CN109962219A - The method that silicium cathode material surface constructs solid electrolyte interface film in situ in advance - Google Patents
The method that silicium cathode material surface constructs solid electrolyte interface film in situ in advance Download PDFInfo
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- CN109962219A CN109962219A CN201910013852.7A CN201910013852A CN109962219A CN 109962219 A CN109962219 A CN 109962219A CN 201910013852 A CN201910013852 A CN 201910013852A CN 109962219 A CN109962219 A CN 109962219A
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- cathode material
- silicium cathode
- solid electrolyte
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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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- 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
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- H—ELECTRICITY
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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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Abstract
The present invention relates to a kind of methods that silicium cathode material surface constructs solid electrolyte interface film in situ in advance, specific step is as follows for this method: appropriate form silicium cathode material adds to (Tris-HCl in suitable hydrochloride buffer, control pH value is 8-10.0), suitable Dopamine hydrochloride is added after 0.5-3 hours in stirring, control Dopamine hydrochloride ratio is silicium cathode material 0.5-8%, continue stirring 12-48 hours, it is filtered after reaction, it is washed through deionized water, then 2-10 hours dry under 60 degree, thus realize that silicium cathode material surface constructs poly- solid electrolyte interface film in advance.Inventive method preparation process is simple, and reaction condition is mild, and synthesized negative electrode material has highly stable cycle performance, is suitble to further large-scale production.
Description
Technical field
The invention belongs to the interleaving techniques fields of material surface engineering and lithium ion battery electrode material, are related to silicon materials table
Face functional group is designed and is constructed.
Background technique
Silicon based anode material is attracted extensive attention due to high energy density, it is considered to be next-generation negative electrode of lithium ion battery
The replacer of material.But electric conductivity, enormousness expansion and the unstable surface solid electrolyte membrane of silicon based anode material difference
Important bottleneck as its application.Researcher by effort in 20 years in the past, by by high conductive material include carbon material,
Metal material and the compound electric conductivity for making silicon based anode material of appropriate silicon source greatly improve, and volume expansion is significantly suppressed, and push
Silicon based anode material is to industrialized development.Currently, Shenzhen City Beiterui New Energy Materials Co., Ltd has been released low
The composite negative pole material product of ratio silicon and graphite, and tesla, U.S. electric vehicle Model 3 is also reported and has used low ratio
Silicium cathode material.As energy density demand is more more and more urgent, silicon based anode material will be had a vast market foreground.
However there is also many deficiencies for the battery product of silicon based anode material at present, such as with silicon ratio in electrode material
Increase, the cycle life of battery significantly decays, and high temperature storing performance deteriorates seriously, and volume expansion is big, and these problems constrain
The further development of silicon based anode material market application.Cause the key factor of these problems first is that silicium cathode material and electrolysis
The surface solid electrolyte membrane formed between matter is not sufficiently stable, and is broken ring repeatedly in cyclic process and is repaired, combined material continuous with being electrolysed
It reacts, this reaction embodies more obvious at high temperature.
Summary of the invention
The purpose of the present invention is to provide the sides that a kind of silicium cathode material surface constructs solid electrolyte interface film in advance in situ
Method, this method simple process, mild condition, the silicon composite cathode material being prepared have high specific capacity and stable circulation
Service life.
The present invention contacts to form what unstable solid electrolyte membrane put forward with electrolyte for silicon based anode material, passes through
Material surface constructs one layer of polymeric membrane in situ, with hydroxyl, carboxyl or amino functional group, in charge and discharge process preferentially with
Lithium reaction generates one layer of passivating film, and feature is to avoid traditional interface dielectric film from generating and repair, in turn with self-repair function
Improve the cyclical stability of silicon based anode material.
According to above-mentioned principle, The technical solution adopted by the invention is as follows:
A kind of method that silicium cathode material surface constructs solid electrolyte interface film in situ in advance, specific step is as follows for this method:
A. silicium cathode material is dissolved in hydrochloride buffer, the pH value for controlling reaction system is 8-10.0, is added after stirring 0.5-3h
Enter Dopamine hydrochloride, the quality for controlling Dopamine hydrochloride is the 0.5~8% of silicium cathode material, continues 12~48h of stirring, reaction knot
It filters, washs after beam, it is dry, it obtains silicium cathode material surface and constructs solid electrolyte interface film in advance in situ.
