CN1789483A - Method for preparing LLTO(lithium lanthanum titanate) film by electron beam heat evaporation - Google Patents
Method for preparing LLTO(lithium lanthanum titanate) film by electron beam heat evaporation Download PDFInfo
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- CN1789483A CN1789483A CN 200510112198 CN200510112198A CN1789483A CN 1789483 A CN1789483 A CN 1789483A CN 200510112198 CN200510112198 CN 200510112198 CN 200510112198 A CN200510112198 A CN 200510112198A CN 1789483 A CN1789483 A CN 1789483A
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Abstract
The invention, belonging to lithium ion hull cell technical field, relates the method for preparation of LLTO used for solid state thin film lithium battery. The invention adopts the electron-beam vapor deposition method to prepare LLTO, comprising the following characteristics: large film deposit area, big deposition rate, and lithium ion ionic conductivity being 2*10-7S/cm. The LiCoO2 or LiMn2O4, LiPON and antiabrasion layer film, which are made with the method of radio-frequency magnetic control sputtering, and the metallic lithium anode film made with the method of vacuum heat evaporation are assembled to solid state thin film lithium battery. The specific capacity of cell is 45mAh/cm2-mum and 24mAh/cm2-mum, and the cycle index is up to 150 times. So the LLTO solid state electrolyte thin film made by the method of electron-beam evaporation can be used in solid state thin film lithium battery.
Description
Technical field
The invention belongs to lithium ion film battery technology, be specifically related to a kind of preparation method of Li-La-Ti oxygen film of the inorganic solid electrolyte as lithium ion full solid thin film battery.
Background technology
Along with the miniaturization of microelectronic device, the miniaturization long lifetime power supply that an urgent demand exploitation is complementary therewith.The all solid state lithium-ion film cell that charges and discharge is compared with other chemical cell, and its specific storage maximum has discharging and recharging the life-span of overlength, and safety performance is good.So all solid state development that charges and discharge lithium-ion film cell has application background widely.Solid-State Thin Film Li-Ion Batteries can be divided into two classes by the polymer dielectric and the inorganic solid electrolyte that adopt.Though polymer electrolyte lithium-ion battery has many advantages, its specific storage and cycle life are all not as good as the inorganic solid electrolyte lithium ion battery.Yet limiting one of the main reasons that all solid state inorganic solid electrolyte lithium-ion film cell uses at present, to be to prepare the sedimentation effect of inorganic solid electrolyte poor, as the LiPON depositing of thin film speed of radio-frequency magnetron sputter method preparation commonly used for per hour less than 0.3 μ m, and quite little with the Li-La-Ti oxygen depositing of thin film area of pulse laser method preparation, make all solid state lithium ion thin-film battery application be difficult to realize promoting based on inorganic solid electrolyte.
The amorphous li lanthanum titanyl Li for preparing among the present invention
xLa
(2-x)/3TiO
3(LLTO, Lithium Lanthanum Titanate) is a kind of stable inorganic electrolyte, has the ionic conductivity height, an advantage such as thermodynamic stability is good and electrochemical window is wide.It has become one of solid electrolyte best in all solid-state thin-film lithium battery.
The existing many reports of the preparation method of Li-La-Ti oxygen film generally are by pulsed laser deposition LLTO target, at Ar+O
2Environment is down by heating deposition Li-La-Ti oxygen film, but sedimentation effect poor (depositional area is little).
Summary of the invention
The objective of the invention is to propose the high method for preparing Li-La-Ti oxygen film of a kind of sedimentation effect, and institute prepares the lithium ion conduction characteristic of film.
The method for preparing Li-La-Ti oxygen film that the present invention proposes is to adopt the electron beam evaporation sedimentation, i.e. deposit film in an electron beam evaporation system, and its step is as follows:
At first the air pressure of vacuum chamber is extracted into 1.0 * 10 with molecular pump
-3Below the Pa, be 2: 0.8～2: 1.2 by the argon gas of two noticeable degree feeding vacuum chamber and the volume flow ratio of oxygen then, the direction that feeds mouth is regulated mixed gas flow and is made the air pressure of vacuum chamber remain on 7 * 10 over against deposition substrate
-2Below the Pa.With electron beam evaporation LLTO film, during evaporation, the output rating of electron beam gun is 300～600 watts.Substrate and LLTO range are from being 30～50 centimetres.Sedimentation rate is 1.0～1.6 μ m per hour.Substrate temperature is a room temperature.
