CN100367562C - Thin film lithium ion cell using silver selenide film as anode material and its preparing method - Google Patents
Thin film lithium ion cell using silver selenide film as anode material and its preparing method Download PDFInfo
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- CN100367562C CN100367562C CNB200610023111XA CN200610023111A CN100367562C CN 100367562 C CN100367562 C CN 100367562C CN B200610023111X A CNB200610023111X A CN B200610023111XA CN 200610023111 A CN200610023111 A CN 200610023111A CN 100367562 C CN100367562 C CN 100367562C
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- thin film
- lithium ion
- silver selenide
- silver
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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 technical field of electrochemistry, particularly to a lithium ion battery which adopts a silver selenide (Ag2Se) thin film as the material of an anode and a preparation method of the lithium ion battery. The thin film material is prepared via the method of pulsed laser deposition, the particle size of the silver selenide (Ag2Se) thin film is 200 to 800 nm, and a crystal structure belongs to an orthorhombic system. The invertible specific capacity of a thin film electrode is 505 mAh/g, and the thin film electrode has a certain characteristic of capacity maintenance 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. The thin film electrode material is suitable for thin film lithium ion batteries.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specially a kind of with silver selenide (Ag
2Se) film is film lithium ion battery of anode material and preparation method thereof.
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 silver selenide (Ag
2Se) film uses this anode material can improve the performance of film lithium ion battery.
Film lithium ion battery provided by the invention, its anode material adopts silver selenide (Ag
2Se) film, this film is made up of nano particle, and particle is of a size of 200-800nm, and distribution of particles is even.So far not about silver selenide (Ag
2Se) material is as the report of lithium ion battery anode material.
The present invention at first finds silver selenide (Ag
2Se) thin-film material has good electrochemical, and reversible specific capacity is 505mAh/g, is higher than the reversible capacity of material with carbon element 372mAh/g, circulates that reversible capacity still has 303mAh/g after 30 times, has Reversible Cycle preferably, therefore, can be used for lithium ion battery.
Preparation method of the present invention mainly is anode material silver selenide (Ag
2Se) preparation of film is to adopt reactive pulse laser method.Be about to the hybrid target of pulse laser ablation silver powder and selenium powder, make required film.Concrete steps are as follows: with silver powder and selenium powder ground and mixed, wherein the amount of substance of selenium powder be silver powder 0.5-1.5 doubly.After the grinding mixture is pressed into the sequin 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 30-45mm, and substrate temperature is 400-500 ℃.Take out reaction chamber in advance to 1-2Pa, feed argon gas,, and keep that pressure is 3-10Pa in the chamber by its flow of a noticeable degree.The 1064nm fundamental frequency that is produced by Nd:YAG obtains 355nm laser behind frequency tripling, laser beam is through inciding after the lens focus on the target, and energy density is about 1-3 joule/cm
2((Jcm
-2).Sedimentation time is required to determine by film thickness, is generally 0.3-1.0h.
All the other steps of the preparation method of film lithium ion battery of the present invention are identical with the preparation method of common film lithium ion battery.
The present invention adopts the hybrid target of pulse laser ablation silver powder and selenium powder directly to prepare the silver selenide film material.This material has good chemical stability.Do not see at present the report that adopts pulsed laser deposition to prepare silver selenide film.
Silver selenide (Ag among the present invention
2Se) structure is determined by x-ray diffractometer (Bruker D8 Advance).X-ray diffracting spectrum shows the silver selenide (Ag that is obtained by the pulse laser reactive deposition
2Se) film is an orthohormbic structure.Measure by ESEM (Philips XL30) and to show, the silver selenide (Ag that makes by the pulse laser reactive deposition
2Se) film is made up of nano particle, and diameter is in the 200-800 nanometer, and distribution of particles is even.
Silver selenide (Ag among the present invention
2Se) electrochemical property test of membrane electrode adopts the battery system of being made up of three electrodes, wherein silver selenide (Ag
2Se) film is 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.
Silver selenide (the Ag that makes on stainless steel substrates by the pulse laser reactive deposition processes among the present invention
2Se) membrane electrode has charge-discharge performance.Silver selenide (Ag
2Se) after membrane electrode and lithium metal were formed battery, its discharge platform appeared at 1.7V, 1.4V, 0.8V and 0.1V (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 300～500mAh/g.Above-mentioned performance shows, silver selenide (Ag
2Se) membrane electrode is a kind of novel anode material, can be widely used in film lithium ion battery.
