CN1447475A - Method for preparing lithium ion solid electrolyte film with high deposition rate - Google Patents
Method for preparing lithium ion solid electrolyte film with high deposition rate Download PDFInfo
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- CN1447475A CN1447475A CN03115668A CN03115668A CN1447475A CN 1447475 A CN1447475 A CN 1447475A CN 03115668 A CN03115668 A CN 03115668A CN 03115668 A CN03115668 A CN 03115668A CN 1447475 A CN1447475 A CN 1447475A
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- film
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- lithium
- nitrogen
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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
Abstract
Azotized Li3PON4 or simplified as lithium phosphor, oxygen and nitrogen (LiPON) is prepared by combination of the pluse laser deposition method and the azote ion source generator. The method provides fast deposition speed reaching to 0.8-2.0 micron m per hour. The conductivity of Li ion of the lithium, phosphor, oxygen and nitrogen film prepared by using the invented method reaches 2-5X10 to the power -6 s/cm. Combining with V2O5 and MoO3 etc. other electrodes as well as the metal lithium film electrode prepared by heat evaporation, the all-solid state film lithium ion battery can be assembled.
Description
Technical field
The present invention relates to the high method for preparing the lithium ion solid electrolyte film of a kind of deposition rate, be specially a kind of preparation nitrogenize Li
3PO
4The method of (abbreviation LiPON) film.Prepared film can be applied to 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, have the specific capacity maximum, it is long to discharge and recharge the life-span, the characteristics that security performance is good.The 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 the report that the new technology that adopts pulsed laser deposition to combine with nitrogen ion source generator prepares LiPON.
Summary of the invention
The objective of the invention is to propose the high method for preparing the lithium ion solid electrolyte film of a kind of deposition rate, thereby improve preparation efficiency, reduce cost.
It among the present invention the method for preparing the lithium ion solid electrolyte film that proposes, be to adopt pulsed laser deposition to combine to deposit lithium phosphorus oxynitride (LiPON) material with the ion source generator, deposition process is carried out in that stainless steel reaction is indoor, adopt the pld (pulsed laser deposition) system, concrete steps are as follows: adopt ultraviolet or visible impulse laser ablation Li
3PO
4Target material, laser energy density are 2～5J/cm
2Adopt electron cyclotron resonace (ECR) or ion-coupled plasma (ICP) method to produce nitrogen ion or atom free radical.The operating power of electron cyclotron resonace (ECR) or ion-coupled plasma (ICP) is greater than 200 watts, as is 200-400 watt; By the high pure nitrogen body flow of noticeable degree feeding reative cell, nitrogen gas purity is more than 99.99%.Thin film deposition is on substrate, and the distance of substrate and target is 2～5cm, and substrate temperature is a room temperature during deposition.The deposition rate of the inventive method is 0.8～2.0 μ m per hour.This speed is greater than nearly 10 times of the method for rf magnetron sputtering.
Among the present invention, ultraviolet or visible impulse laser can be obtained after frequency tripling or two frequencys multiplication by the fundamental frequency that a Nd:YAG (Spectra Physics) produces.Target material is by imported L i
3PO
4(99.99%) powder is pressed into disk, makes through 600 ℃ of annealing 2h.
Scanning electron microscopy among the present invention (SEM, Cambridge S-360, the U.S.) is used to observe the section of film to estimate its thickness; Photoelectron spectroscopy (XPS, self-control) and infrared fourier spectrometer (FTIR, Bruker IFS 113V, Germany) film etc. are 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.Show that by ESEM mensuration film is nano particle and forms, 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 above-mentioned two kinds of methods preparation, show Li through XPS and EDX mensuration, P, the existence of O and N element, the content of N is between 7%～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 V
2O
5, with MoO
3Wait the lithium metal membrane electrode of other membrane electrode and prepared by heat evaporation to be 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.These results show: based on the LiPON electrolytic thin-membrane that combines with nitrogen ion source generator with the electron beam heating means and pulsed laser deposition combines with nitrogen ion source generator and prepares, 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.
The invention is further illustrated by the following examples for embodiment.
Embodiment 1
Among the present invention, adopt the pulsed laser deposition preparation that combines with nitrogen ion source generator.Pld (pulsed laser deposition) carries out in that stainless steel reaction is indoor.532nm visible impulse laser is obtained after two frequencys multiplication by the fundamental frequency that a Nd:YAG (Spectra Physics) produces.Depositing used laser energy density is 4J/cm
2Nitrogen ion source generator is produced by an electron cyclotron resonace (ECR) device.The operating power of cyclotron resonance device is at 300 watts.By the high pure nitrogen body flow (99.99%) in noticeable degree feeding cyclotron resonance chamber, the nitrogen plasma of generation freely is diffused into pulsed laser deposition chamber, and the direction of diffusing opening is on deposition substrate.Regulating nitrogen flow makes the air pressure of laser reactive chamber remain on 2 * 10
-2Pa.Substrate and LiPO
3The distance of target is 3.5 centimetres.The temperature of substrate is a normal temperature.Sedimentation time 1.5 hours.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.Deposition rate is at 1.0 μ m per hour.LiPO
3Target is by imported L i
3PO
4(99.99%) powder is pressed into disk, makes through 600 ℃ of annealing 2h.
