CN100505388C - FeLiWO4 anode film material and its making method - Google Patents
FeLiWO4 anode film material and its making method Download PDFInfo
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- CN100505388C CN100505388C CNB2007100391471A CN200710039147A CN100505388C CN 100505388 C CN100505388 C CN 100505388C CN B2007100391471 A CNB2007100391471 A CN B2007100391471A CN 200710039147 A CN200710039147 A CN 200710039147A CN 100505388 C CN100505388 C CN 100505388C
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- magnetron sputtering
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the lithium ion film battery technology area, specifically relates to a positive electrode material tungstate ferric lithium film (LiFe (WO4) 2) which applies to the entire solid film lithium battery and its preparation method, the invention uses the radio frequency magnetron sputtering sedimentation method prepare amorphous material tungstenic acid ferric lithium film. Combined the lithium phosphorus oxygen nitrogen (LiPON) solidstate electrolyte film by radio frequency magnetron sputtering preparation and the metal lithium negative film by the vacuum hotly evaporate preparation, composing the solid state film lithium battery. The battery specific capacity can reach 104 mAh/cm2-u m; the cycle-index can reach 150 times. These results indicated that, the radio frequency magnetron sputtering method prepare LiFe (WO4) 2 positive electrodes films, can apply to the entire solid state film lithium battery.
Description
Technical field
The invention belongs to lithium ion film battery technology, be specifically related to a kind of wolframic acid iron lithium film as all solid-state thin-film lithium battery positive electrode and preparation method thereof.The present invention relates to adopt first the method for rf magnetron sputtering to prepare wolframic acid iron lithium film (LiFe (WO
4)
2).This technology has successfully prepared the film with amorphous state characteristic, and its main feature is to form good interface with the solid electrolyte film, has high electronic conductivity, can be applied to all solid-state thin-film lithium battery.
Background technology
Along with the miniaturization of microelectronic component, the miniaturization long-life 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 capacity maximum has discharging and recharging the life-span of overlength, and security performance is good.So all solid state development that charges and discharge lithium-ion film cell has application background widely.In order to develop jumbo solid-State Thin Film Li-Ion Batteries, the selection of anode film material is particularly important.The LiCoO of typical layer structure
2, LiNi
xCo
1-xO
2LiMn with spinel structure
2O
4Be applied to all solid-state thin-film lithium battery.But cobalt element is poisonous and cobalt costs an arm and a leg, and has limited LiCoO
2And LiNi
xCo
1-xO
2Application in battery.LiMn
2O
4Then easily undergo phase transition, cause capacity attenuation in the 3V zone.These thin-film materials all must be handled in the heating deposit or through subsequent anneal, and preparation condition harshness, and the film of preparation is crystalline structure can not form the interface of matched well with the solid electrolyte film, easily causes the hull cell short circuit.
Summary of the invention
The objective of the invention is to propose a kind of electronic conductivity height, need not annealing in process, preparation condition is simple, can be as thin-film material of all solid-state thin-film lithium battery positive pole and preparation method thereof.
The anode film material that can be used as all solid-state thin-film lithium battery that the present invention proposes is a kind of amorphous state wolframic acid iron lithium film, and it is synthetic by high temperature solid state reaction by lithium carbonate, iron oxide and tungsten oxide, and its molecular formula is LiFe (WO
4)
2This film surface is level and smooth, is light blue, is unbodied amorphous structure, can form the matched well interface with the solid electrolyte film.Because wolframic acid iron lithium film has two electrochemical reaction activated centres, can become one of anode film material that specific capacity is the highest in all solid-state thin-film lithium battery.
The method for preparing wolframic acid iron lithium film that the present invention proposes is to adopt the rf magnetron sputtering sedimentation, i.e. deposit film on a magnetic control sputtering 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, fed the volume flow of vacuum chamber argon gas and oxygen then by noticeable degree, the flow-rate ratio of argon gas and oxygen is 2:1～4:1, and the direction that feeds mouth is over against deposition substrate, regulate mixed gas flow the air pressure of vacuum chamber is remained on below the 1.5Pa, deposit LiFe (WO with rf magnetron sputtering
4)
2Film, during deposition, radio frequency power output is 30～40 watts, and substrate and wolframic acid iron lithium range be from being 5～7 centimetres, and deposition rate is 25～50nm per hour, and substrate temperature is a room temperature.Among the present invention, wolframic acid iron lithium target is made by high temperature solid state reaction.