Among the present invention, the LLTO target is by Li
2CO
3, La
2O
3And TiO
2Powder by 1: 1: 4 mole metering than in air through 800～1000 ℃ of annealing 7～10 hours, compressing tablet is made then.Because the distance of target and substrate is bigger, so have big depositional area, depositional area than the solid electrolyte film of other method such as present rf magnetron sputtering, pulsed laser deposition preparation is big tens times, thereby has improved preparation efficiency, and this production to reality is significant.
The present invention is in preparation process, with the surface and the section of scanning electronic microscope (SEM, Cambridge S-360, the U.S.) observation film, with surface topography and the estimated thickness of controlling it.Measured by scanning electronic microscope, show that film is nanoparticle and forms, their size is no more than 300 nanometers, and particle distribution is even.Determine that with x-ray diffractometer (Rigata/Max-C) membrane structure, X-ray diffracting spectrum show that sedimentary film is unbodied non-crystal structure.Measure film chemical with photoelectron spectrum (XPS, self-control) and form and film microstructure, show Li in the film, La, Ti and O element exist.
Method in conjunction with magnetically controlled DC sputtering, " sandwich " structure of assembling metal Au/LLTO/ metal A u, by the ionic conductivity of ac impedance technology (electrochemical workstation Chi660a) measurement LLTO film, the result shows that the ionic conductivity of LLTO film can reach 2 * 10
-7S/cm.
The present invention is in conjunction with the LiCoO of rf magnetron sputtering preparation
2, LiMn
2O
4The metallic lithium membrane electrode that LiPON (LiPON) protective layer film of membrane electrode, rf magnetron sputtering preparation (prevent the LLTO film from contact with the lithium film react) and vacuum thermal evaporation prepare is assembled into all solid-state thin-film lithium battery.All solid-state thin-film lithium battery LiCoO
2The specific storage of/LLTO/LiPON/Li is 45mAh/cm
2-μ m, cycle index can reach 150 times; LiMn
2O
4The specific storage of/LLTO/LiPON/Li battery is 24mAh/cm
2-μ m, cycle index can reach 150 times.These results show: based on the LLTO electrolytic thin-membrane with the preparation of electron beam thermal evaporation method, these all solid-state thin-film lithium batteries of assembling have the favorable charge-discharge performance.
Description of drawings
Fig. 1 is the Electronic Speculum figure (600 watts of electron beam gun power) of LLTO film.
Fig. 2 is the alternating-current impedance spectrogram of Au/LLTO/Au " sandwich " structure.
Fig. 3 is LiCoO
2The charging and discharging curve of/LLTO/LiPON/Li battery.
Embodiment
Embodiment 1
Among the present invention, adopt the electron beam evaporation method to prepare Li-La-Ti oxygen (LLTO) solid state electrolyte film.Vacuum system at a cover electron beam evaporation is carried out.At first the air pressure of vacuum chamber is extracted into 1.0 * 10 with molecular pump
-3Pa feeds the argon gas of vacuum chamber by two noticeable degree then and the throughput ratio of oxygen is 2: 1, and the direction that feeds mouth is regulated mixed gas flow and made the air pressure of vacuum chamber remain on 7 * 10 over against deposition substrate
-2Pa.During evaporation, the power of electron beam gun output is 600 watts.Substrate and LiPO
3Range is from being 30 centimetres.Sedimentation rate is 1.6 μ m per hour.Substrate temperature is a room temperature.With stainless steel substrates or be coated with the stainless steel substrates of electrode film, sheet glass or the sheet glass etc. that is coated with the Au film are substrate.The LLTO target is by Li
2CO
3(98%), La
2O
3(99.95%) and TiO
2(98%) powder by 1: 1: 4 mole metering than in air through 900 ℃ of annealing 8h, be pressed into disk then and make.
Show that by X-ray diffraction mensuration sedimentary film is unbodied non-crystal structure.Measured by stereoscan photograph and to show that film forms (accompanying drawing 1) by the particle that is approximately 300 nanometers, particle distribution is even, free of pinholes.Show Li by photoelectron spectrum mensuration, La, Ti and O element exist.
In conjunction with the method for vacuum thermal evaporation Au, " sandwich " structure of assembling metal Au/LLTO/ metal A u, the ionic conductivity of having been measured the LLTO film by ac impedance technology is 2 * 10
-7S/cm (accompanying drawing 2).
