CN100341172C - Film lithium ion battery using stannous selenide film as anode material and its preparation method - Google Patents
Film lithium ion battery using stannous selenide film as anode material and its preparation method Download PDFInfo
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- CN100341172C CN100341172C CNB2005100296980A CN200510029698A CN100341172C CN 100341172 C CN100341172 C CN 100341172C CN B2005100296980 A CNB2005100296980 A CN B2005100296980A CN 200510029698 A CN200510029698 A CN 200510029698A CN 100341172 C CN100341172 C CN 100341172C
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- film
- lithium ion
- thin film
- ion battery
- stannous selenide
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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 belongs to the field of electrochemical techniques, particularly to a lithium ion battery of which the anode material adopts a nano size stannous selenide (SnSe) thin film and a preparation method thereof. The thin film material is prepared via a pulsed laser deposition method, the particle size of the stannous selenide (SnSe) thin film is 15 to 50 nm, and crystal structure belongs to an orthorhombic system. The specific capacity of a thin film electrode is 681mAh/g, and the thin film electrode has good stability in the process of repeated charge and discharge. The thin film electrode material has the advantages of good chemical stability, high specific capacity and simple preparation method, and the thin film electrode material is suitable for thin film lithium ion batteries.
Description
Technical field
The invention belongs to technical field of electrochemistry, being specifically related to a kind of is the film lithium ion battery and preparation method thereof of anode material with the stannous selenide film.
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 film lithium ion battery that charges and discharge is compared with other chemical cell, and its specific capacity is big, and it is long to discharge and recharge the life-span, and security performance is good.In order to make solid-State Thin Film Li-Ion Batteries have good performance, key technology is to seek the specific capacity height, having extended cycle life anode that irreversible capacity loss is few and cathode material.
Summary of the invention
The object of the present invention is to provide a kind of new film lithium ion battery, its anode material adopts stannous selenide (SnSe) film, uses this anode material can improve the performance of film lithium ion battery greatly.
Film lithium ion battery provided by the invention, its anode material adopts stannous selenide (SnSe) film, and this film is made up of nano particle, and particle is of a size of the 15-50 nanometer, and distribution of particles is even.So far not about the report of any metal selenide material as lithium ion battery anode material.
The present invention finds that at first stannous selenide (SnSe) thin-film material has good electrochemical, reversible specific capacity is 583mAh/g, the reversible capacity that is higher than tinbase composite oxides 462mAh/g, the reversible capacity loss is 30% after 40 times and circulate, has Reversible Cycle preferably, therefore, can be used as lithium ion battery.
Preparation method of the present invention mainly is the preparation of anode material stannous selenide (SnSe) film, is to adopt reactive pulsed laser deposition.Be about to the hybrid target that pulse laser ablation is made up of glass putty and selenium powder, make required film.Concrete steps are as follows: with glass putty and selenium powder ground and mixed, wherein the amount of substance of selenium powder be glass putty 1.3-1.6 doubly; After the grinding mixture is pressed into the disk that diameter is 10-15mm, as the used target of pulsed laser deposition, adopts stainless steel substrates as substrate, the distance of substrate and target is 35-42mm, and substrate temperature is 400-450 ℃; Take out reaction chamber in advance to 1-2Pa, feed argon gas,, and keep that pressure is 2-8Pa in the chamber by its flow of a noticeable degree; The 1064nm fundamental frequency that is produced by the Nd:YAG laser obtains 355nm laser behind frequency tripling, laser beam is through inciding after the lens focus on the target, and energy density is about 1.5-2.5Jcm
-2Sedimentation time is required to determine by film thickness, is generally 0.4-0.8h.
All the other steps of the preparation method of film lithium ion battery of the present invention are identical with common preparation method.
The present invention adopts the hybrid target of pulse laser ablation glass putty and selenium powder directly to prepare the stannous selenide film material.This material has good chemical stability.All adopt commodity stannous selenide (SnSe) in the present report for preparing stannous selenide film about pulsed laser deposition, do not see the report of direct employing glass putty and selenium powder hybrid target.
