CN101673846A - All solid state lithium ion thin-film battery - Google Patents

All solid state lithium ion thin-film battery Download PDF

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Publication number
CN101673846A
CN101673846A CN200910044488A CN200910044488A CN101673846A CN 101673846 A CN101673846 A CN 101673846A CN 200910044488 A CN200910044488 A CN 200910044488A CN 200910044488 A CN200910044488 A CN 200910044488A CN 101673846 A CN101673846 A CN 101673846A
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film
solid electrolyte
sintered sheets
solid state
lithium ion
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CN200910044488A
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吴显明
何则强
麻明友
陈上
肖卓炳
刘建本
陈良钢
陈善文
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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

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Abstract

The invention discloses an all solid state lithium ion thin-film battery, which is formed by taking Li1.3Al0.3Ti1.7(Po4)3 solid electrolyte sintered discs as the electrolyte and substrate, and respectively depositing LiCoO2 or LiMn2O4 thin films as an anode and Li4Ti5O12 or LiMn2O4 thin films as an cathode at both sides of the sintered discs, wherein the thicknesses of the anode and the cathode ofthe battery is below 20 microns, and the thicknesses of the Li1.3Al0.3Ti1.7(Po4)3 solid electrolyte sintered discs are below 1.5 mm. In the invention, the internal resistance and the thickness of thethin film battery can not be increased, and the preparation of the thin film battery is more convenient; in addition, the battery is in an all solid state and can be applied to the integration fieldand the high-temperature environment and can avoid using additive substrates.

