CN108390030A - One kind is towards SiO2The surface modification method of/C cathode - Google Patents
One kind is towards SiO2The surface modification method of/C cathode Download PDFInfo
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- CN108390030A CN108390030A CN201810096319.7A CN201810096319A CN108390030A CN 108390030 A CN108390030 A CN 108390030A CN 201810096319 A CN201810096319 A CN 201810096319A CN 108390030 A CN108390030 A CN 108390030A
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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
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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
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Abstract
The invention belongs to technical field of lithium ion, provide one kind towards SiO2The surface modification method of/C cathode；The present invention is by the method for physical vapour deposition (PVD) (PVD) or atomic layer deposition (ALD), in SiO2/ C negative terminal surfaces deposit one layer of lithium ion conductor buffer layer, are located at SiO2Between/C cathode and solid electrolyte；The lithium ion conductor buffer layer uses Li1+xTi2‑xMx(P O4)3, wherein 0≤x<2, M=Al, Ga, In, Sc；Or La2/3‑xLi3xTiO3；Or LiOH.By in SiO2Increase by one layer of lithium ion conductor cushioning layer material between/C cathode and solid electrolyte, form artificial SEI films, inhibits bad side reaction between electrode and electrolyte contacts interface to occur, effectively improve the structural stability of negative material, reduce Si O in charge and discharge process2/ C negative electrode volumes change the negative effect brought, to improve cycle performance of battery.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to by SiO2/ C negative materials carry out surface and repair
Decorations enhance negative pole structure stability, reduce negative electrode volume variation, inhibit the bad side reaction of Si and electrolyte, reduce interface resistance
It is anti-, promote battery performance.
Background technology
Currently, lithium ion battery is widely used to the electronic equipments such as mobile phone, notebook, digital camera and electric vehicle
On, the demand with market to lithium ion battery increasingly increases, to lithium ion battery in charge-discharge velocity, security performance and cycle
Requirement in performance is also higher and higher.
The theoretical specific capacity of simple substance silicon materials is about 4200mAh/g, the reason of significantly larger than present commercial graphite cathode material
By specific capacity (372mAh/g), therefore causes researchers and greatly pay close attention to；But silicon materials are poor in charge and discharge process
Cyclical stability limit its application in business.It is generally acknowledged that silicon based anode material Li ions in charge and discharge process
Embedded abjection causes active material powder of detached, cycle performance to be deteriorated with the change dramatically of volume.Use composite material can be with
Bulk effect is effectively relieved, so as to improve the cycle performance of material, such as SiO2/ C composite negative poles；The oxide of silicon is also that one kind can
The material of silicon substrate bulk effect, in process of intercalation for the first time, Li is effectively relieved+With SiO2It reacts and generates inert Li2O
And Li4SiO4, generated in-situ nano Si and inert substance are evenly dispersed, on the one hand these inert substances can buffer the body of Si
Product expansion, on the other hand prevents the reunion of nano Si, so as to improve electrode cycle performance.
To promote lithium battery capacity, it is common method to promote charging/discharging voltage, but in existing electrolyte, lithium under high voltage
Salt Li PF6Decomposing the micro HF generated also can be to SiO2/ C composite negative poles cause to corrode, and cause SiO2The capacity of/C composite negative poles
Decay too fast, cycle life is short, limits its commercial applications.Electrode surface coating modification be it is a kind of effectively inhibit electrode with
The method of the bad side reaction of electrolyte.
Invention content
The purpose of this patent is in view of the foregoing drawbacks, to provide one kind towards SiO2The surface modification method of/C cathode；It is logical
The method for crossing physical vapour deposition (PVD) (PVD) or atomic layer deposition (ALD), in SiO2/ C composite negative pole film surfaces deposit one layer
The higher finishing coat of ionic conductivity prevents electrode and electrolysis as artificial solid electrolyte interface film (artificial SEI films)
Bad side reaction occurs (corrosion of the hydrofluoric acid (HF) generated in electrolyte under such as high voltage to electrode), improves between liquid
SiO2The structural stability of/C negative materials, to promote battery performance.