Stannous selenide among the present invention (SnSe) structure is determined by x-ray diffractometer (Bruker D8 Advance).X-ray diffracting spectrum shows that stannous selenide (SnSe) film that is obtained by the pulse laser reactive deposition is an orthohormbic structure, and has a spot of metallic tin to exist.Show that by ESEM (Philips XL30) mensuration be made up of nano particle stannous selenide (SnSe) film that the pulse laser reactive deposition makes, diameter is in the 15-50 nanometer, and distribution of particles is even.The composition of film is characterized by x-ray photoelectron power spectrum (XPS).The result shows and consists of tin and selenium that wherein tin has two kinds of valence states, integration Sn3d
5/2With Se 3p
3/2The area of XPS spectrum can be estimated the Sn that consists of of film
0.1(SnSe)
0.9
The electrochemical property test of stannous selenide among the present invention (SnSe) membrane electrode adopts the battery system of being made up of three electrodes, and wherein stannous selenide (SnSe) film is used as work electrode, and the high purity lithium sheet is used separately as to electrode and reference electrode.Electrolyte is 1M LiPF
6+ EC+DMC (V/V=1/1).Battery is assemblied in the drying box of applying argon gas and carries out.The experiment that discharges and recharges of battery is carried out on blue electricity (Land) battery test system.
The stannous selenide that is made on stainless steel substrates by the pulse laser reactive deposition processes among the present invention (SnSe) membrane electrode has charge-discharge performance.After stannous selenide (SnSe) membrane electrode and lithium metal were formed battery, its discharge platform appeared at 1.30V and 0.28V (with respect to Li/Li
+).At voltage range 2.50-0.01V and current density 10 μ A/cm
2The time, this membrane electrode specific capacity remains on 400～681mAh/g.Above-mentioned performance shows that the stannous selenide film electrode is a kind of novel anode material, can be widely used in film lithium ion battery.
Embodiment
Embodiment
The present invention adopts reactive pulsed laser deposition to prepare stannous selenide (SnSe) film, and color is a grey.During preparation, in the hybrid target, the amount of substance of selenium powder is 1.5 times of glass putty, and the diameter of target is 13mm, and adopting the stainless steel of cleaning is substrate, and the distance of substrate and target is 38mm, and substrate temperature is 400 ℃, takes out reaction chamber in advance to 2Pa, feeds argon gas, keeps air pressure 5Pa.The fundamental frequency that is produced by the Nd:YAG laser produces the 355nm pulse laser through frequency tripling, and the repetition rate of laser is 10Hz, and pulse duration is 10ns, on the hybrid target of laser beam through inciding glass putty and selenium powder after the lens focus.Energy density is 2Jcm
-2, sedimentation time is 0.5 hour.
Show that by X-ray diffraction mensuration the film of deposition is the stannous selenide (SnSe) and a spot of metallic tin of polycrystalline orthohormbic structure.The x-ray photoelectron power spectrum has shown the peak of Sn and Se, and the composition of film is estimated as Sn
0.1(SnSe)
0.9Show that by stereoscan photograph mensuration be made up of the particle that diameter is about 20 nanometers stannous selenide (SnSe) film that the pulse laser reactive deposition makes, distribution of particles is even, free of pinholes.
The electrochemical property test result of stannous selenide (SnSe) membrane electrode is as follows:
1, stannous selenide (SnSe) membrane electrode can be at 10 μ A/cm
2Carry out charge and discharge cycles under the charge-discharge velocity.In voltage range 0.01-2.5V, discharge capacity can reach 681mAh/g for the first time, and 40 capacity attenuations that circulate are less, and the reversible capacity loss is about 44%.Efficiency for charge-discharge is 113%.
2, the cyclic voltammetric of stannous selenide (SnSe) membrane electrode test shows, in first time discharge process, can observe four discharge potential peaks, respectively at 1.2V, 0.73V, 0.57V and 0.23V.After the circulation, the peak at 1.2V place moves to 1.0V for the second time, and the peak at 0.73V place disappears, and the peak at 0.57V place moves to 0.50V, and the peak at 0.23V place is constant.Four peaks can both have been observed in all charging processes respectively at 0.50V, 0.65V, 0.80V and 1.9V.
3, after stannous selenide (SnSe) the membrane electrode electrochemical reaction, the test of x-ray photoelectron power spectrum shows the existence of lithium-tin alloy in the membrane electrode of electrochemical reaction.
4, after stannous selenide (SnSe) membrane electrode electrochemical reaction recharged, X-ray diffraction and x-ray photoelectron power spectrum test disclosing solution film surface had generated stannous selenide (SnSe), and have part tin to exist.