Above-mentioned silicium cathode material is pure silicon powder, and partial size is 0.1 ~ 1 micron.
Above-mentioned silicium cathode material is that the carbon silicon after carbon-coated nano silicon is primary or offspring, particle size range 0.1-15 are micro-
Rice.
In above-mentioned carbon coating step, using precursor pitch, glucose, phenolic resin as carbon source, carbon coating method includes
Hydro-thermal method, liquid phase coating, solid phase cladding and chemical vapor deposition (CVD) method etc..
The quality of above-mentioned Dopamine hydrochloride is the 0.5~8% of silicium cathode material.
Above-mentioned hydrochloride buffer is Tris-HCl.
Present invention has the advantage that dopamine can be with the spy of polymerization film formation on any surface under the conditions of certain pH value
Point.Realize that solid polymer electrolyte interfacial film is constructed on silicon based anode material surface in advance by in-situ polymerization.Film thickness can root
Regulated and controled according to silicon materials volume expansion, which has selfreparing function in silicon volume expansion and contraction process
Energy.
Detailed description of the invention
Fig. 1 is the XRD diffraction curve of sample synthesized by according to embodiments of the present invention one and two；
Fig. 2 is circulation longevity of the gained sample sample in contrast under the current density of 200mA/g according to embodiments of the present invention one
Order curve；
Fig. 3 is the cycle life curve of two sample according to embodiments of the present invention and comparative sample under the current density of 200mA/g.
Specific embodiment
It is the contents of the present invention to be described in further detail by embodiment, but the present invention is not limited to following reality below
Apply example, all silicon and silica-base material surface construction polymer films of being related to are as can repair protecting for solid electrolyte interface film
In range.
Embodiment one
(1) 0.3 gram of Si powder (100-200 nanometers of granularity) is weighed to add in 100 milliliters of Tris-HCl buffer, 1500 turns/
After minute dispersion 2.5 hours, 0.01 gram of Dopamine hydrochloride is added, continues stirring 24 hours, is taken out after reaction with filter membrane
Filter, deionized water washing is then 10 hours dry under 60 degree, and it is negative to obtain the pre- silicon for constructing solid polyelectrolyte interfacial film
Pole material product；
(2) electrode material and alginic acid for preparing above-mentioned (1) according to traditional lithium-ion battery negative electrode material electrode preparation method
Sodium binder, carbon black conductive agent, are distributed in deionized water according to mass ratio 8:1:1, and stirring forms uniform dispersion.Then it uses
Spreader is coated on copper foil, and 60 degree after drying 12 hours, rolling, punching, weighing, removed in vacuo residual solvent are moved into glove box.
It is that then loop test is carried out, and compare with nanometer silicon sample at button cell to electrode assembling with lithium piece.
Embodiment two
(1) weighing 0.3 gram of carbon silicium cathode material, (nanometer silicon face carries out the carbon silicon obtained then pre-coated is carbonized after using pitch
Material) (1-5 microns of offspring particle size range) add in 100 milliliters of Tris-HCl buffer, 1500 revs/min of dispersions
After 2.5 hours, 0.015 gram of Dopamine hydrochloride is added, continue stirring 24 hours, filtered after reaction with filter membrane, go from
Sub- water washing obtains pre- constructing solid polyelectrolyte interfacial film carbon silicium cathode material then dry 10 hours under 60 degree
Product；
(2) electrode material and alginic acid for preparing above-mentioned (1) according to traditional lithium-ion battery negative electrode material electrode preparation method
Sodium binder, carbon black conductive agent, are distributed in deionized water according to mass ratio 8:1:1, and stirring forms uniform dispersion.Then it uses
Spreader is coated on copper foil, and 60 degree after drying 12 hours, rolling, punching, weighing, removed in vacuo residual solvent are moved into glove box.
