CN106252720B - A kind of preparation method of high ionic conductivity electrolytic thin-membrane - Google Patents
A kind of preparation method of high ionic conductivity electrolytic thin-membrane Download PDFInfo
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- CN106252720B CN106252720B CN201610769271.2A CN201610769271A CN106252720B CN 106252720 B CN106252720 B CN 106252720B CN 201610769271 A CN201610769271 A CN 201610769271A CN 106252720 B CN106252720 B CN 106252720B
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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 present invention relates to a kind of preparation methods of high ionic conductivity electrolytic thin-membrane, belong to technical field of lithium ion.The present invention uses IV race's element doping and the thin film low temperature deposition method far below room temperature, improves the disordering degree of film chemical key and mode and the microstructure of film, realizes that the ionic conductivity for effectively improving film electrolyte layer reaches 10‑5S/cm magnitude, the discharge current of film lithium ion battery can be increased order of magnitude greater, the large current discharging capability of film energy-storage battery is effectively improved, the disadvantage of existing film energy-storage battery discharge capability deficiency is greatly solved, has expanded the application direction of film energy-storage battery.
Description
Technical field
The present invention relates to a kind of preparation methods of high ionic conductivity electrolytic thin-membrane, and in particular to one kind is stored up for film
The preparation method of the electrolyte layer of energy lithium ion battery, belongs to technical field of lithium ion.
Background technique
Film energy storage lithium ion battery has important application in micro-nano field of electronic devices.But at present commercialization lithium from
Electrolyte-LiPON ionic conductivity in sub- hull cell can only achieve 10-6S/cm magnitude, with heavy-current discharge
Application requirement there are a certain distance.Therefore a kind of electrolytic thin-membrane that ionic conductivity is high is needed, is suitable for high current and puts
The application requirement of electricity.
Summary of the invention
In view of the demand, the purpose of the present invention is to provide a kind of preparation sides of high ionic conductivity electrolytic thin-membrane
Method, the method may be implemented electrolytic thin-membrane chemical bond and mode and highly disorderedization of membrane structure control, make film
The ionic conductivity of electrolyte layer improves a magnitude on the basis of existing, solves electrolytic thin-membrane and does not adapt to larger electric discharge
The application of electric current.
To achieve the purpose of the present invention, technical solution below is provided:
It selects lithium metasilicate and lithium phosphate molar ratio for the composite target material of 0.2:1~0.5:1, is evacuated to 5~6 × 10-4Pa,
Substrate temperature is reduced between 100~220K and maintaining this temperature.It is passed through High Purity Nitrogen, flow is 10~30sccm, keeps pressure
For 0.1~3Pa.Open rf magnetron sputtering, power be 50~300W, pre-sputter cleaning composite target material 5~30min of surface, with
Remove surface contaminants.100~220K low temperature depositing, 1~8h is carried out, a kind of high ionic conductivity electrolytic thin-membrane is obtained.
Described, High Purity Nitrogen is the nitrogen that purity is greater than 99.999%.
Preferably, the composite target material is prepared using ceramic post sintering method.
Preferably, reducing base reservoir temperature to 100~220K is realized by logical liquid nitrogen.
Beneficial effect
(1) the method for the invention forms reticulated conductive channel by IV race element doping, and rationally controls the nitrogen of material
Content and chemical bonding mode, and pass through the system of the low temperature thin film deposition method realization highly disordered electrolytic thin-membrane of film
It is standby, the ionic conductivity of electrolytic thin-membrane can be made to improve a magnitude, it is same correspondingly to significantly improve film energy-storage battery
Under the conditions of discharge capability, greatly solve the disadvantage of existing film energy-storage battery discharge capability deficiency, expanded film energy storage
The application direction of battery.
(2) the method for the invention is applicable to all kinds of micro-nano type energy storage devices, is particularly suitable for integrated information
Memory device.
Specific embodiment
Test method in following embodiment
Ionic conductivity: " sandwich " structure that electrolytic thin-membrane/metal Al obtained by solution metal Al/ embodiment is formed
Electrochemical impedance spectroscopy obtain, " sandwich " structure be substrate on plate attached one layer of metal Al, pass through following reality on metal Al
It applies example and plates attached one layer of high ionic conductivity electrolytic thin-membrane, then to plate on above-mentioned electrolytic thin-membrane attached one layer of metal Al such a
Structure.Electrochemical impedance spectroscopy is measured by CORRTEST INSTRUMENTS CS350 electrochemical workstation, and selection impedance~
Frequency scanning, frequency range 1Hz-100000Hz, DC potential 1V, alternating-current magnitude 5mV.
Magnetron sputtering coater used is Kurt Lay Cisco System Co. (Kurt J.Lesker Company) in embodiment
3000C magnetron sputtering coater.
Embodiment 1
Lithium metasilicate and lithium phosphate molar ratio are chosen as the composite target material of 0.2:1, magnetron sputtering coater vacuum chamber is put into, takes out
Vacuum is to 5 × 10-4The plate-like circulation line that liquid nitrogen injects below base-tray is cooled to 100K to substrate and kept by Pa, to
Vacuum chamber is passed through High Purity Nitrogen (purity is greater than 99.999% nitrogen), and flow control 10sccm, holding pressure is 0.1Pa, is beaten
Open rf magnetron sputtering power supply, power 50W, pre-sputter cleaning composite target material surface 30min.Open magnetron sputtering coater gear
Plate carries out 100K low temperature depositing 8h, obtains a kind of high ionic conductivity electrolytic thin-membrane.