Description

A kind of all solid state lithium ion thin-film battery
Technical field
The present invention relates to a kind of all solid state lithium ion thin-film battery.
Background technology
As all solid state lithium ion thin-film battery of a branch of lithium ion battery, owing to become aspects such as circuit, micro equipment to be with a wide range of applications, be subjected to various countries scholar's extensive concern at smart card, CMOS basis set, become the new focus of Study on Li-ion batteries using.
The research of lithium-ion film cell is at present all carried out on silicon chip or other substrate.Generally be to deposit anode thin film on substrate, the deposition solid electrolytic thin-membrane deposits negative film (or being reversed) at last then.Because there is extra substrate in hull cell, development work is comparatively loaded down with trivial details.Although with lithium phosphorus oxynitride (LiPON) amorphous thin film is that solid electrolyte, lithium metal are the LiMn of negative pole development 2O 4/ LiPON/Li or LiCoO 2/ LiPON/Li hull cell performance is [J.B.Bates relatively better, N.J.Dudney, B.Neudecker, et al.Solid State Ionics 135 (2000) 33], but because the fusing point (about 180 ℃) of lithium is lower than welding temperature (250 ℃-260 ℃), thereby can cause the fusing of cathode of lithium to destroy battery during welding, thereby be difficult to be applied to integrated field.
The inventor is at research Li 1.3Al 0.3Ti 1.7(PO 4) 3Find during the lithium ion solid electrolyte sintered sheets, although the Li of preparation 1.3Al 0.3Ti 1.7(PO 4) 3Sintered sheets thickness is less than 1mm, and the pressure during compressing tablet is less, does not add flux, but the sintered sheets of preparation has suitable intensity, not easy fracture.So with this sintered sheets as solid electrolyte the time again the double as substrate make lithium-ion film cell, can avoid using extra substrate.
The ionic conductivity of LiPON solid electrolyte film at present of greatest concern is 2.3 * 10 -6S.cm -1[X.Yu, J.B.Bates, G.E.Jellison, et al.J.Electrochem.Soc.144 (1997) 524.], Li 1.3Al 0.3Ti 1.7(PO 4) 3The ionic conductivity of solid electrolyte sintered sheets is 7 * 10 -4S.cm -1[H.Aono, E.Sugimoto, Y.Sadaoka, et al.J.Electrochem.Soc.136 (1989) L590.].More as can be known, under the identical situation of area, the thick Li of 300 μ m 1.3Al 0.3Ti 1.7(PO 4) 3The resistance difference of the LiPON solid electrolyte film that sintered sheets and 1 μ m are thick is few.Therefore be that the lithium-ion film cell of solid electrolyte is compared with there being extra substrate (thickness of general substrate is more than 300 μ m) to adopt the thick LiPON of 1 μ m, adopt Li 1.3Al 0.3Ti 1.7(PO 4) 3Sintered sheets prepares lithium-ion film cell as solid electrolyte and double as substrate, and the internal resistance of hull cell and thickness can not increase, but makes the making of hull cell more convenient.
Summary of the invention
Purpose of the present invention aims to provide a kind of all solid state lithium ion thin-film battery based on the solid electrolyte sintered sheets.
Li 1.3Al 0.3Ti 1.7(PO 4) 3Be a kind of lithium ion solid electrolyte of function admirable, its ionic conductivity can reach 7 * 10 -4S.cm -1, the intensity of sintered sheets is big, not easy fracture.The present invention adopts solid phase reaction and the synthetic Li of sol-gel process 1.3Al 0.3Ti 1.7(PO 4) 3Sintered sheets is with Li 1.3Al 0.3Ti 1.7(PO 4) 3The solid electrolyte sintered sheets deposits LiCoO as electrolytical while double as substrate respectively in the both sides of sintered sheets 2Or LiMn 2O 4Film is as anodal, Li 4Ti 5O 12Or LiMn 2O 4Film forms as negative pole.Its Li 1.3Al 0.3Ti 1.7(PO 4) 3The thickness of solid electrolyte sintered sheets is below 1.5mm, and the positive and negative electrode film thickness is below 20 μ m.
Adopt Li 1.3Al 0.3Ti 1.7(PO 4) 3Sintered sheets prepares lithium-ion film cell as solid electrolyte and double as substrate, and the internal resistance of hull cell and thickness can not increase, but makes the making of hull cell more convenient.And battery is all solid state, can be used for integrated field and hot environment, can avoid using extra substrate.
