CN100367546C - Method for producing tin-based oxide thin film positive pole - Google Patents
Method for producing tin-based oxide thin film positive pole Download PDFInfo
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- CN100367546C CN100367546C CNB2005100175083A CN200510017508A CN100367546C CN 100367546 C CN100367546 C CN 100367546C CN B2005100175083 A CNB2005100175083 A CN B2005100175083A CN 200510017508 A CN200510017508 A CN 200510017508A CN 100367546 C CN100367546 C CN 100367546C
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- tin
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- oxide thin
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- based oxide
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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
Abstract
The present invention relates to a method for preparing metal-oxide thin films with low cost, simple operation and large area. The anode preparation of suggested tin base oxide thin film adopts an adjoined method of vacuum deposition and thermal oxidation assisted by an oxygen ion generator. The deposition is carried out in a stainless steel coating chamber with a vacuum evaporation coating system, a base plate is fixed on a rotating disc and is arranged in a vacuum coating machine. Evaporator source material is high purity tin and is heated by a molybdenum boat or resistance wires, and the working vacuum degree of the coating chamber is 10<-2 > to 10<-4 >mTorr. The metallic tin thin film is led with pure oxygen after deposition, so the vacuum degree in the vacuum chamber is 1.0 to 10<-2 >mTorr, oxygen ions can be generated via opening the oxygen ion generator, and the present invention can prepare the tin base oxide thin films in the conditions of 300 to 500 DEG C. The thickness of the oxygenized thin films in the present invention is 2 to 4 times of that of metal films, the deposition rate of the oxide is 600 to 1000nm/h, compared with other methods, the present invention has obvious efficiency increase.
Description
Technical field
But the present invention relates to the method for low, the simple to operate large-area preparation metal-oxide film of a kind of cost, be specially a kind of method for preparing tin-based oxide thin film positive pole.Prepared film can be used as anode material and is applied to solid-State Thin Film Li-Ion Batteries.
Background technology
The progress of microelectronics industry and the miniaturization of electronic device, microminiaturization, integrated making it drop to very low level to the power and the electric current of power supply, and this just requires power supply also must finish the revolution of miniaturization, microminiaturization.All solid-state thin-film lithium battery has high-energy-density, high voltage, has extended cycle life, the security performance advantages of higher is subject to people's attention.Yet current ic manufacturing process majority still adopts the Reflow Soldering technology, and to～250 ℃, all parts are soldered in moment by transient heating for device in this process.With the lithium metal be anode film lithium cell since the low melting point (～181 ℃) of lithium with destroyed.In addition, lithium metal is very active, very easily reacts with airborne oxygen and water vapour etc., and preparation lithium membrane equipment requires very high.Like this, in order to reduce preparation cost and to improve the lithium battery performance, the preparation of novel anode film becomes a main direction of all solid-state thin-film lithium battery research.Study the nitrogen oxide that many anode materials are silicon (as SiTON), nitride in this respect (as Sn
3N
4) wait lithium intercalation compound and metal oxide (as SnO
x) film.When they constitute battery system with suitable electrolyte, negative electrode and other annex, in charge and discharge process, lithium ion shuttles between anode and cathode, and the precipitating and the break-off of metallic state lithium do not occur, this battery be otherwise known as lithium ion battery or rocking chair type battery.Compare with film lithium cell, film lithium ion battery has advantages such as cost is low, fail safe is good.Yet the one of the main reasons that limits the solid-State Thin Film Li-Ion Batteries application at present is to prepare poor, the cost height of efficient of electrode film.Prepare SnO as magnetron sputtering technique commonly used
xDepositing of thin film speed is lower than 200nm/h.Film size depends on the size of magnetic control target, and the size of magnetic control target directly has influence on the price of target and equipment, thereby influences the cost of film.Pulsed laser deposition technique also is preparation high-quality SnO
xA kind of effective ways of film, but prepared film size only has 2～3cm
2, industrialization is difficulty relatively.
Tin-based oxide (SnO
x) film has high melt point, can bear the temperature of Reflow Soldering; Be difficult for air in oxygen and aqueous vapor react, the preparation environmental requirement is lower; Have higher specific capacity and excellent cycle performance.Therefore, SnO
xFilm is to study more a kind of solid-State Thin Film Li-Ion Batteries anode material at present.At present, the SnO that is used for solid-State Thin Film Li-Ion Batteries
xThe existing many reports of method for manufacturing thin film are as magnetron sputtering method, electrostatic spray method, chemical vapour deposition technique, electron-beam vapor deposition method, sol-gel process and pulsed laser deposition etc.Deposition rate is low, cost is high or be difficult to shortcomings such as large-area film deposition but these preparation methods exist.Before the present invention, find no and adopt vacuum evaporation to prepare SnO with the new technology that the oxonium ion source generator combines
xThe report of film.
