CN101457343A - Method for preparing lithium ion solid electrolyte film - Google Patents
Method for preparing lithium ion solid electrolyte film Download PDFInfo
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- CN101457343A CN101457343A CNA200710151036XA CN200710151036A CN101457343A CN 101457343 A CN101457343 A CN 101457343A CN A200710151036X A CNA200710151036X A CN A200710151036XA CN 200710151036 A CN200710151036 A CN 200710151036A CN 101457343 A CN101457343 A CN 101457343A
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- solid electrolyte
- film
- sputtering
- electrolyte film
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Abstract
The invention belongs to a method for preparing a lithium ion solid electrolyte film, which is characterized in that the method comprises the preparation processes as follows: distance between target material and a substrate is adjusted by amphi position ion-source sputtering equipment; subsequently, a sputtering chamber is vacuumed and N2 and Ar are pumped into the required sputtering chamber; a plasma generator is adjusted to generate plasmas; a traction electric field is started to sputter the plasmas onto the surface of the target material, thus starting sputtering the solid electrolyte film. By the uniform sputtering of the amphi position plasma sputtering on the target material, the sputtered material deposits on the substrate more uniformly; the uniformity of the film-forming by sputtering is especially improved to a great extent during a process of preparing large-area films; the amphi position ion-source puttering method leads the solid electrolyte film to have better uniformity, higher utilization ratio of the target material, higher film preparation speed and more deposition adjusting parameters so as to adjust the internal stress of the film layer, and the preparation method is suitable for preparing large-area solid electrolyte films and is especially suitable for industrial preparation of film batteries.
Description
Technical field
The invention belongs to mineral-type lithium ion solid electrolyte technical field of material, particularly relate to a kind of preparation method of lithium ion solid electrolyte film.
Background technology
Reduction gradually along with microminiaturization, filming and the unit consumption of energy thereof of electron device, film lithium cell worldwide comes into one's own day by day, compare with common lithium ion battery, film lithium cell has littler volume, longer work-ing life, process of charging and better stable security faster, and it all has broad application prospects in fields such as electronics, communication, medical treatment; As the normally lithium ion solid electrolyte film of electrolyte, the preparation of this film and performance thereof are huge to the property effect of film lithium cell in film lithium cell; The lithium ion solid electrolyte film not only is used for film lithium cell, can also act in the middle of the lithium cell of non-film, such as solid lithium battery, liquid state or colloidal electrolyte lithium cell etc.
Solid electrolyte film can adopt multiple existing film preparation mode to obtain, the methods of having announced at present such as adopting rf magnetron sputtering, vacuum thermal evaporation and reactive chemical vapour deposition of having reported for work is obtained, but all there is deficiency separately respectively in these methods.
With LiPON type solid electrolyte film the most frequently used in the film lithium cell is example, and the prepared LiPON lithium ion conductivity performance that goes out of diverse ways is approximate substantially, but the difference of different methods is mainly reflected in aspects such as simplification, expansion property, preparation efficiency.Generalized case, vacuum thermal evaporation are comparatively simple, but the solid electrolyte of this method preparation breaks easily owing to the internal stress effect in process of cooling; The material area of chemical gaseous phase depositing process preparation is less, usually less than 1cm
2, be difficult to practicability; And rf magnetron sputtering can finely overcome the problem that above method runs into, so being still to be used at present studying and to prepare LiPON, this method adopts maximum means, problems such as but this method exists sedimentation velocity slow, and the material internal stress is difficult to be controlled, and target utilization is low.
Summary of the invention
The present invention is for solving problems of the prior art, and a kind of big area, internal stress is adjustable, film speed is higher method for preparing lithium ion solid electrolyte film are provided.
The present invention for solving the technical scheme that technical problem adopted that exists in the known technology is:
Method for preparing lithium ion solid electrolyte film is characterized in: preparation process is as follows: adopt amphi position ion source sputtering equipment, regulate the distance between target and substrate, then sputtering chamber is vacuumized, then feed N
2With Ar to required vacuum chamber; Regulate plasma generator and produce plasma body, start the traction electric field plasma jet is arrived target material surface, beginning sputter solid electrolyte film.