Specific embodiments
Embodiment 1
At first with the lithium acetate of stoichiometric proportion and manganese acetate heating for dissolving after small amount of deionized water, add EGME and obtain LiMn 2O 4Precursor solution, solution concentration are 0.3mol/L.Lithium acetate with stoichiometric proportion is dissolved in EGME again, treats to dissolve fully the back and adds Ti (OC 4H 9) 4And constantly stir, obtain the Li of 0.2mol/L 4Ti 5O 12Precursor solution.With Li 4Ti 5O 12The precursor solution spray pyrolysis is at Li 1.3Al 0.3Ti 1.7(PO 4) 3Solid electrolyte sintered sheets one side, sintered sheets temperature are controlled at 380 ℃.Then a side has been deposited Li 4Ti 5O 12The Li of film 1.3Al 0.3Ti 1.7(PO 4) 3Sintered sheets 800 ℃ of heat treatment 5 minutes in the short annealing system.After the heat treatment with LiMn 2O 4The precursor solution spray pyrolysis is at Li 1.3Al 0.3Ti 1.7(PO 4) 3The opposite side of sintered sheets, the sintered sheets temperature is controlled at 350 ℃, has deposited LiMn 2O 4Behind the film in the short annealing system 750 ℃ of heat treatments obtained the LiMn that open circuit voltage is about 2.4V in 5 minutes 2O 4/ Li 1.3Al 0.3Ti 1.7(PO 4) 3/ Li 4Ti 5O 12All solid state lithium ion thin-film battery.At Li 1.3Al 0.3Ti 1.7(PO 4) 3The LiMn of sintered sheets both sides deposition 2O 4, Li 4Ti 5O 12Film thickness below 20 μ m, Li 1.3Al 0.3Ti 1.7(PO 4) 3The thickness of solid electrolyte sintered sheets is below 1.5mm.In the whole process, nozzle and Li 1.3Al 0.3Ti 1.7(PO 4) 3The distance of solid electrolyte sintered sheets is 8cm,
Embodiment 2
At first with the lithium acetate of stoichiometric proportion and cobalt acetate heating for dissolving after small amount of deionized water, add the LiCoO that EGME obtains 0.3mol/L 2Precursor solution.Lithium acetate with stoichiometric proportion is dissolved in EGME in addition, treats to dissolve fully the back and adds Ti (OC 4H 9) 4And constantly stir, obtain the Li of 0.2mol/L 4Ti 5O 12Precursor solution.With LiCoO 2Precursor solution, Li 4Ti 5O 12Precursor solution difference spray pyrolysis is at Li 1.3Al 0.3Ti 1.7(PO 4) 3The both sides of solid electrolyte sintered sheets, the temperature of sintered sheets are controlled at 380 ℃, nozzle and Li 1.3Al 0.3Ti 1.7(PO 4) 3The distance of solid electrolyte sintered sheets is 8cm.Li 1.3Al 0.3Ti 1.7(PO 4) 3Both sides have deposited Li respectively 4Ti 5O 12And LiCoO 2800 ℃ of heat treatment 5 minutes in the short annealing system obtains the LiCoO that open circuit voltage is about 2.2V behind the film 2/ Li 1.3Al 0.3Ti 1.7(PO 4) 3/ Li 4Ti 5O 12All solid state lithium ion thin-film battery.At Li 1.3Al 0.3Ti 1.7(PO 4) 3The LiCoO of sintered sheets both sides deposition 2, Li 4Ti 5O 12Film thickness below 20 μ m, Li 1.3Al 0.3Ti 1.7(PO 4) 3The thickness of solid electrolyte sintered sheets is below 1.5mm.
Embodiment 3
At first with the lithium acetate of stoichiometric proportion and manganese acetate heating for dissolving after small amount of deionized water, add EGME and obtain LiMn 2O 4Precursor solution, solution concentration are 0.3mol/L.Then with LiMn 2O 4Precursor solution difference spray pyrolysis is at Li 1.3Al 0.3Ti 1.7(PO 4) 3The both sides of solid electrolyte sintered sheets, Li 1.3Al 0.3Ti 1.7(PO 4) 3Solid electrolyte sintered sheets temperature is controlled at 350 ℃, nozzle and Li 1.3Al 0.3Ti 1.7(PO 4) 3The distance of solid electrolyte sintered sheets is 8cm.Then both sides have been deposited LiMn 2O 4The Li of film 1.3Al 0.3Ti 1.7(PO 4) 3Solid electrolyte sintered sheets in the short annealing system in 750 ℃ of heat places 5 minutes obtains the LiMn that open circuit voltage is about 1.2V 2O 4/ Li 1.3Al 0.3Ti 1.7(PO 4) 3/ LiMn 2O 4All solid state lithium ion thin-film battery.At Li 1.3Al 0.3Ti 1.7(PO 4) 3The LiMn of sintered sheets both sides deposition 2O 4Film thickness below 20 μ m, Li 1.3Al 0.3Ti 1.7(PO 4) 3The thickness of solid electrolyte sintered sheets is below 1.5mm.