Therefore, nanometer stannous selenide (SnSe) membrane electrode can be used as the anode material of lithium ion battery.
Claims (2)
1, a kind of film lithium ion battery is characterized in that anode adopts stannous selenide film, and this film is a polycrystalline structure, is made up of nano particle, and particle is of a size of the 15-50 nanometer, and distribution of particles is even.
2, a kind of preparation method of lithium ion battery as claimed in claim 1, the pulse laser reactive deposition processes is adopted in the preparation that it is characterized in that the anode material stannous selenide film, concrete steps are: with glass putty and selenium powder ground and mixed, wherein the amount of substance of selenium powder be glass putty 1.3-1.6 doubly; After the grinding mixture is pressed into the disk that diameter is 10-15mm, as the used target of pulsed laser deposition, adopts stainless steel substrates as substrate, the distance of substrate and target is 35-42mm, and substrate temperature is 400-450 ℃; Take out reaction chamber in advance to 1-2Pa, feed argon gas,, and keep that pressure is 2-8Pa in the chamber by its flow of a noticeable degree; The 1064nm fundamental frequency that is produced by the Nd:YAG laser obtains 355nm laser behind frequency tripling, laser beam is through inciding after the lens focus on the target, and energy density is 1.5-2.5Jcm
-2
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| CNB2005100296980A CN100341172C (en) | 2005-09-15 | 2005-09-15 | Film lithium ion battery using stannous selenide film as anode material and its preparation method |
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| CNB2005100296980A CN100341172C (en) | 2005-09-15 | 2005-09-15 | Film lithium ion battery using stannous selenide film as anode material and its preparation method |
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| CN100341172C true CN100341172C (en) | 2007-10-03 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391035C (en) * | 2006-08-03 | 2008-05-28 | 复旦大学 | Thin film lithium battery using diselenid nickel thin film as cathode material and its preparation method |
| CN100395908C (en) * | 2006-08-03 | 2008-06-18 | 复旦大学 | Negative pole material for lithium battery and producing method thereof |
| CN100423330C (en) * | 2006-10-26 | 2008-10-01 | 复旦大学 | Ferrous selenide cathode material for lithium cell and preparing process thereof |
| CN101237040B (en) * | 2008-01-10 | 2011-03-23 | 复旦大学 | A Se indium copper anode material for lithium ion battery and its making method |
| CN105810922B (en) * | 2016-06-06 | 2019-04-05 | 中南大学 | A kind of lithium ion/sodium-ion battery composite negative pole material and preparation method thereof |
| CN110117769A (en) * | 2019-05-20 | 2019-08-13 | 陕西科技大学 | A kind of preparation method of selenizing tin thin film |
| CN114645257A (en) * | 2022-03-15 | 2022-06-21 | 北京大学深圳研究生院 | Stannous selenide p-type semiconductor film and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1021913A (en) * | 1996-07-05 | 1998-01-23 | Hitachi Ltd | Battery chargeable and dischargeable reversibly for plural times |
| EP1039568A1 (en) * | 1998-09-18 | 2000-09-27 | Canon Kabushiki Kaisha | Electrode material for negative pole of lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure, and method for manufacturing said electrode structure and said lithium secondary cell |
| CN1327275A (en) * | 2000-06-06 | 2001-12-19 | 中国科学院物理研究所 | Secondary lithium cell having negative pole of carbon with deposited nanometer alloy on its surface |
| CN1505188A (en) * | 2002-11-30 | 2004-06-16 | 中南大学 | Composite nano metallic negative electrode material for lithium ion battery and method for making same |
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- 2005-09-15 CN CNB2005100296980A patent/CN100341172C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1021913A (en) * | 1996-07-05 | 1998-01-23 | Hitachi Ltd | Battery chargeable and dischargeable reversibly for plural times |
| EP1039568A1 (en) * | 1998-09-18 | 2000-09-27 | Canon Kabushiki Kaisha | Electrode material for negative pole of lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure, and method for manufacturing said electrode structure and said lithium secondary cell |
| CN1327275A (en) * | 2000-06-06 | 2001-12-19 | 中国科学院物理研究所 | Secondary lithium cell having negative pole of carbon with deposited nanometer alloy on its surface |
| CN1505188A (en) * | 2002-11-30 | 2004-06-16 | 中南大学 | Composite nano metallic negative electrode material for lithium ion battery and method for making same |
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