CN1447473A - Method for preparing lithium ion solid electrolyte film with large area - Google Patents
Method for preparing lithium ion solid electrolyte film with large area Download PDFInfo
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- CN1447473A CN1447473A CN03115669A CN03115669A CN1447473A CN 1447473 A CN1447473 A CN 1447473A CN 03115669 A CN03115669 A CN 03115669A CN 03115669 A CN03115669 A CN 03115669A CN 1447473 A CN1447473 A CN 1447473A
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- film
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The film of lithium, phosphor, oxygen and nitrogen (LiPON) is deposited by using the combination of the electron beam heating method and the mitrogen ion source generator. Comparing with the method of radio frequency magnetron sputtering, the deposited area is increased nearly 10 times. The conductivity of Li ion of the LiPON film prepared by the invention can reach 2-5X10 to the power -6 s/cm. Combining with electrodes of the thin film of Ag0.5V2O5 etc. and the metal Li film electrodes, thin film Li ion battery in full solid state can be assembled.
Description
Technical field
The present invention relates to a kind of method of energy large-area preparation lithium ion solid electrolyte film, be specially a kind of preparation nitrogenize Li
3PO
4The method of (abbreviation LiPON) film, prepared film can be applied to the preparation of solid-State Thin Film Li-Ion Batteries.
Background technology
Along with the miniaturization of microelectronic component, the miniaturization long-life power supply that an urgent demand exploitation is complementary therewith.Because all solid state lithium-ion film cell that charges and discharge compares with other chemical cell, it is big to have specific capacity, and it is long to discharge and recharge the life-span, the characteristics that security performance is good, and all solid state development that charges and discharge lithium-ion film cell has broad application background.Solid-State Thin Film Li-Ion Batteries can be divided into two classes by the polymer and the inorganic solid electrolyte that adopt.Though polymer electrolyte lithium-ion battery has many advantages, its specific capacity and cycle life is all not as good as inorganic solid lithium ion battery, but also has many shortcomings, as electrolyte and electrode interface instability, and easy crystallization, bad mechanical property is to responsive to temperature etc.Yet limiting one of the main reasons that all solid state inorganic solid lithium ion hull cell uses at present, to be to prepare the deposition efficiency of inorganic solid electrolyte poor, the deposition rate that is equipped with LiPON as magnetron sputtering commonly used is per hour less than 0.3 μ m, and depositional area depends on the size of magnetic control target during production.Make all solid state lithium ion thin-film battery application be difficult to realize applying based on inorganic solid electrolyte.
The existing many reports of the preparation method of lithium phosphorus oxynitride are generally by rf magnetron sputtering Li
3PO
4Target is at N
2Or He+N
2Environment is down by the reactive deposition lithium phosphorus oxynitride.In addition, also the someone adopts thermal evaporation to prepare lithium phosphorus oxynitride with the technology that Assisted by Ion Beam (IBDA) combines.But deposition efficiency poor (deposition rate is low little with depositional area) is difficult to practical application.We had reported openly once also that pulsed laser deposition prepared lithium phosphorus oxynitride under blanket of nitrogen.Because the pressure of nitrogen is at 1～50Pa in the deposition process, the physical property of deposit film is poor, and rough surface is difficult to apply in the preparation solid-State Thin Film Li-Ion Batteries.Before the present invention, find no about adopting the electron beam heating means to combine and prepare the report of LiPON inorganic electrolyte film with nitrogen ion source generator.
Summary of the invention
The objective of the invention is to propose a kind ofly can increase depositional area, improves the method for preparing the lithium-ion electrolyte film of deposition efficiency.
The method for preparing the lithium ion solid electrolyte film that the present invention proposes is to adopt the electron beam heating means lithium deposition phosphorous oxynitride LiPON thin-film material that combines with nitrogen ion source generator.Deposition process is carried out in the electron beam evaporation system, and concrete steps are as follows: at first with molecular pump the air pressure of vacuum chamber is extracted into 10
-3Pa; The generator of being furnished with nitrogen ion or atom free radical at this vacuum chamber simultaneously, such as ion-coupled plasma (ICP) or electron cyclotron resonace (ECR), the operating power of ion-coupled plasma (ICP) or electron cyclotron resonace generators such as (ECR) is greater than 150 watts, as adopting 150-400 watt; By the high pure nitrogen body flow in noticeable degree feeding ion-coupled plasma chamber, the purity of nitrogen makes the nitrogen plasma of generation freely be diffused into the evaporation vacuum chamber more than 99.99%, and the direction of diffusing opening is on deposition substrate; Regulate nitrogen flow, make the air pressure of vacuum reaction chamber remain on 10
-2Pa; Use electron beam heating evaporation LiPO
3Film, during evaporation, the power of electron gun output is 200～6000 watts, comparatively appropriate output power is 400-1000 watt; Substrate and LiPO
3Range is from being 30～50 centimetres, and deposition rate is controlled at per hour 0.2～0.6 μ m.