The present invention can also adopt following technical measures to realize:
Method for preparing lithium ion solid electrolyte film is characterized in: described amphi position plasma splash equipment comprises emission electromagnetic field, rotation substrate, many targets substrate, vacuum pump, battery coil, radio-frequency antenna, plasma body and silica tube.
Method for preparing lithium ion solid electrolyte film is characterized in: the distance between described target and substrate is 4cm-20cm.
Method for preparing lithium ion solid electrolyte film is characterized in: described sputtering chamber is evacuated to 10
-2Below the Pa.
Method for preparing lithium ion solid electrolyte film is characterized in: described feeding N
2With Ar to required pressure in vacuum tank be 0.1Pa-10Pa.。
Advantage and positively effect that the present invention has are: by adopting the even sputter of amphi position plasma sputtering to target, make by sputter material to deposit to more uniformly in the substrate, particularly in the process of preparation large area film, can improve the homogeneity of spatter film forming significantly; Amphi position ion source sputtering method, make solid electrolyte film have better homogeneity, higher target utilization, higher film preparation speed, more laydown adjustment parameter and can regulate the rete internal stress, be fit to preparation large-area solid electrolytic thin-membrane, be particularly useful for the preparation of industrialization of hull cell.
Description of drawings
Fig. 1 is the schematic diagram of the present invention with amphi position plasma splash equipment;
Fig. 2 uses the target situation for the common sputtering equipment of the present invention;
Fig. 3 is an amphi position plasma splash equipment target service condition of the present invention;
Fig. 4 uses Li for the sputter of the common rf magnetron sputtering platform of the present invention
3PO
4Target;
The Li that Fig. 5 uses for amphi position rf magnetron sputtering platform sputter of the present invention
3PO
4Target, obviously the amphi position sputter has higher target utilization;
The synoptic diagram that Fig. 6 can control the internal stress of film for amphi position plasma splash equipment of the present invention on a large scale by air pressure in the control film-forming process and power.
Label among the figure is respectively: be the emission electromagnetic field 1.; 2. be the rotation substrate; 3. be many targets substrate; 4. vacuum pump; 5. plasma buncs coil; 6. be radio-frequency antenna; 7. be plasma body; 8. be silica tube.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, enumerate following examples now, and conjunction with figs. is described in detail as follows:
Please refer to Fig. 1-Fig. 6: adopt Li
3PO
4Target, preparation LiPON solid electrolyte film.At first adopt common rf magnetron sputtering platform shown in Figure 4 to prepare the LiPON film, its basic preparation process is: at first regulate the distance between target and substrate, then sputtering chamber is evacuated to 5 * 10
-3Pa then feeds the N that contains 0%-5%Ar
2To required pressure in vacuum tank, regulate radio-frequency power supply to the power of setting, beginning sputter LiPON, sputtering time is 10 hours, this method obtains LiPON film speed 0.2 μ m/h-0.3 μ m/h.
Fig. 5 adopts amphi position plasma splash equipment to prepare the LiPON film, and basic preparation process is: at first regulate the distance between target and substrate, then sputtering chamber is evacuated to 5 * 10
-3Pa then feeds the N of certain flow ratio
2With Ar to required pressure in vacuum tank; Regulate plasma generator and produce plasma body, start the traction electric field plasma jet is arrived target material surface, beginning sputter LiPON, sputtering time is 10 hours, this method obtains the LiPON film speed near 0.5 μ m/h, and obviously the amphi position sputter has higher target utilization.
Fig. 6 utilizes amphi position plasma splash equipment to prepare the conductive layer of solid electrolyte film, can see the internal stress that this equipment can be controlled film on a large scale by air pressure in the control film-forming process and power.
It adopts novel vacuum system membrane means---amphi position ion source sputter, this method adopts the sputter principle that is different from common rf magnetron sputtering, thereby have better uniformity of film, higher target utilization, higher film preparation speed, have more laydown adjustment parameter simultaneously and can regulate the rete internal stress.This method is fit to the preparation and the research of large-area solid electrolytic thin-membrane, is particularly useful for the preparation of industrialization of hull cell.