LiCoO in conjunction with the rf magnetron sputtering preparation
2The metallic lithium membrane electrode of LiPON (LiPON) the protective layer film of membrane electrode, rf magnetron sputtering preparation and vacuum thermal evaporation preparation, all solid-state thin-film lithium battery LiCoO that is assembled into
2The specific storage of/LLTO/LiPON/Li is about 45mAh/cm
2-μ m (accompanying drawing 3), cycle index can reach 150 times.
Embodiment 2
At first the air pressure of vacuum chamber is extracted into 1.0 * 10 with molecular pump
-3Pa feeds the argon gas of vacuum chamber by two noticeable degree then and the throughput ratio of oxygen is 2: 1, and the direction that feeds mouth is regulated mixed gas flow and made the air pressure of vacuum chamber remain on 5 * 10 over against deposition substrate
-2Pa.During evaporation, the power of electron beam gun output is 300 watts.Substrate and LiPO
3Range is from being 30 centimetres.Sedimentation rate is 1.0 μ m per hour.Substrate temperature is a room temperature.With stainless steel substrates or be coated with the stainless steel substrates of electrode film, sheet glass or the sheet glass etc. that is coated with the Au film are substrate.The LLTO target is by Li
2CO
3(98%), La
2O
3(99.95%) and TiO
2(98%) powder by 1: 1: 4 mole metering than in air through 900 ℃ of annealing 8h, be pressed into disk then and make.
Show that by X-ray diffraction mensuration sedimentary film is unbodied non-crystal structure.Measured by stereoscan photograph and to show that film is made up of the particle that is approximately 100 nanometers, particle distribution is even, free of pinholes.Show Li by photoelectron spectrum mensuration, La, Ti and O element exist.
In conjunction with the method for vacuum thermal evaporation Au, " sandwich " structure of assembling metal Au/LLTO/ metal A u, the ionic conductivity of having been measured the LLTO film by ac impedance technology is 1 * 10
-7S/cm.
LiMn in conjunction with the rf magnetron sputtering preparation
2O
4The metallic lithium membrane electrode of LiPON (LiPON) the protective layer film of membrane electrode, rf magnetron sputtering preparation and vacuum thermal evaporation preparation, all solid-state thin-film lithium battery LiMn that is assembled into
2O
4The specific storage of/LLTO/LiPON/Li is about 24mAh/cm
2-μ m, cycle index can reach 150 times.
Therefore, adopt the LLTO film of electron beam evaporation method preparation to can be applicable in all solid-state thin-film lithium battery as the solid state electrolyte film.The characteristics of this method are to have big depositional area and fast sedimentation rate, compare with the solid electrolyte film of other method preparation such as present rf magnetron sputtering, pulsed laser deposition, depositional area is big tens times, compare sedimentation rate with rf magnetron sputtering fast nearly 20 times, improved the production efficiency of preparation solid electrolyte film greatly, this is significant to actual production.
Claims (2)
1, a kind of preparation method of Li-La-Ti oxygen solid state electrolyte film is characterized in that adopting the electron beam evaporation sedimentation, and concrete steps are: at first with molecular pump the air pressure of vacuum chamber is extracted into 1.0 * 10
-3Below the Pa, be 2: 0.8～2: 1.2 by the argon gas of two noticeable degree feeding vacuum chamber and the volume flow ratio of oxygen then, the direction that feeds mouth is regulated mixed gas flow and is made the air pressure of vacuum chamber remain on 7 * 10 over against deposition substrate
-2Below the Pa; With electron beam heating evaporation Li-La-Ti oxygen film, during evaporation, the output rating of electron beam gun is 300～600 watts, and substrate and Li-La-Ti oxygen range be from being 30～50 centimetres, and sedimentation rate is 1.0～1.6 μ m per hour, and substrate temperature is a room temperature.