Among the present invention, LiPO
3Target is by Li
3PO
4(99.99% purity) powder is pressed into disk, makes in about 2 hours through 600 ℃ of annealing.Substrate can adopt stainless steel substrates or be coated with stainless steel substrates, the glass of electrode film or be coated with glass of Al film etc.The present invention is because the distance of target and substrate (distance that rf magnetron sputtering hits with substrate is 10cm) greatly, has big depositional area, than big nearly 10 times of the depositional area of the solid electrolyte film of other method preparation such as present rf magnetron sputtering, improved deposition efficiency, this production to reality is significant, thereby has improved preparation efficiency.
The present invention can adopt the section of scanning electron microscopy (SEM, Cambridge S-360, the U.S.) observation film, to estimate its thickness; Photoelectron spectroscopy (XPS) and infrared fourier spectrometer (FTIR, Bruker IFS 113V, Germany) film etc. is used to characterize the chemical composition and the membrane structure of film.
The membrane structure for preparing among the present invention is determined by x-ray diffractometer (Rigata/Max-C).X-ray diffracting spectrum shows that the film that obtains is unbodied non crystalline structure.Measured by ESEM and to show that film is made up of nano particle, their diameter is respectively about 20～50 nanometers, and distribution of particles is even.The composition of film is characterized by x-ray photoelectron power spectrum (XPS) and electron loss spectrum (EDX).
By the lithium phosphorus oxynitride (LiPON) of method for preparing, show Li through XPS and EDX mensuration, P, the existence of O and N element, the content of N is between 3%～18%.Infrared spectrum records and belongs to PO
3The 1050cm of stretching vibration
-1The peak.
In conjunction with the method for thermal evaporation, " sandwich " structure of assembling metal Al/LIPON/ metal A l is by the ionic conductivity of ac impedance technology (electrochemical workstation Chi660a) measurement LiPON film.The result shows that the Li ionic conductance of LIPON film is 2～5 * 10
-6S/cm.
The present invention is in conjunction with Ag
0.5V
2O
5Lithium metal membrane electrode Deng membrane electrode and prepared by heat evaporation is assembled into solid-State Thin Film Li-Ion Batteries.These solid-State Thin Film Li-Ion Batteries of assembling have the favorable charge-discharge performance.
The glassy state LiPON Li for preparing among the present invention
3PO
4N
x(LIPON,
LiThium
PHosphorous
OXy
nItride) being a kind of stable inorganic electrolyte, having advantages such as the good and wide electrochemical window of ionic conductivity height, thermodynamic stability is wide, is one of solid electrolyte best in all solid-state thin-film lithium battery.
Embodiment
Below by the embodiment the inventive method of further making a deposition.
Embodiment adopts the electron beam heating means to combine with nitrogen ion source generator.The vacuum system that is implemented in a cover electron beam evaporation of this method is carried out.At first the air pressure of vacuum chamber is extracted into 1.0 * 10 with molecular pump
-3Pa.This vacuum system is furnished with the device of an ion-coupled plasma (ICP) simultaneously.The operating power of ion-coupled plasma device is at 250 watts.By the high pure nitrogen body flow (99.99%) in noticeable degree feeding ion-coupled plasma chamber, the nitrogen plasma of generation freely is diffused into the evaporation vacuum chamber, and the direction of diffusing opening is on deposition substrate.Regulating nitrogen flow makes the air pressure of vacuum reaction chamber remain on 2 * 10
-2Pa.During evaporation, 400 watts of the power of electron gun output.Substrate and LiPO
3Range is from being 40 centimetres.Deposition rate is at 0.4 μ m per hour.The temperature of substrate is a normal temperature.With stainless steel substrates or be coated with the stainless steel substrates of electrode film, glass or the glass etc. that is coated with the Al film are substrate.LiPO
3Target is by imported L i
3PO
4(99.99%) powder is pressed into disk, makes in 2 hours through 600 ℃ of annealing.
Show that by X-ray diffraction mensuration the film of deposition is unbodied non crystalline structure.Measured by stereoscan photograph and to show that film is made up of the particle that diameter is approximately 30 nanometers, distribution of particles is even, free of pinholes.
In conjunction with the method for thermal evaporation Al, assembling metal Al/LiPO
3" sandwich " structure of/metal A l has been measured LiPO by ac impedance technology
3The Li ionic conductance of film is 2 * 10
-6S/cm.
Ag in conjunction with the pulse laser preparation
0.5V
2O
5The lithium metal membrane electrode assembling Ag of membrane electrode and prepared by heat evaporation
0.5V
2O
5//LiPON/Li solid-State Thin Film Li-Ion Batteries.The specific capacity of battery is 45mAh/cm
2. μ m, nearly 100 times of cycle-index.
Therefore, adopt the electron beam heating means LiPON film for preparing that combines with nitrogen ion source generator to can be applicable in the solid-State Thin Film Li-Ion Batteries as electrolytic thin-membrane.Its feature is to have big depositional area, and the solid electrolyte film for preparing than other methods such as present rf magnetron sputterings can deposit big nearly 10 times area, has improved the production efficiency of preparation solid electrolyte film.This is significant to actual production.