Description of drawings
Fig. 1 is silver selenide (Ag
2Se) XRD spectra of film.The diffraction maximum of stainless steel substrate represented in asterisk among the figure, the crystal face indexes of this diffraction maximum of numeral in the bracket.
Embodiment
Embodiment 1
Adopt reactive pulsed laser deposition to prepare silver selenide (Ag among the present invention
2Se) film, color are black.During preparation, in the hybrid target, the amount of substance of selenium powder is 0.75 times of silver powder, 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 450 ℃, 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, on the hybrid target of laser beam through inciding silver powder 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 silver selenide (Ag of polycrystalline orthohormbic structure
2Se) (accompanying drawing 1).Show the silver selenide (Ag that makes by the pulse laser reactive deposition by stereoscan photograph mensuration
2Se) film is made up of the particle that diameter is about 400 nanometers, and distribution of particles is even, free of pinholes.
Silver selenide (Ag
2Se) the electrochemical property test result of membrane electrode is as follows:
1, silver selenide (Ag
2Se) 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 768mAh/g for the first time, and reversible capacity is 505mAh/g, and 30 capacity that circulate remain on 303mAh/g.
2, silver selenide (Ag
2Se) cyclic voltammetric of membrane electrode test is presented at for the first time in the discharge process, can observe five discharge potential peaks, respectively at 2.37V, 1.58V, 1.23V, 0.74 and 0.01V.After the circulation, the peak at 2.37V and 1.2V place disappears for the second time, and the peak at 0.74V place moves to 0.78V, and all the other peaks are constant.Three peaks can both have been observed in all charging processes respectively at 0.12V, 0.35V and 2.1V.
3, silver selenide (Ag
2Se) after the membrane electrode electrochemical reaction, X-ray diffraction has shown the existence of lithium silver alloy in the membrane electrode of electrochemical reaction.
4, silver selenide (Ag
2Se) the membrane electrode electrochemical reaction recharges in the process, and X-ray diffraction has shown the generation and the disappearance of the diffraction maximum of argent in the film.
Therefore, silver selenide (Ag
2Se) membrane electrode can be used as the anode material of lithium ion battery.
In the foregoing description, each parameter is changed in aforesaid scope, can obtain required silver selenide film, its chemical property parameter is similar or identical with embodiment 1 result, so do not enumerate one by one.Film all has good electrochemical as the film lithium ion battery of anode material thus.
Claims (2)
1. a film lithium ion battery is characterized in that anode adopts silver selenide film, and this film is a polycrystalline structure, is made up of nano particle, and particle is of a size of the 200-800 nanometer, and distribution of particles is even.
2. the preparation method of a film 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 silver selenide film, concrete steps are: with silver powder and selenium powder ground and mixed, wherein the amount of substance of selenium powder be silver powder 0.5-1.5 doubly.After the grinding mixture is pressed into the sequin 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 30-45mm, and substrate temperature is 400-500 ℃; Take out reaction chamber in advance to 1-2Pa, feed argon gas,, and keep that pressure is 3-10Pa in the chamber by its flow of a noticeable degree; Laser beam energy density is 1-3 joule/cm
2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610023111XA CN100367562C (en) | 2006-01-05 | 2006-01-05 | Thin film lithium ion cell using silver selenide film as anode material and its preparing method |
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|---|---|---|---|
| CNB200610023111XA CN100367562C (en) | 2006-01-05 | 2006-01-05 | Thin film lithium ion cell using silver selenide film as anode material and its preparing method |
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| CN1822426A CN1822426A (en) | 2006-08-23 |
| CN100367562C true CN100367562C (en) | 2008-02-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101875785B1 (en) * | 2016-11-17 | 2018-07-06 | 한국과학기술연구원 | Cathode material for rechargeable magnesium battery and its preparation method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115285946A (en) * | 2021-09-14 | 2022-11-04 | 许昌学院 | Ultrahigh-performance flexible silver selenide film with (201) dominant crystal face orientation and power generation device |
| CN114113275A (en) * | 2021-11-19 | 2022-03-01 | 冯大伟 | Research method of silver selenide in copper anode mud refining |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08250119A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN1262533A (en) * | 1999-01-28 | 2000-08-09 | 中国科学院物理研究所 | Secondary lithium battery |
-
2006
- 2006-01-05 CN CNB200610023111XA patent/CN100367562C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08250119A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN1262533A (en) * | 1999-01-28 | 2000-08-09 | 中国科学院物理研究所 | Secondary lithium battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101875785B1 (en) * | 2016-11-17 | 2018-07-06 | 한국과학기술연구원 | Cathode material for rechargeable magnesium battery and its preparation method |
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