CN101882677B - Lithium selenide-antimony selenide cathode material for lithium ion battery and preparation method - Google Patents
Lithium selenide-antimony selenide cathode material for lithium ion battery and preparation method Download PDFInfo
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- CN101882677B CN101882677B CN2009100508728A CN200910050872A CN101882677B CN 101882677 B CN101882677 B CN 101882677B CN 2009100508728 A CN2009100508728 A CN 2009100508728A CN 200910050872 A CN200910050872 A CN 200910050872A CN 101882677 B CN101882677 B CN 101882677B
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Abstract
The invention belongs to the technical field of electrochemistry, and in particular relates to a lithium selenide-antimony selenide (Li2Se-Sb3Se2) nano composite material for a cathode of a lithium ion battery and a preparation method. The material is a thin film and prepared by a reactive pulse laser precipitation method. An electrode prepared from the thin film has high charge-discharge cycle reversibility, the first specific capacity of 118mAh/g, the reversible specific capacity of 57mAh/g, and the capacity of 48mAh/g after the electrode is cycled for 40 times. The material provided by the invention has the advantages of high chemical stability, high specific capacity, simple preparation method, and suitability for the lithium ion battery.
Description
Technical field
The invention belongs to technical field of electrochemistry, relate to the cathode material that is used for lithium ion battery, be specifically related to a kind of lithium selenide-antimony triselenide cathode material that is used for lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is the vital power supply of notebook computer, camera, mobile phone and other Communication Equipment, and might be used for automobile and other vehicles as green energy resource.At present commercially available lithium ion battery mainly is made up of carbon-based anode material, liquid organic electrolyte and the transition metal oxide cathode material that contains lithium.In order further to improve the performance of lithium ion battery, people study, seek the better new material of electrode material performance than present use.In addition, along with the miniaturization of microelectronic component, the lithium ion battery that an urgent demand exploitation is complementary therewith, for example film lithium ion battery etc.
Summary of the invention
The object of the present invention is to provide cathode material of a kind of well behaved lithium ion battery and preparation method thereof.
The cathode material that is used for lithium ion battery provided by the present invention is a kind of lithium selenide-antimony triselenide nano-complex (Li with orthohormbic structure
2Se-Sb
2Se
3) material, this type of material has good electrochemical, can be used as the cathode material of high performance lithium ion battery.
Lithium selenide-antimony triselenide nano-complex (the Li that is used for cathode material for lithium ion battery provided by the present invention
2Se-Sb
2Se
3) be form of film, the thickness of its thin-film material is 0.2-1 μ m.
Lithium selenide-antimony triselenide nano-complex (the Li that is used for cathode material for lithium ion battery provided by the present invention
2Se-Sb
2Se
3) film adopts the preparation of reactive pulsed laser deposition.It comprises:
(1) compressing tablet after antimony powder and the selenium powder ground and mixed is processed the used target of pulsed laser deposition, wherein the weight ratio of antimony powder and selenium powder is 1 to 1 to 1 to 6, and the area on the surface 50% to 80% of target covers the high-purity lithium sheet.
(2) substrate adopts stainless steel substrates, platinized platinum or gold-plated monocrystalline silicon piece, and substrate temperature is 200-300 ℃, and the distance of substrate and target is 25-50mm.
(3) the 1064nm fundamental frequency that is produced by neodymium-doped yttrium pyralspite laser obtains the 355nm pulse laser behind frequency tripling, laser beam is through inciding after the lens focus on the above-mentioned target, and deposition obtains lithium selenide-antimony triselenide nano-complex (Li on substrate in argon gas atmosphere
2Se-Sb
2Se
3) film.
The depositing of thin film time is required to confirm by film thickness, was generally 0.2-1.0 hour.Film thickness can be measured by ESEM, and the weight of film obtains according to substrate weight difference before and after the electronic balance weighing.
Further, the lithium selenide-antimony triselenide nano-complex (Li that is used for cathode material for lithium ion battery provided by the present invention
2Se-Sb
2Se
3) the reactive pulsed laser deposition preparation condition of film is preferably: the weight ratio of antimony powder and selenium powder is 1 to 2 to 1 to 4 in the target, and the area of the surface coverage high-purity lithium sheet of target is 60% to 70%.