Summary of the invention
The objective of the invention is to propose the preparation method of the high tin-based oxide thin film positive pole of a kind of deposition, thereby improve preparation efficiency, reduce cost.
The preparation that proposes among the present invention is used for the method for solid-State Thin Film Li-Ion Batteries anode film, is the method that adopts the auxiliary thermal oxidation of vacuum evaporation and oxonium ion generator to combine, preparation tin-based oxide thin film positive pole material; Be deposited in the stainless steel coating chamber and carry out, adopt the vacuum evaporation coating system, substrate is fixed on the rotating circular disk and places vacuum coating equipment, and evaporation source material is a high purity tin, adopts the heating of molybdenum boat or resistance wire, and the working vacuum degree of coating chamber is 10
-2～10
-4MTorr; Feed pure oxygen after the metallic tin thin film deposition, the vacuum degree that makes coating chamber is 1.0～10
-2MTorr opens oxonium ion generator and produces oxonium ion; Oxidation prepares tin-based oxide thin film under 300～500 ℃ of conditions.The thickness of oxidation rear film is metallic film～2.4 times among the present invention, and the deposition rate of oxide is 600～1000nm/h, with other method mutually specific efficiency obviously improve.
Substrate can be stainless steel thin slice, gold-plated monocrystalline silicon piece, gold-plated sheet glass, gold-plated alumina wafer etc. among the present invention.
Oxidization time among the present invention is 2～4h.
Scanning electron microscopy among the present invention (SEM, Cambridge S-360, the U.S.) is used for the section of viewing film to estimate the thickness of film; Photoelectron spectroscopy (XPS, Perkin Elmer PHI 5000C, the U.S.), X-ray energy spectrum (EDX, Philips XL30, the U.S.) 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 (XRD, Semis D8, Germany).Show the tin-based oxide (SnO that obtains
x) film is crystalline structure.Show that by scanning electron microscopy mensuration film is nano particle and forms, they are of a size of about 30～80nm, and distribution of particles is even.
SnO among the present invention
xThe electro-chemical test of film adopts two electrode systems and three-electrode system, wherein SnO respectively
xFilm is a work electrode, and high-purity Li sheet is to electrode and reference electrode.The 1M LiPF that electrolyte is produced for Merck company
6/ EC+DMC (w/w=1/1).Battery is equipped in the dry glove box of Ar atmosphere protection and carries out.The battery charging/discharging test is carried out on the LAND cell tester, and the Chi660a electrochemical workstation is used in the cyclic voltammetric test.
SnO
x/ LiPF
6/ Li battery system has higher battery capacity and good cycle performance.These results show: adopt the auxiliary thermal oxidation process of vacuum evaporation technology and oxonium ion generator to prepare a kind of well behaved anode material that can be used for solid-State Thin Film Li-Ion Batteries.
Embodiment
Further describe the present invention below by example.
Embodiment 1
Among the present invention, adopt the auxiliary thermal oxidation process of vacuum evaporation technology and oxonium ion generator.Be deposited in the stainless steel bell jar and carry out, at first be fixed on the stainless steel substrate that cleans up on the rotating circular disk and place in the vacuum coating equipment (DM-450A type, Beijing instrument plant).Source material is high-purity glass putty, the molybdenum boat heating.The working vacuum degree of coating chamber is 6 * 10
-3MTorr uses film thickness monitoring instrument (LHC-2) control deposition rate and film thickness.Deposition rate and film thickness be respectively 0.1nm/s and～100nm.The metal Sn thin film deposition finishes the back and feeds pure oxygen, and with the flow of noticeable degree pure oxygen, the vacuum degree that makes coating chamber is 0.1mTorr.Open electron cyclotron resonace (ECR) oxonium ion generator, 300 watts of power, oxidation 2.0h obtains SnO under 500 ℃ condition
xFilm,
Presenting white through the oxidation rear film, show that by X-ray diffraction mensuration the film of deposition is a crystalline structure, is SnO and SnO
2Compound.Scanning electron microscopy is measured and to be shown that film is made up of for the particle of～60nm particle diameter, and distribution of particles is even, and free of pinholes, free from flaw and substrate are in conjunction with tight.
EDAX results shows that the atomicity ratio of Sn and O is 1: 1.7 in the film, and promptly prepared film is SnO
1.7This film consists of SnO and SnO
2Compound, SnO and SnO
2The ratio of amount of substance be about 3: 7.
Assembling SnO
1.7/ LiPF
6/ Li battery system is at 10 μ A/cm
2The time after 100 circulations, still have the reversible capacity of 610mAh/g, each capacitance loss is less than 0.1%.Can bear bigger current density, as at 40 μ A/cm
2The time, still having the reversible capacity of 470mAh/g after 100 circulations, capacity attenuation is less.