It is then to carry out loop test at button cell to electrode assembling, and compare as shown in Figure 3 with preceding sample is reacted with lithium piece.Very
Obviously, cyclical stability significantly improves.
Claims (7)
1. a kind of method that silicium cathode material surface constructs solid electrolyte interface film in situ in advance, the specific steps of this method are such as
Under:
A. silicium cathode material is dissolved in hydrochloride buffer, the pH value for controlling reaction system is 8-10.0, is stirred 0.5-3 hours
After Dopamine hydrochloride is added, control Dopamine hydrochloride quality be silicium cathode material 0.5~8%, it is small to continue stirring 12~48
When, it filters, washs after reaction, it is dry, it obtains silicium cathode material surface and constructs solid electrolyte interface film in advance in situ.
2. according to method described in claim l, it is characterised in that the silicium cathode material is pure silicon powder, and partial size is 0.1 ~ 1 micro-
Rice.
3. according to method described in claim l, it is characterised in that the silicium cathode material is the carbon silicon after carbon-coated nano silicon
Primary or offspring, 0.1-15 microns of particle size range.
4. according to the method described in claim 3, it is characterized in that in the carbon coating step, with precursor pitch, glucose,
Phenolic resin is as carbon source.
5. according to the method described in claim 4, it is characterized in that the carbon coating method includes hydro-thermal method, liquid phase coating, consolidates
Mutually cladding or chemical vapour deposition technique.
6. according to method described in claim l, it is characterised in that the quality of the Dopamine hydrochloride is the 0.5 of silicium cathode material
~8%.
7. according to method described in claim l, it is characterised in that the hydrochloride buffer is Tris-HCl.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591089A (en) * | 2019-08-27 | 2019-12-20 | 南京理工大学 | Preparation method of micro/nano core-shell structure Si @ PDA |
| CN111525107A (en) * | 2020-04-20 | 2020-08-11 | 南昌大学 | Novel synthesis method of organic micromolecule coated silicon negative electrode material |
| CN113937296A (en) * | 2021-12-17 | 2022-01-14 | 浙江锂威能源科技有限公司 | Silica negative electrode material, preparation method thereof, negative electrode plate and secondary battery |
| CN114597407A (en) * | 2020-12-07 | 2022-06-07 | 中国科学院大连化学物理研究所 | Zinc cathode and preparation method and application thereof |
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| CN105226260A (en) * | 2015-10-19 | 2016-01-06 | 中南大学 | A kind of preparation method of lithium ion battery silicon based anode material |
| CN108336311A (en) * | 2017-08-16 | 2018-07-27 | 中天储能科技有限公司 | A kind of preparation method of the silicon-carbon cathode material of doping Argent grain |
| CN109065848A (en) * | 2018-06-25 | 2018-12-21 | 深圳市清新电源研究院 | A kind of silicon-carbon composite electrode material of hollow structure and preparation method thereof |
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| CN110591089A (en) * | 2019-08-27 | 2019-12-20 | 南京理工大学 | Preparation method of micro/nano core-shell structure Si @ PDA |
| CN110591089B (en) * | 2019-08-27 | 2022-06-28 | 南京理工大学 | Preparation method of micro/nano core-shell structure Si @ PDA |
| CN111525107A (en) * | 2020-04-20 | 2020-08-11 | 南昌大学 | Novel synthesis method of organic micromolecule coated silicon negative electrode material |
| CN111525107B (en) * | 2020-04-20 | 2022-06-14 | 南昌大学 | Novel synthesis method of organic micromolecule coated silicon negative electrode material |
| CN114597407A (en) * | 2020-12-07 | 2022-06-07 | 中国科学院大连化学物理研究所 | Zinc cathode and preparation method and application thereof |
| CN114597407B (en) * | 2020-12-07 | 2024-03-19 | 中国科学院大连化学物理研究所 | Zinc cathode and preparation method and application thereof |
| CN113937296A (en) * | 2021-12-17 | 2022-01-14 | 浙江锂威能源科技有限公司 | Silica negative electrode material, preparation method thereof, negative electrode plate and secondary battery |
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Application publication date: 20190702 |