The present invention is in preparation process, with the surface and the section of scanning electron microscopy (SEM, Cambridge S-360, the U.S.) observation film, with surface topography and the estimated thickness of controlling it.Measured by scanning electron microscopy, show that film surface is level and smooth, no particle shows.Determine that with x-ray diffractometer (Rigata/Max-C) membrane structure, X-ray diffracting spectrum show that the film of deposition is unbodied non crystalline structure.
Analyze the reaction mechanism of wolframic acid iron lithium film in electrochemical process with photoelectron spectroscopy (XPS, self-control) and transmission electron microscope (TEM, JEOL 2010).The photoelectron spectroscopy test shows only exists ferric iron and sexavalence tungsten in film.By electrochemistry embedding lithium, ferric iron and sexavalence tungsten all show electro-chemical activity, and ferric iron is reduced into ferrous iron, and sexavalence tungsten is reduced into the tungsten of tetravalence and pentavalent.Transmission electron microscope shows LiFe (WO
4)
2Part can take place in charge and discharge process decompose, form the catabolite of nanometer crystal formation.
The present invention is in conjunction with containing lithium hexafluoro phosphate (LiPF
6) organic electrolyte EC-DMC and metal lithium sheet be assembled into liquid simulated battery.Li/LiFe (WO
4)
2The specific capacity of simulated battery is 198mAh/g, and cycle-index can reach 300 times.These results show: based on the LiFe (WO with the radio frequency magnetron sputtering method preparation
4)
2Film can be used as the positive electrode of secondary chargeable lithium battery.
The present invention is assembled into all solid-state thin-film lithium battery in conjunction with LiPON (LiPON) the solid electrolyte film of rf magnetron sputtering preparation and the lithium metal membrane electrode of vacuum thermal evaporation preparation.All solid-state thin-film lithium battery Li/LiPON/LiFe (WO
4)
2The specific capacity of/Pt is 104mAh/cm
2-μ m, cycle-index can reach 150 times.These results show: based on the LiFe (WO with the radio frequency magnetron sputtering method preparation
4)
2Anode film material, all solid-state thin-film lithium battery of assembling has the favorable charge-discharge performance.
Description of drawings
Fig. 1 is Li/LiFe (WO
4)
2The charging and discharging curve of liquid simulated battery.
Fig. 2 is Li/LiPON/LiFe (WO
4)
2The charging and discharging curve of/Pt all-solid-state battery.
Fig. 3 is Li/LiPON/LiFe (WO
4)
2The stable circulation linearity curve of/Pt all-solid-state battery.
Embodiment
Embodiment 1
Among the present invention, adopt the rf magnetron sputtering deposition process to prepare wolframic acid iron lithium (LiFe (WO
4)
2) anode thin film.Vacuum system at a cover magnetron sputtering deposition is carried out.At first the air pressure of vacuum chamber is extracted into 1.0 * 10 with molecular pump
-3Pa, feed the argon gas of vacuum chamber and the volume flow of oxygen by noticeable degree then, the flow-rate ratio of argon gas and oxygen is 2:1～4:1, the direction that feeds mouth is regulated mixed gas flow and is made the air pressure of vacuum chamber remain on 1.2Pa, during deposition over against deposition substrate, radio frequency power output is 40 watts, substrate and wolframic acid iron lithium range be from being 5 centimetres, and deposition rate is 35nm per hour, and substrate temperature is a room temperature.With the Pt sheet is substrate, and wolframic acid iron lithium target is synthetic by high temperature solid state reaction.
Show that by X-ray diffraction mensuration the film of deposition is unbodied non crystalline structure.Show that film surface is level and smooth, no granule boundary by stereoscan photograph mensuration.Show LiFe (WO by photoelectron spectroscopy mensuration
4)
2Li in the film, Fe, the mol ratio of W and O element is 1.01:0.92:1.97:8, and has ferric iron and sexavalence tungsten in film.
Be assembled into liquid simulated battery Li/LiFe (WO in conjunction with organic electrolyte EC-DMC that contains lithium hexafluoro phosphate (LiPF6) and metal lithium sheet
4)
2, its specific capacity is about 198mAh/g (accompanying drawing 1), and cycle-index can reach 300 times.
Embodiment 2
Adopt the rf magnetron sputtering deposition process to prepare wolframic acid iron lithium (LiFe (WO
4)
2) anode thin film.At first the air pressure of vacuum chamber is extracted into 1.0 * 10 with molecular pump
-3Pa, be 3:1 by the argon gas of two noticeable degree feeding vacuum chamber and the flow-rate ratio of oxygen then, the direction that feeds mouth is over against deposition substrate, regulating mixed gas flow makes the air pressure of vacuum chamber remain on 1.2Pa, during deposition, radio frequency power output is 40 watts, and substrate and wolframic acid iron lithium range are from being 5 centimetres, deposition rate is 35nm per hour, and substrate temperature is a room temperature.With the Pt sheet is substrate, and wolframic acid iron lithium target is synthetic by high temperature solid state reaction.