Embodiment 2
Among the present invention, adopt the auxiliary thermal oxidation process of vacuum evaporation technology and oxonium ion generator.The gold-plated monocrystalline silicon substrate that at first will clean up is fixed on the rotating circular disk and places in the vacuum coating equipment (DM-450A type, Beijing instrument plant).Source material is high-purity glass putty, the molybdenum boat heating.The working vacuum degree of coating chamber is 1 * 10
-2MTorr uses film thickness monitoring instrument (LHC-2) control deposition rate and film thickness.Deposition rate and film thickness be respectively 0.08nm/s and～100nm.The metal Sn thin film deposition finishes the back and feeds pure oxygen, and with the flow of noticeable degree pure oxygen, the vacuum degree that makes coating chamber is 1.0mTorr.Open electron cyclotron resonace (ECR) oxonium ion generator, 350 watts of power, oxidation 3.0h obtains SnO under 450 ℃ condition
xFilm presents white through the oxidation rear film, measures by X-ray diffraction to show that the film of deposition is a crystalline structure, and be SnO and SnO
2Compound.Scanning electron microscopy is measured and to be shown that film is made up of for the particle of～40nm particle diameter, and distribution of particles is even, and free of pinholes, free from flaw and substrate are in conjunction with tight.
EDAX results shows that the atomicity ratio of Sn and O is 1: 1.6 in the film, and promptly prepared film is SnO
1.6This film consists of SnO and SnO
2Compound, SnO and SnO
2The ratio of amount of substance be about 2: 3.
Assembling SnO
1.6/ LiPF
6/ Li battery system is at 10 μ A/cm
2The time after 100 circulations, still have the reversible capacity of 570mAh/g, each capacitance loss is less than 0.1%.Can bear bigger current density, as at 40 μ A/cm
2The time, still having the reversible capacity of 450mAh/g after 100 circulations, capacity attenuation is less.
Embodiment 3
Among the present invention, adopt the auxiliary thermal oxidation process of vacuum evaporation technology and oxonium ion generator.The gold-plated sheet glass that at first will clean up is fixed on the rotating circular disk and places in the vacuum coating equipment (DM-450A type, Beijing instrument plant).Source material is high-purity reguline metal tin, the molybdenum boat heating.The working vacuum degree of coating chamber is 8 * 10
-4MTorr uses film thickness monitoring instrument (LHC-2) control deposition rate and film thickness.Deposition rate and film thickness be respectively 0.12nm/s and～100nm.The metal Sn thin film deposition finishes the back and feeds pure oxygen, and with the flow of noticeable degree pure oxygen, the vacuum degree that makes coating chamber is 9 * 10
-1MTorr.Open ion coupling plasma (ICP) oxonium ion generator, 400 watts of power, oxidation 3.5h obtains SnO under 400 ℃ condition
xFilm,
Presenting white through the oxidation rear film, show that by X-ray diffraction mensuration the film of deposition is a crystalline structure, is SnO and SnO
2Compound.Scanning electron microscopy is measured and to be shown that film is made up of for the particle of～40nm particle diameter, and distribution of particles is even, and free of pinholes, free from flaw and substrate are in conjunction with tight.
EDAX results shows that the atomicity ratio of Sn and O is 1: 1.5 in the film, and promptly prepared film is SnO
1.5This film consists of SnO and SnO
2Compound, SnO and SnO
2The ratio of amount of substance be about 1: 1.
Assembling SnO
1.5/ LiPF
6/ Li battery system is at 10 μ A/cm
2The time after 100 circulations, still have the reversible capacity of 580mAh/g, each capacitance loss is less than 0.1%.Can bear bigger current density, as at 40 μ A/cm
2The time, still having the reversible capacity of 455mAh/g after 100 circulations, capacity attenuation is less.
Embodiment 4
Among the present invention, adopt the auxiliary thermal oxidation process of vacuum evaporation technology and oxonium ion generator.The gold-plated alumina wafer that at first will clean up is fixed on the rotating circular disk and places in the vacuum coating equipment (DM-450A type, Beijing instrument plant).Source material is the high purity tin silk, the resistance wire heating.The working vacuum degree of coating chamber is 2 * 10
-4MTorr uses film thickness monitoring instrument (LHC-2) control deposition rate and film thickness.Deposition rate and film thickness be respectively 0.15nm/s and～100nm.The metal Sn thin film deposition finishes the back and feeds pure oxygen, and with the flow of noticeable degree pure oxygen, the vacuum degree that makes coating chamber is 5 * 10
-2MTorr.Open ion coupling plasma (ICP) oxonium ion generator, 450 watts of power, oxidation 4.0h obtains SnO under 300 ℃ condition
xFilm,
Presenting white through the oxidation rear film, show that by X-ray diffraction mensuration the film of deposition is a crystalline structure, is SnO and SnO
2Compound.Scanning electron microscopy is measured and to be shown that film is made up of for the particle of～40nm particle diameter, and distribution of particles is even, and free of pinholes, free from flaw and substrate are in conjunction with tight.
