characterised in that：It is described
Hydrothermal reaction condition be：Reaction temperature is 120~250 DEG C, the reaction time for 2~for 24 hours；The hydro-thermal reaction number is 1
~2 times.
8. a kind of preparation method of composite negative electrode material of lithium ion battery as described in claim 1, it is characterised in that：It is described
Ion-exchange reaction temperature for room temperature, the reaction time is 24~72h；Drying mode is is freeze-dried, pressure 60MPa, when
Between be 48~72h.
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| CN108172778A (en) * | 2017-11-29 | 2018-06-15 | 合肥国轩高科动力能源有限公司 | A kind of Si/SiOxThe preparation method of/rGO anode materials |
| CN109503166B (en) * | 2018-09-29 | 2021-07-23 | 广东凯金新能源科技股份有限公司 | Graphite cathode material for platform type lithium ion battery and preparation method thereof |
| CN109873150A (en) * | 2019-03-14 | 2019-06-11 | 西北师范大学 | The method for preparing nanometer silicon composite material as raw material using palygorskite |
| CN110265635B (en) * | 2019-05-14 | 2022-05-17 | 江苏大学 | Preparation method of silicon-carbon composite negative electrode material of lithium ion battery |
| CN113488624A (en) * | 2021-07-08 | 2021-10-08 | 中国恩菲工程技术有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN113415804B (en) * | 2021-07-29 | 2022-07-29 | 厦门海辰新能源科技有限公司 | Carbon-silicon three-dimensional structure composite material and preparation method thereof |
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| CN103035890B (en) * | 2011-10-09 | 2015-07-08 | 海洋王照明科技股份有限公司 | Silicon and graphene composite electrode material and preparation method thereof |
| CN103579627A (en) * | 2012-07-25 | 2014-02-12 | 海洋王照明科技股份有限公司 | Graphene-tin composite material, preparation method of graphene-tin composite material, lithium ion battery and preparation method of lithium ion battery |
| CN103346325B (en) * | 2013-06-28 | 2015-12-23 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium ion battery negative material, its preparation method and lithium ion battery |
| CN103441247B (en) * | 2013-08-15 | 2015-11-04 | 广州市香港科大***研究院 | A kind of high performance silicon/graphene oxide negative material constructed based on chemical bond and preparation method thereof |
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