Claims (1)

1, a kind of all solid state lithium ion thin-film battery is characterized in that with Li 1.3Al 0.3Ti 1.7(PO 4) 3The solid electrolyte sintered sheets deposits just very LiCoO as electrolytical while double as substrate respectively in the both sides of sintered sheets 2Or LiMn 2O 4Film and negative pole are Li 4Ti 5O 12Or LiMn 2O 4Film; The positive and negative electrode film thickness below 20 μ m, Li 1.3Al 0.3Ti 1.7(PO 4) 3The thickness of solid electrolyte sintered sheets is below 1.5mm.
CN200910044488A 2009-09-28 2009-09-28 All solid state lithium ion thin-film battery Pending CN101673846A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102299383A (en) * 2011-07-20 2011-12-28 宁波大学 Mist pyrolysis preparation method of all-solid-state film lithium battery
CN102324586A (en) * 2011-06-24 2012-01-18 中国科学院上海微系统与信息技术研究所 Micro-energy system with high weight ratio energy density and method and application thereof
CN102456928A (en) * 2011-07-20 2012-05-16 宁波大学 Spray pyrolysis battery manufacturing method of double-layer film all-solid-state film lithium battery
CN104167562A (en) * 2014-07-14 2014-11-26 宁波大学 All-solid-state thin film battery based on electrostatic spray pyrolysis combined with flame spraying and preparation method
CN105655563A (en) * 2016-03-30 2016-06-08 吉首大学 Composite cathode material for lithium ion batteries and method for manufacturing composite cathode material
CN110085917A (en) * 2019-04-28 2019-08-02 天津瑞晟晖能科技有限公司 All-solid lithium-ion battery and preparation method thereof and electrical equipment
CN110233298A (en) * 2019-07-09 2019-09-13 珠海冠宇电池有限公司 A kind of preparation method of novel all-solid lithium-ion battery
CN111129571A (en) * 2019-12-20 2020-05-08 中国电子科技集团公司第十八研究所 All-solid-state thin film lithium battery with self-supporting structure and preparation method
CN113380971A (en) * 2021-06-07 2021-09-10 吉首大学 Composite negative electrode material of thin-film lithium ion battery and preparation method thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324586A (en) * 2011-06-24 2012-01-18 中国科学院上海微系统与信息技术研究所 Micro-energy system with high weight ratio energy density and method and application thereof
CN102324586B (en) * 2011-06-24 2015-04-22 中国科学院上海微系统与信息技术研究所 Micro-energy system with high weight ratio energy density and method and application thereof
CN102456928A (en) * 2011-07-20 2012-05-16 宁波大学 Spray pyrolysis battery manufacturing method of double-layer film all-solid-state film lithium battery
CN102456928B (en) * 2011-07-20 2014-10-08 宁波大学 Spray pyrolysis battery manufacturing method of double-layer film all-solid-state film lithium battery
CN102299383A (en) * 2011-07-20 2011-12-28 宁波大学 Mist pyrolysis preparation method of all-solid-state film lithium battery
CN104167562B (en) * 2014-07-14 2016-08-17 宁波大学 All-solid-state thin film battery based on electrostatic spray pyrolysis combined with flame spraying and preparation method
CN104167562A (en) * 2014-07-14 2014-11-26 宁波大学 All-solid-state thin film battery based on electrostatic spray pyrolysis combined with flame spraying and preparation method
CN105655563A (en) * 2016-03-30 2016-06-08 吉首大学 Composite cathode material for lithium ion batteries and method for manufacturing composite cathode material
CN105655563B (en) * 2016-03-30 2018-02-27 吉首大学 A kind of composite cathode material for lithium ion cell and preparation method thereof
CN110085917A (en) * 2019-04-28 2019-08-02 天津瑞晟晖能科技有限公司 All-solid lithium-ion battery and preparation method thereof and electrical equipment
CN110233298A (en) * 2019-07-09 2019-09-13 珠海冠宇电池有限公司 A kind of preparation method of novel all-solid lithium-ion battery
CN110233298B (en) * 2019-07-09 2021-10-26 珠海冠宇电池股份有限公司 Preparation method of novel all-solid-state lithium ion battery
CN111129571A (en) * 2019-12-20 2020-05-08 中国电子科技集团公司第十八研究所 All-solid-state thin film lithium battery with self-supporting structure and preparation method
CN113380971A (en) * 2021-06-07 2021-09-10 吉首大学 Composite negative electrode material of thin-film lithium ion battery and preparation method thereof

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Open date: 20100317