2, the preparation method of Li-La-Ti oxygen solid state electrolyte film according to claim 1, its characteristics are that described Li-La-Ti oxygen target is by Li
2CO
3, La
2O
3And TiO
2Powder by 1: 1: 4 mole metering than in air through 800～1000 ℃ of annealing 7～10 hours, compacting forming then.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450933C (en) * | 2006-12-15 | 2009-01-14 | 清华大学 | Manufacture method of lithium lanthanum titanium oxide |
| CN101971408A (en) * | 2008-07-25 | 2011-02-09 | 丰田自动车株式会社 | Li-la-ti-o composite solid electrolyte material containing silicon and synthesizing method thereof |
| CN102844927A (en) * | 2010-04-13 | 2012-12-26 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| CN102859779A (en) * | 2010-04-13 | 2013-01-02 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| CN102870266A (en) * | 2010-04-13 | 2013-01-09 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| CN105206869A (en) * | 2015-09-25 | 2015-12-30 | 山东玉皇新能源科技有限公司 | Method for electrochemically preparing solid electrolyte lithium lanthanum titanium oxides |
| CN105206870A (en) * | 2015-09-25 | 2015-12-30 | 山东玉皇新能源科技有限公司 | Method for electrochemically preparing solid electrolyte lithium lanthanum titanium oxides |
| CN106252720A (en) * | 2016-08-30 | 2016-12-21 | 兰州空间技术物理研究所 | A kind of preparation method of high ionic conductivity electrolytic thin-membrane |
| US9570748B2 (en) | 2012-10-12 | 2017-02-14 | Ut-Battelle, Llc | Lipon coatings for high voltage and high temperature Li-ion battery cathodes |
| CN106654172A (en) * | 2016-12-28 | 2017-05-10 | 中天储能科技有限公司 | Lithium metal negative plate with multiple protections |
| CN110120547A (en) * | 2019-05-20 | 2019-08-13 | 新乡芯蕴智能科技有限公司 | Preparation method and dielectric film for all-solid lithium-ion battery dielectric film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191654C (en) * | 2003-03-06 | 2005-03-02 | 复旦大学 | Method for preparing lithium ion solid electrolyte film with large area |
-
2005
- 2005-12-29 CN CNB2005101121983A patent/CN100422381C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450933C (en) * | 2006-12-15 | 2009-01-14 | 清华大学 | Manufacture method of lithium lanthanum titanium oxide |
| CN101971408A (en) * | 2008-07-25 | 2011-02-09 | 丰田自动车株式会社 | Li-la-ti-o composite solid electrolyte material containing silicon and synthesizing method thereof |
| CN101971408B (en) * | 2008-07-25 | 2016-04-27 | 丰田自动车株式会社 | Siliceous Li-La-Ti oxygen composite solid electrolyte material and preparation method thereof |
| CN102844927A (en) * | 2010-04-13 | 2012-12-26 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| CN102859779A (en) * | 2010-04-13 | 2013-01-02 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| CN102870266A (en) * | 2010-04-13 | 2013-01-09 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| CN102844927B (en) * | 2010-04-13 | 2014-11-05 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| CN102870266B (en) * | 2010-04-13 | 2015-05-27 | 丰田自动车株式会社 | Solid electrolyte material, lithium battery, and manufacturing method for solid electrolyte material |
| US9570748B2 (en) | 2012-10-12 | 2017-02-14 | Ut-Battelle, Llc | Lipon coatings for high voltage and high temperature Li-ion battery cathodes |
| US10424792B2 (en) | 2012-10-12 | 2019-09-24 | Ut-Battelle Llc | Lipon coatings for high voltage and high temperature Li-ion battery cathodes |
| US9837665B2 (en) | 2012-10-12 | 2017-12-05 | Ut-Battelle, Llc | Lipon coatings for high voltage and high temperature Li-ion battery cathodes |
| CN105206870A (en) * | 2015-09-25 | 2015-12-30 | 山东玉皇新能源科技有限公司 | Method for electrochemically preparing solid electrolyte lithium lanthanum titanium oxides |
| CN105206869A (en) * | 2015-09-25 | 2015-12-30 | 山东玉皇新能源科技有限公司 | Method for electrochemically preparing solid electrolyte lithium lanthanum titanium oxides |
| CN106252720A (en) * | 2016-08-30 | 2016-12-21 | 兰州空间技术物理研究所 | A kind of preparation method of high ionic conductivity electrolytic thin-membrane |
| CN106252720B (en) * | 2016-08-30 | 2019-09-27 | 兰州空间技术物理研究所 | A kind of preparation method of high ionic conductivity electrolytic thin-membrane |
| CN106654172A (en) * | 2016-12-28 | 2017-05-10 | 中天储能科技有限公司 | Lithium metal negative plate with multiple protections |
| CN110120547A (en) * | 2019-05-20 | 2019-08-13 | 新乡芯蕴智能科技有限公司 | Preparation method and dielectric film for all-solid lithium-ion battery dielectric film |
| CN110120547B (en) * | 2019-05-20 | 2021-03-09 | 河南固锂电技术有限公司 | Preparation method of electrolyte membrane for all-solid-state lithium ion battery and electrolyte membrane |
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