The ionic conductivity of test gained electrolytic thin-membrane is 1.03 × 10-5S/cm。
Embodiment 2
Lithium metasilicate and lithium phosphate molar ratio are chosen as the composite target material of 0.5:1, is put into magnetron sputtering coater vacuum chamber,
It is evacuated to 6 × 10-4The plate-like circulation line that liquid nitrogen injects below base-tray is cooled to 220K to substrate and kept by Pa,
It is passed through High Purity Nitrogen (purity is greater than 99.999% nitrogen) to vacuum chamber, flow control 30sccm, holding pressure is 3Pa, is beaten
Open rf magnetron sputtering power supply, power 300W, pre-sputter cleaning composite target material surface 5min.Open magnetron sputtering coater gear
Plate carries out 220K low temperature depositing 1h, obtains a kind of high ionic conductivity electrolytic thin-membrane.
The ionic conductivity of test gained electrolytic thin-membrane is 1.45 × 10-5S/cm。
Embodiment 3
Lithium metasilicate and lithium phosphate molar ratio are chosen as the composite target material of 0.33:1, is put into magnetron sputtering coater vacuum
Room is evacuated to 5.5 × 10-4Pa cools down the plate-like circulation line that liquid nitrogen injects the Work piece rotary disc that abutting places substrate to it
It to 150K and keeps, is passed through High Purity Nitrogen (purity is greater than 99.999% nitrogen) to vacuum chamber, flow control 20sccm is kept
Pressure is 0.5Pa, opens rf magnetron sputtering power supply, power 200W, pre-sputter cleaning composite target material surface 10min.It opens
Magnetron sputtering coater baffle carries out 150K low temperature depositing 2h, obtains a kind of high ionic conductivity electrolytic thin-membrane.
The ionic conductivity of test gained electrolytic thin-membrane is 3.2 × 10-5S/cm。
The present invention includes but is not limited to above embodiments, it is all carried out under the principle of spirit of that invention it is any equivalent
Replacement or local improvement, all will be regarded as within protection scope of the present invention.
Claims (3)
1. a kind of preparation method of high ionic conductivity electrolytic thin-membrane, it is characterised in that: concrete operations are as follows:
It selects lithium metasilicate and lithium phosphate molar ratio for the composite target material of 0.2:1~0.33:1, is evacuated to 5~5.5 × 10-4Pa,
Substrate temperature is reduced between 100~150K and this temperature is maintained, is passed through High Purity Nitrogen, flow is 10~20sccm, keeps pressure
0.1~0.5Pa, open rf magnetron sputtering, power be 50~200W, pre-sputter cleaning composite target material 10~30min of surface, into
Row 100~150K, 2~8h of low temperature depositing, obtains a kind of high ionic conductivity electrolytic thin-membrane；
The High Purity Nitrogen is the nitrogen that purity is greater than 99.999%.
2. a kind of preparation method of high ionic conductivity electrolytic thin-membrane as described in claim 1, it is characterised in that: described
Composite target material is prepared using ceramic post sintering method.
3. a kind of preparation method of high ionic conductivity electrolytic thin-membrane as described in claim 1, it is characterised in that: reduce base
Bottom temperature to 100~220K is realized by logical liquid nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610769271.2A CN106252720B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of high ionic conductivity electrolytic thin-membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610769271.2A CN106252720B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of high ionic conductivity electrolytic thin-membrane |
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| CN106252720A CN106252720A (en) | 2016-12-21 |
| CN106252720B true CN106252720B (en) | 2019-09-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108530054A (en) * | 2018-05-15 | 2018-09-14 | 北京科技大学 | The preparation method of target used in a kind of all solid state electrolyte thin film sputtering |
| CN111883759A (en) * | 2020-07-29 | 2020-11-03 | 黄杰 | Nano-silicon composite material with core-shell structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789483A (en) * | 2005-12-29 | 2006-06-21 | 复旦大学 | Method for preparing LLTO(lithium lanthanum titanate) film by electron beam heat evaporation |
| CN101414674A (en) * | 2008-08-05 | 2009-04-22 | 华南师范大学 | Cathode material for lithium ion battery tin/carbon nanometer multilayer film, and preparation method and application thereof |
| CN103144393A (en) * | 2013-04-02 | 2013-06-12 | 南开大学 | Silicon-based thin film material with sandwich structure and preparation method and application thereof |
-
2016
- 2016-08-30 CN CN201610769271.2A patent/CN106252720B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789483A (en) * | 2005-12-29 | 2006-06-21 | 复旦大学 | Method for preparing LLTO(lithium lanthanum titanate) film by electron beam heat evaporation |
| CN101414674A (en) * | 2008-08-05 | 2009-04-22 | 华南师范大学 | Cathode material for lithium ion battery tin/carbon nanometer multilayer film, and preparation method and application thereof |
| CN103144393A (en) * | 2013-04-02 | 2013-06-12 | 南开大学 | Silicon-based thin film material with sandwich structure and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《Plasma Diagnostic Studies of the influence of Process Variables upon the Atomic and Molecular Species Ejected From》;Wachs A L，et al.;《 Journal of Vacuum Science & Technology A vacuum Surface & Films》;19980630;第2页第1段、第3页第2段、第4页第2段、图3 * |
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