EDAX results shows that the atomicity ratio of Sn and O is 1: 1.4 in the film, and promptly prepared film is SnO
1.4This film consists of SnO and SnO
2Compound, SnO and SnO
2The ratio of amount of substance be about 3: 2.
Assembling SnO
1.4/ LiPF
6/ Li battery system is at 10 μ A/cm
2The time after 100 circulations, still have the reversible capacity of 600mAh/g, each capacitance loss is less than 0.1%.Can bear bigger current density, as at 40 μ A/cm
2The time, still having the reversible capacity of 400mAh/g after 100 circulations, capacity attenuation is less.
To sum up, adopt the auxiliary thermal oxidation process of vacuum evaporation technology and oxonium ion generator under lower temperature, to prepare a kind of well behaved anode material that can be used for solid-State Thin Film Li-Ion Batteries.Cost than present other method is low, the efficient height, as deposition rate is 5～6 times that magnetron sputtering method prepares tin-based oxide thin film, it is 500～1000 times that pulsed laser deposition technique prepares the tin-based oxide thin film area, for the preparation of solid-State Thin Film Li-Ion Batteries anode film provides a kind of new method.
Claims (4)
1. the preparation method of a tin-based oxide thin film positive pole is characterized in that: the method that adopts the auxiliary thermal oxidation of vacuum evaporation and oxonium ion generator to combine, preparation tin-based oxide thin film positive pole material; Be deposited in the stainless steel coating chamber and carry out, adopt the vacuum evaporation coating system, substrate is fixed on the rotating circular disk and places vacuum coating equipment, and evaporation source material is a high purity tin, adopts the heating of molybdenum boat or resistance wire, and the working vacuum degree of coating chamber is 10
-2～10
-4MTorr; Feed pure oxygen after the metallic tin thin film deposition, the vacuum degree that makes coating chamber is 1.0～10
-2MTorr opens oxonium ion generator and produces oxonium ion; Oxidation prepares tin-based oxide thin film under 300～500 ℃ of conditions.
2. the preparation method of tin-based oxide thin film positive pole according to claim 1, it is characterized in that: described oxidization time is 2～4 hours.
3. the preparation method of tin-based oxide thin film positive pole according to claim 1 is characterized in that: described substrate is stainless steel thin slice, gold-plated monocrystalline silicon piece, gold-plated sheet glass, gold-plated alumina wafer.
4. the preparation method of tin-based oxide thin film positive pole according to claim 1 is characterized in that: adopt the section of sem observation film, to estimate its thickness.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100175083A CN100367546C (en) | 2005-04-05 | 2005-04-05 | Method for producing tin-based oxide thin film positive pole |
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| CNB2005100175083A CN100367546C (en) | 2005-04-05 | 2005-04-05 | Method for producing tin-based oxide thin film positive pole |
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| CN100367546C true CN100367546C (en) | 2008-02-06 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477485A (en) * | 1982-07-12 | 1984-10-16 | Nippondenso Co., Ltd. | Process for forming an electrode of an organic cell |
| EP0489483A1 (en) * | 1990-12-03 | 1992-06-10 | Ensci, Inc. | Process for coating a substrate with tin oxide and uses for coated substrates |
| CN1182288A (en) * | 1996-10-25 | 1998-05-20 | 日本电池株式会社 | Negative electrode active material for lithium secondary battery and manufacturing method |
| CN1475798A (en) * | 2003-07-10 | 2004-02-18 | 上海大学 | Manufacturing method of stannic dioxide nano sensor |
-
2005
- 2005-04-05 CN CNB2005100175083A patent/CN100367546C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477485A (en) * | 1982-07-12 | 1984-10-16 | Nippondenso Co., Ltd. | Process for forming an electrode of an organic cell |
| EP0489483A1 (en) * | 1990-12-03 | 1992-06-10 | Ensci, Inc. | Process for coating a substrate with tin oxide and uses for coated substrates |
| CN1182288A (en) * | 1996-10-25 | 1998-05-20 | 日本电池株式会社 | Negative electrode active material for lithium secondary battery and manufacturing method |
| CN1475798A (en) * | 2003-07-10 | 2004-02-18 | 上海大学 | Manufacturing method of stannic dioxide nano sensor |
Non-Patent Citations (2)
| Title |
|---|
| 锂离子电池负极材料的研究进展. 杨宁等.电工材料，第3期. 2004 * |
| 锂离子电池锡基负极材料研究概况. 雷钢铁等.电池，第31卷第6期. 2001 * |
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