To achieve the above object, the technical solution adopted by the present invention is：
One kind is towards SiO2The surface modification method of/C cathode, which is characterized in that in SiO2/ C negative terminal surfaces deposit one layer of lithium
Ion conductor buffer layer is located at SiO2Between/C cathode and solid electrolyte；The lithium ion conductor buffer layer uses Li1+ xTi2-xMx(PO4)3, wherein 0≤x<2, M=Al, Ga, In, Sc；Or La2/3-xLi3xTiO3, wherein 0<x<2/3；Or
LiOH。
The beneficial effects of the present invention are：
The present invention passes through in SiO2Increase by one layer of lithium ion conductor cushioning layer material, shape between/C cathode and solid electrolyte
At artificial SEI films, inhibits bad side reaction between electrode and electrolyte contacts interface to occur, effectively improve the structure of negative material
Stability reduces SiO in charge and discharge process2/ C negative electrode volumes change the negative effect brought, to improve cycle performance of battery.
Simultaneously；SiO2The fine and close lithium ion conductor buffer layer of/C negative terminal surfaces sputtering coats such as nucleocapsid surrounding phase ratio, only on surface with other
One layer of buffer layer is coated, rather than most of particle is coated one by one, that is, is conducive to reduce interface impedance, and reduce complex process
Degree, and realize electronics (SiO2The effect of C in/C cathode) it is led with the double of ion (effect of lithium ion conductor buffer layer)
It is logical, on the basis of not reducing battery performance itself, interface side reaction is inhibited to occur, while stablizing negative pole structure, reduces boundary
Face impedance improves circulating battery stability.
Description of the drawings
Fig. 1 is magnetron sputtering method in embodiment in SiO2/ C negative terminal surfaces prepare the flow chart of cushioning layer material.
Specific implementation mode
The present invention is described in further details with reference to the accompanying drawings and examples.
Physical vaporous deposition (such as rf magnetron sputtering, evaporation) and atomic layer deposition strategy are mainly used in the present invention
(ALD) by lithium ion conductor buffer layer uniform deposition in SiO2/ C negative terminal surfaces；One kind is provided in the present embodiment towards SiO2/ C is negative
The surface modification method of pole, by rf magnetron sputtering in SiO2/ C negative terminal surfaces deposit one layer of lithium ion conductor buffer layer, position
In SiO2Between/C cathode and solid electrolyte；Lithium ion conductor buffer layer uses Li0.35La0.56TiO3；Detailed process such as Fig. 1
It is shown.
In the present embodiment, SiO2Prepared by/C negative materials uses following scheme：
1, tetraethoxysilane (TEOS) is mixed with ethyl alcohol and distilled water with vigorous stirring, and acetic acid is then added as acid
Property catalyst；Obtained mixture is stirred 15 minutes, a certain amount of ammonium hydroxide is then added as basic catalyst；
After gelation, gel is aged 3 days in ethanol at ambient temperature, then by the every 12 hours use of the solution of ageing
Fresh ethyl alcohol replaces 4 times, to remove unreacted chemical substance and ensure that perfect solution exchanges；
Wet gel is dried at room temperature for 1 day, it is then 2 days dry at 80 DEG C, obtain required porous silica；
Use planetary ball mill using ethyl alcohol as medium at room temperature with the constant rotational speed of 400rpm porous silica
Ball milling 5 hours；It is added to a certain amount of sucrose as carbon source in ball milling slurry with vigorous stirring, then uses rotary evaporator
Drying composite；
At 900 DEG C, N2It is heat-treated under atmosphere, obtains SiO2/ C negative materials.
2, sucrose is dissolved in deionized water with continuous stirring, then, different amounts of SiO2Nano particle (7nm diameters)
It is added in sucrose solution, the SiO2Weight ratio with sucrose is 5:8 to 1:8；
Then with magnetic stirrer mixture to ensure SiO2Dispersion in the solution, then steams moisture at 60 DEG C
It is dry to obtain solid mixture；Mixture is heated 3 hours in nitrogen atmosphere in 900 DEG C, cooled to room temperature；Obtaining has respectively
The carbon-coated SiO of kind carbon content2Nano particle.
SiO2Prepared by/C cathode pole pieces uses following scheme：
First, solvent is used as by using n-methyl-2-pyrrolidone (NMP), by SiO2/ C negative materials, acetylene black
(AB) and Kynoar (PVDF) is with mass ratio 70:15:15 mix；
Then, electrode slurry is coated on copper foil；At ambient temperature, then dry in 70 DEG C~90 DEG C baking ovens
Afterwards, electrode film is suppressed to and is cut into the SiO of a diameter of 8mm2/ C cathode pole pieces.