Being deposited on LiPON film on glass is pale red.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.
XPS and EDX result have shown Li, P, and the existence of O and N element, the content of N is roughly 12%.The results of FT-IR is at 1050cm
-1Peak PO
3Stretching vibration.
In conjunction with the method for thermal evaporation Al, " sandwich " structure of assembling metal Al/LiPON/ metal A l, the Li ionic conductance of having been measured the LiPON film by ac impedance technology is 2 * 10
-6S/cm.
V in conjunction with the pulse laser preparation
2O
5The lithium metal membrane electrode of membrane electrode and prepared by heat evaporation is assembled into V
2O
5//LiPON/Li solid-State Thin Film Li-Ion Batteries.The specific capacity of battery is 23mAh/cm
2. μ m, nearly 100 times of cycle-index.
V in conjunction with the pulse laser preparation
2O
5The lithium metal membrane electrode of membrane electrode and prepared by heat evaporation is assembled into MoO
3//LiPON/Li solid-State Thin Film Li-Ion Batteries.The specific capacity of battery is 55mAh/cm
2. μ m, nearly 30 times of cycle-index.
Therefore, the method that is combined with nitrogen ion source generator by pulsed laser deposition has prepared lithium phosphorus oxynitride and can be applicable in the solid-State Thin Film Li-Ion Batteries as electrolytic thin-membrane.Its feature is to have fast film deposition rate.Than fast nearly ten times of the solid electrolyte film of other method preparation such as present rf magnetron sputtering.
Claims (3)
1, a kind of preparation method of lithium ion solid electrolyte film, it is characterized in that adopting impulse light deposition method to combine with nitrogen ion source generator, lithium deposition phosphorous oxynitride thin-film material, deposition process is carried out in the stainless steel reaction chamber, adopt the pld (pulsed laser deposition) system, concrete steps are as follows: adopt ultraviolet or visible impulse laser ablation Li
3PO
4Thin target material, laser energy density are 2～5J/cm
2Adopt electron cyclotron resonace (ECR) or ion-coupled plasma (ICP) method to produce nitrogen ion or atom free radical, the operating power of electron cyclotron resonace (ECR) or ion-coupled plasma (ICP) is greater than 200 watts; Feed the high pure nitrogen body flow of reative cell by a noticeable degree; Thin film deposition is on substrate, and the distance of substrate and target is 2～5cm, and substrate temperature is a room temperature during deposition.
2, preparation method according to claim 1 is characterized in that ultraviolet or visible impulse laser are obtained after frequency tripling or two frequencys multiplication by the fundamental frequency that a Nd:YAG produces.
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 |
|---|---|---|---|
| CNB031156681A CN1191655C (en) | 2003-03-06 | 2003-03-06 | Method for preparing lithium ion solid electrolyte film with high deposition rate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031156681A CN1191655C (en) | 2003-03-06 | 2003-03-06 | Method for preparing lithium ion solid electrolyte film with high deposition rate |
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|---|---|
| CN1447475A true CN1447475A (en) | 2003-10-08 |
| CN1191655C CN1191655C (en) | 2005-03-02 |
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ID=28050461
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328808C (en) * | 2004-04-23 | 2007-07-25 | 中国科学院物理研究所 | Nitrogen phosphate anode material for secondary lithium battery and uses thereof |
| GB2493022A (en) * | 2011-07-21 | 2013-01-23 | Ilika Technologies Ltd | Vapour deposition process for the preparation of a phosphate compound |
| 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 |
|---|---|---|---|---|
| CN100391034C (en) * | 2006-01-12 | 2008-05-28 | 复旦大学 | Lithium battery electrode material Li2S/Co nanometer compound film and its preparation method |
-
2003
- 2003-03-06 CN CNB031156681A patent/CN1191655C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328808C (en) * | 2004-04-23 | 2007-07-25 | 中国科学院物理研究所 | Nitrogen phosphate anode material for secondary lithium battery and uses thereof |
| 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 |
| US11923532B2 (en) | 2017-04-17 | 2024-03-05 | Robert Bosch Gmbh | Pre-lithiated silicon-based anode, and manufacturing method thereof |
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| Publication number | Publication date |
|---|---|
| CN1191655C (en) | 2005-03-02 |
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