In conjunction with LiPON (LiPON) the protective layer film of rf magnetron sputtering preparation and the lithium metal membrane electrode of vacuum thermal evaporation preparation, all solid-state thin-film lithium battery Li/LiPON/LiFe (WO that is assembled into
4)
2The specific capacity of/Pt is about 104mAh/cm
2-μ m (accompanying drawing 2), cycle-index can reach (accompanying drawing 3) 150 times.
Embodiment 3
Adopt the rf magnetron sputtering deposition process to prepare wolframic acid iron lithium (LiFe (WO
4)
2) anode thin film.At first the air pressure of vacuum chamber is extracted into 1.0 * 10 with molecular pump
-3Pa, be 2:1 by the argon gas of two noticeable degree feeding vacuum chamber and the flow-rate ratio of oxygen then, the direction that feeds mouth is over against deposition substrate, regulating mixed gas flow makes the air pressure of vacuum chamber remain on 1.0Pa, during deposition, radio frequency power output is 40 watts, and substrate and wolframic acid iron lithium range are from being 5 centimetres, deposition rate is 40nm per hour, and substrate temperature is a room temperature.With the Pt sheet is substrate, and wolframic acid iron lithium target is synthetic by high temperature solid state reaction.
In conjunction with LiPON (LiPON) the protective layer film of rf magnetron sputtering preparation and the lithium metal membrane electrode of vacuum thermal evaporation preparation, all solid-state thin-film lithium battery Li/LiPON/LiFe (WO that is assembled into
4)
2The specific capacity of/Pt is about 101mAh/cm
2-μ m, cycle-index can reach 150 times.
Therefore, adopt the LiFe (WO of rf magnetron sputtering deposition process preparation
4)
2Film can be applicable in all solid-state thin-film lithium battery as anode film material.The characteristics of this film are surface smoothings, and preparation condition is simple, need not annealing in process, have the electronic conductivity height, can form the matched well interface with the solid electrolyte film, and volume and capacity ratio is big.
Claims (2)
1. the anode film material of an all solid-state thin-film lithium battery is characterized in that by lithium carbonate, iron oxide and tungsten oxide by the synthetic amorphous state wolframic acid iron lithium thin-film material of high temperature solid state reaction, molecular formula is LiFe (WO
4)
2
2. the preparation method of an anode film material as claimed in claim 1 is characterized in that adopting the rf magnetron sputtering 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, feed the argon gas of vacuum chamber and the volume flow of oxygen by noticeable degree then, the flow-rate ratio of argon gas and oxygen is 2:1～4:1, and the direction that feeds mouth is regulated mixed gas flow the air pressure of vacuum chamber is remained on below the 1.5Pa over against deposition substrate; With rf magnetron sputtering deposition wolframic acid iron lithium film, during deposition, radio frequency power output is 30～40 watts, and substrate and wolframic acid iron lithium range be from being 5～7 centimetres, and deposition rate is 25～50nm per hour, and substrate temperature is a room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100391471A CN100505388C (en) | 2007-04-05 | 2007-04-05 | FeLiWO4 anode film material and its making method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100391471A CN100505388C (en) | 2007-04-05 | 2007-04-05 | FeLiWO4 anode film material and its making method |
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| Publication Number | Publication Date |
|---|---|
| CN101034740A CN101034740A (en) | 2007-09-12 |
| CN100505388C true CN100505388C (en) | 2009-06-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100391471A Expired - Fee Related CN100505388C (en) | 2007-04-05 | 2007-04-05 | FeLiWO4 anode film material and its making method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855421B (en) * | 2012-11-30 | 2016-07-13 | 纳米新能源（唐山）有限责任公司 | Self-charging film lithium ion battery |
| CN106784988A (en) * | 2015-11-24 | 2017-05-31 | 中国航空工业集团公司北京航空材料研究院 | A kind of flexible all solid-state thin-film lithium battery and its production method |
| CN106067548B (en) * | 2016-08-13 | 2018-10-23 | 杭州富阳伟文环保科技有限公司 | A kind of SnO2/ iron tungstate lithium/carbon composite nano-material and preparation method thereof |
| CN107315298B (en) * | 2017-07-07 | 2020-04-28 | 中国航发北京航空材料研究院 | Brown electrochromic charge storage electrode and preparation method thereof |
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