SiO2/ C cathode pole piece surface modifications：In SiO by way of magnetron sputtering2/ C negative plates surface sputters one layer of cause
Close Li0.33La0.56TiO3Electrolytic thin-membrane；
(1) Li is used0.33La0.56TiO3Target, Li0.33La0.56TiO3Be in perovskite (LLTO) type solid electrolyte from
The solid electrolyte of electron conductivity highest (1mS/cm), lithium excessively mainly make up the missing of lithium in sputtering process；According to operation stream
Journey installs target, while the SiO that will be cut out2/ C pole pieces are fixed in stainless steel base；
(2) back end vacuum pressure is extracted into less than 5.0 × 10-4Pa；
(3) base reservoir temperature is warming up to 50-120 DEG C；
(4) adjustment air pressure is 0.5-1.5Pa, and sputtering atmosphere is：Argon gas:Oxygen=7:3；
(5) sputtering power is：80-120W；
(6) sputtering time is：5-20min；
(7) it after sputtering, shuts down according to equipment shutdown process；
(8) battery assembling is carried out according to battery assembling flow path.
The above description is merely a specific embodiment, any feature disclosed in this specification, except non-specifically
Narration, can be replaced by other alternative features that are equivalent or have similar purpose；Disclosed all features or all sides
Method or in the process the step of, other than mutually exclusive feature and/or step, can be combined in any way.
Claims (1)
1. one kind is towards SiO2The surface modification method of/C cathode, which is characterized in that in SiO2/ C negative terminal surfaces deposit one layer of lithium from
Sub- conductor buffer layer is located at SiO2Between/C cathode and solid electrolyte；The lithium ion conductor buffer layer uses Li1+xTi2-xMx
(PO4)3, wherein 0≤x<2, M=AL, Ga, In, Sc；Or La2/3-xLi3xTiO3, wherein 0<x<2/3；Or LiOH.
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| CN201810096319.7A CN108390030A (en) | 2018-01-31 | 2018-01-31 | One kind is towards SiO2The surface modification method of/C cathode |
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| CN201810096319.7A CN108390030A (en) | 2018-01-31 | 2018-01-31 | One kind is towards SiO2The surface modification method of/C cathode |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364700A (en) * | 2019-05-31 | 2019-10-22 | 南方科技大学 | Silica composite material, preparation method thereof and lithium ion battery |
| CN111326727A (en) * | 2020-03-09 | 2020-06-23 | 洛阳联创锂能科技有限公司 | Multi-component silicon-oxygen negative electrode material for lithium ion battery and preparation method thereof |
| CN114976023A (en) * | 2022-07-28 | 2022-08-30 | 江苏蓝固新能源科技有限公司 | Conductor material, preparation method thereof, coated electrode material and battery |
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| JP2009277381A (en) * | 2008-05-12 | 2009-11-26 | Sumitomo Electric Ind Ltd | Lithium battery |
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| KR20140137718A (en) * | 2013-05-23 | 2014-12-03 | 주식회사 엘지화학 | Method for preparing electrode comprising inorganic coating layer, electrode prepared by the method, and secondary battery comprising the electrode |
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2018
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Patent Citations (6)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364700A (en) * | 2019-05-31 | 2019-10-22 | 南方科技大学 | Silica composite material, preparation method thereof and lithium ion battery |
| CN110364700B (en) * | 2019-05-31 | 2021-09-03 | 南方科技大学 | Silica composite material, preparation method thereof and lithium ion battery |
| CN111326727A (en) * | 2020-03-09 | 2020-06-23 | 洛阳联创锂能科技有限公司 | Multi-component silicon-oxygen negative electrode material for lithium ion battery and preparation method thereof |
| CN114976023A (en) * | 2022-07-28 | 2022-08-30 | 江苏蓝固新能源科技有限公司 | Conductor material, preparation method thereof, coated electrode material and battery |
| CN114976023B (en) * | 2022-07-28 | 2022-09-30 | 江苏蓝固新能源科技有限公司 | Conductor material, preparation method thereof, coated electrode material and battery |
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