The sputter of amphi position ion source is a kind of novel method for manufacturing thin film, it by one independently plasma generator produce plasma body than high 2-3 order of magnitude high density of common rf magnetron sputtering process ionic medium bulk concentration, these plasma bodys are ejected into target material surface under effect of electric field then, and the target material sputter gone out form needed film.Fig. 1 is the schematic diagram of amphi position plasma sputtering equipment, comprise emission electromagnetic field 1, rotation substrate 2, many targets substrate 3, vacuum pump 4, plasma buncs coil 5, radio-frequency antenna 6, plasma body 7 and silica tube 8, this equipment is by the plasma source that utilizes radio frequency power to produce, plasma buncs coil 5, the sputter system film system that grid bias power supply etc. are formed, described amphi position plasma sputtering equipment is in the vacuum chamber side, plasma source produces plasma body 7, and plasma body 7 is directed on the target under the effect of emission electromagnetic field 1, form high density plasma 7 on the target surface, target is connected with grid bias power supply simultaneously, thereby realize efficient controlled plasma sputtering, the separate design of amphi position plasma sputtering equipment and vacuum chamber is to realize the controlled key of splash-proofing sputtering process parameter wide region, and this wide controllability makes specific application can determine the processing parameter optimization.
Owing to adopted a kind of so special sputter principle, plasma body " bombardment " target material surface uniformly under the effect in magnetic field, actual effect such as Fig. 2 are the target of common radio-frequency sputtering be etched out " runway ", because target has only a circle ring by sputter, so when the preparation large area film, be unfavorable for forming uniform thin film; And Fig. 3 is the target material surface quilt even " etching " through the amphi position plasma sputtering, and just the amphi position plasma sputtering to the even sputter of target, can make by sputter material to deposit to more uniformly in the substrate, particularly in the process of preparation large area film, can improve the homogeneity of spatter film forming significantly
On the other hand, clearly, the amphi position plasma sputtering has also improved utilization ratio to sputtering target material greatly to the even sputter of target, and this method has reached 90% to the utilization ratio of target generally speaking, and common sputter only has about 30% the utilization ratio of target.
Simultaneously, because the plasma body of this sputter equipment is by plasma body independently the source to take place to produce, the plasma ion density that this high efficiency plasma body source is produced is 10
13/ cm
3To 10
14/ cm
3, approximately than the high 2-3 of a common radio-frequency sputtering process ionic medium volume ion density order of magnitude.So highdensity plasma body like this can carry out the more bombardment of crypto set to target, and improve film preparation speed, particularly for O is arranged
2Or N
2The reactive plasma sputtering of participating in, because reactant gases is used as plasma source and further is incorporated in the target as sputter storehouse, so reactant gas has than plasma density much higher under the common sputtering condition, then can greatly promote the chemical reaction in the sputter procedure, and improve the film speed of reactive sputtering.
Because the particular principles of this amphi position plasma sputtering, the separate design of plasma producing apparatus and vacuum chamber has realized that the splash-proofing sputtering process parameter wide region is controlled, and this wide controllability makes specific application can determine the processing parameter optimization.For the electrolytical preparation of lithium ion thin film, this equipment has more laydown adjustment parameter, can be by the adjusting rete internal stress that the change of deposition parameter is come, the internal stress that can in very large range control solid electrolyte film by air pressure in the control film-forming process and power.
Adopt the sputter of amphi position ion source to obtain the LiPON film, its film preparation speed is near 0.5 μ m/h, and common radio-frequency sputtering is generally 0.2 μ m/h-0.3 μ m/h; Fig. 4 and Fig. 5 are the situations that distinct device uses target, and Fig. 4 is that target is used in common sputter, and Fig. 5 is the target that the amphi position sputter is used, and obviously the amphi position sputter has higher target utilization; In the scope of diameter 100mm, amphi position sputter film thickness error is in 4%, and common plated film has then surpassed 5%.