Claims (3)
1, a kind of preparation method of lithium ion solid electrolyte film, it is characterized in that adopting the electron beam heating means to combine with nitrogen ion source generator, lithium deposition phosphorous oxynitride thin-film material, deposition process is carried out in the electron beam evaporation system, and concrete steps are as follows: with molecular pump the air pressure of vacuum chamber is extracted into 10
-3Pa; Be furnished with ion-coupled plasma (ICP) or electron cyclotron resonace (ECR) simultaneously at this vacuum chamber, operating power is greater than 150 watts, feed the high pure nitrogen body flow in ion-coupled plasma chamber by a noticeable degree, make the nitrogen plasma of generation freely be diffused into the evaporation vacuum chamber, the direction of diffusing opening is on deposition substrate; Make the air pressure of vacuum reaction chamber remain on 10
-2Pa; Use electron beam heating evaporation LiPO
3Film, during evaporation, the power of electron gun output is 200～6000 watts, substrate and LiPO
3Range is from being 30～50 centimetres, and deposition rate is controlled at per hour 0.2～0.6 μ m.
2, preparation method according to claim 1, when it is characterized in that the electron beam heating evaporation film, the power output of electron gun is 400-1000 watt.
3, preparation method according to claim 1 is characterized in that adopting the section of sem observation film, to estimate its thickness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03115669XA CN1191654C (en) | 2003-03-06 | 2003-03-06 | Method for preparing lithium ion solid electrolyte film with large area |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03115669XA CN1191654C (en) | 2003-03-06 | 2003-03-06 | Method for preparing lithium ion solid electrolyte film with large area |
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| Publication Number | Publication Date |
|---|---|
| CN1447473A true CN1447473A (en) | 2003-10-08 |
| CN1191654C CN1191654C (en) | 2005-03-02 |
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ID=28050462
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03115669XA Expired - Fee Related CN1191654C (en) | 2003-03-06 | 2003-03-06 | Method for preparing lithium ion solid electrolyte film with large area |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346524C (en) * | 2005-07-28 | 2007-10-31 | 复旦大学 | Device and method for preparing solid thin-membrane lithium battery by in-situ deposition |
| CN101652496B (en) * | 2007-04-06 | 2012-10-03 | H.E.F.公司 | Oxynitride sputtering target |
| GB2493022A (en) * | 2011-07-21 | 2013-01-23 | Ilika Technologies Ltd | Vapour deposition process for the preparation of a phosphate compound |
| CN105449216A (en) * | 2015-11-18 | 2016-03-30 | 何整风 | Lithium battery |
| WO2016095275A1 (en) * | 2014-12-19 | 2016-06-23 | 深圳市华星光电技术有限公司 | Vapor deposition apparatus |
| CN111430806A (en) * | 2020-03-03 | 2020-07-17 | 桂林电子科技大学 | Fluorophosphate film solid electrolyte and preparation method and application thereof |
| US11923532B2 (en) | 2017-04-17 | 2024-03-05 | Robert Bosch Gmbh | Pre-lithiated silicon-based anode, and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422381C (en) * | 2005-12-29 | 2008-10-01 | 复旦大学 | Method for preparing LLTO(lithium lanthanum titanate) film by electron beam heat evaporation |
-
2003
- 2003-03-06 CN CNB03115669XA patent/CN1191654C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346524C (en) * | 2005-07-28 | 2007-10-31 | 复旦大学 | Device and method for preparing solid thin-membrane lithium battery by in-situ deposition |
| CN101652496B (en) * | 2007-04-06 | 2012-10-03 | H.E.F.公司 | Oxynitride sputtering target |
| GB2493022A (en) * | 2011-07-21 | 2013-01-23 | Ilika Technologies Ltd | Vapour deposition process for the preparation of a phosphate compound |
| GB2493022B (en) * | 2011-07-21 | 2014-04-23 | Ilika Technologies Ltd | Vapour deposition process for the preparation of a phosphate compound |
| US9533886B2 (en) | 2011-07-21 | 2017-01-03 | Ilika Technologies Ltd. | Vapour deposition process for the preparation of a phosphate compound |
| WO2016095275A1 (en) * | 2014-12-19 | 2016-06-23 | 深圳市华星光电技术有限公司 | Vapor deposition apparatus |
| CN105449216A (en) * | 2015-11-18 | 2016-03-30 | 何整风 | Lithium battery |
| CN105449216B (en) * | 2015-11-18 | 2018-10-23 | 何整风 | A kind of lithium battery |
| US11923532B2 (en) | 2017-04-17 | 2024-03-05 | Robert Bosch Gmbh | Pre-lithiated silicon-based anode, and manufacturing method thereof |
| CN111430806A (en) * | 2020-03-03 | 2020-07-17 | 桂林电子科技大学 | Fluorophosphate film solid electrolyte and preparation method and application thereof |
| CN111430806B (en) * | 2020-03-03 | 2021-09-24 | 桂林电子科技大学 | Fluorophosphate film solid electrolyte and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1191654C (en) | 2005-03-02 |
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Granted publication date: 20050302 Termination date: 20100306 |