Claims (5)
1. method for preparing lithium ion solid electrolyte film, it is characterized in that: preparation process is as follows: adopt amphi position ion source sputtering equipment, regulate the distance between target and substrate, then sputtering chamber is vacuumized, then feed N
2With Ar to required vacuum chamber; Regulate plasma generator and produce plasma body, start the traction electric field plasma jet is arrived target material surface, beginning sputter solid electrolyte film.
2. the method for preparing lithium ion solid electrolyte film that requires according to claim 1 is characterized in that: described amphi position plasma splash equipment comprises emission electromagnetic field, rotation substrate, many targets substrate, vacuum pump, battery coil, radio-frequency antenna, plasma body and silica tube.
3. the method for preparing lithium ion solid electrolyte film that requires according to claim 1 is characterized in that: the distance between described target and substrate is 4cm-20cm.
4. the method for preparing lithium ion solid electrolyte film that requires according to claim 1, it is characterized in that: described sputtering chamber is evacuated to 10
-2Below the Pa.
5. the method for preparing lithium ion solid electrolyte film that requires according to claim 1 is characterized in that: described feeding N
2With Ar to required pressure in vacuum tank be 0.1Pa-10Pa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710151036XA CN101457343A (en) | 2007-12-14 | 2007-12-14 | Method for preparing lithium ion solid electrolyte film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710151036XA CN101457343A (en) | 2007-12-14 | 2007-12-14 | Method for preparing lithium ion solid electrolyte film |
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| CN101457343A true CN101457343A (en) | 2009-06-17 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104395496A (en) * | 2012-07-18 | 2015-03-04 | 拉波特株式会社 | Deposition device and deposition method |
| CN106264849A (en) * | 2016-08-18 | 2017-01-04 | 孟玲 | It is precious that water is warmed up in the heating capable of circulation of a kind of charging property |
| CN107425176A (en) * | 2017-07-07 | 2017-12-01 | 福建猛狮新能源科技有限公司 | A kind of all-solid lithium-ion battery and preparation method thereof |
| CN109065944A (en) * | 2018-08-06 | 2018-12-21 | 汉能移动能源控股集团有限公司 | Preparation method of solid electrolyte membrane |
| CN109088104A (en) * | 2018-08-06 | 2018-12-25 | 汉能移动能源控股集团有限公司 | Flexible solid-state battery and preparation 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 |
| CN114318273A (en) * | 2020-09-30 | 2022-04-12 | 戴森技术有限公司 | Method and apparatus for sputter deposition |
| CN114930567A (en) * | 2019-11-15 | 2022-08-19 | 戴森技术有限公司 | Method of forming crystalline layer, method of forming battery half cell |
-
2007
- 2007-12-14 CN CNA200710151036XA patent/CN101457343A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104395496A (en) * | 2012-07-18 | 2015-03-04 | 拉波特株式会社 | Deposition device and deposition method |
| US9453278B2 (en) | 2012-07-18 | 2016-09-27 | Labotec Limited | Deposition device and deposition method |
| CN106264849A (en) * | 2016-08-18 | 2017-01-04 | 孟玲 | It is precious that water is warmed up in the heating capable of circulation of a kind of charging property |
| CN107425176A (en) * | 2017-07-07 | 2017-12-01 | 福建猛狮新能源科技有限公司 | A kind of all-solid lithium-ion battery and preparation method thereof |
| CN109065944A (en) * | 2018-08-06 | 2018-12-21 | 汉能移动能源控股集团有限公司 | Preparation method of solid electrolyte membrane |
| CN109088104A (en) * | 2018-08-06 | 2018-12-25 | 汉能移动能源控股集团有限公司 | Flexible solid-state battery and preparation method thereof |
| CN114930567A (en) * | 2019-11-15 | 2022-08-19 | 戴森技术有限公司 | Method of forming crystalline layer, method of forming battery half cell |
| 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 |
| CN114318273A (en) * | 2020-09-30 | 2022-04-12 | 戴森技术有限公司 | Method and apparatus for sputter deposition |
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Open date: 20090617 |