Among the present invention, lithium selenide-antimony triselenide nano-complex (Li
2Se-Cu
3Se
2) crystal structure of film is confirmed by transmission electron microscope(TEM), and unbodied Li
2The checkout equipment of Se component is plasma-induced coupling (ICP) atomic emission spectrum and secondary ion mass spectroscopy (SIMS).SEAD figure shows the lithium selenide-antimony triselenide nano-complex (Li that is made by method provided by the invention
2Se-Sb
2Se
3) there is the Sb of the polycrystalline orthohormbic structure of nanometer size in the film
2Se
3, and atomic emission spectrum has provided the ratio of three kinds of elements in the film, Li: Sb: Se=0.76: 1.00: 1.88, Li in the film is described
2Se and Sb
2Se
3Ratio approximately be 0.76: 1.The mensuration of secondary ion mass spectroscopy shows, the lithium selenide that on substrate, deposits-antimony triselenide nano-complex (Li
2Se-Sb
2Se
32) in the film, Li, Sb, three kinds of elements of Se successively decrease to the content distribution of inside from the surface of film, the constituent content in the substrate increases progressively.
Lithium selenide provided by the present invention-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) film can directly process the lithium ion cell film electrode.Electrochemical property test adopts the battery system of being made up of three electrodes, wherein, and lithium selenide-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) film is as work electrode, 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.
Among the present invention, the lithium selenide-antimony triselenide nano-complex (Li that on substrates such as stainless steel substrates, makes by the pulse laser reactive deposition processes
2Se-Sb
2Se
3) membrane electrode all has charge-discharge performance, the discharge platform of charging reaction for the first time appears at 2.5 and 3.2V (with respect to Li+/Li), and the platform of discharge process appears at 2.0V.For the second time discharge process with the first time discharge process compare, irreversible discharge capacity loss is 50%, but in circulation subsequently, the capacity of the 40 discharge is secondary more than 95%.At voltage range 1.7-3.5V and current density 5 μ A/cm
2The time, lithium selenide-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) membrane electrode specific capacity preceding 40 times the circulation in remain on 48~118mAh/g.
Above-mentioned performance shows, lithium selenide-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) be one type of novel cathode material, can be applicable to lithium ion battery.
For the ease of understanding, below will describe in detail of the present invention through concrete accompanying drawing and embodiment.What need particularly point out is; Instantiation and accompanying drawing only are in order to explain; Obviously those of ordinary skill in the art can explain according to this paper, within the scope of the invention the present invention is made various corrections and change, and these corrections and change are also included in the scope of the present invention.
Description of drawings
Fig. 1: lithium selenide-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) SEAD (SAED) image of film, marked the pairing Sb of diffraction ring among the figure
2Se
3Crystal face indexes.
Fig. 2: lithium selenide-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) secondary ion mass spectroscopy (SIMS) collection of illustrative plates of film, wherein, transverse axis is a sputtering time, corresponding distance from the film surface to inside, and the longitudinal axis is the secondary ion abundance, corresponding to constituent content.
Specific embodiments
Embodiment 1:
Adopt reactive pulsed laser deposition to prepare the lithium selenide-antimony triselenide nano-complex (Li that is used for cathode material for lithium ion battery of the present invention
2Se-Sb
2Se
3) film: antimony powder and selenium powder compressing tablet after 1 to 2 ground and mixed is processed the used target of pulsed laser deposition; Target surface coverage 50% high-purity lithium sheet; The distance of stainless steel substrate and target is 25mm; Substrate temperature is 200 ℃, and the 1064nm fundamental frequency that is produced by neodymium-doped yttrium pyralspite laser obtains the 355nm pulse laser behind frequency tripling, and laser beam is through inciding after the lens focus on the target; In argon gas atmosphere, on substrate, deposit 0.2 hour, can obtain lithium selenide of the present invention-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) film.
Embodiment 2:
Adopt reactive pulsed laser deposition to prepare the lithium selenide-antimony triselenide nano-complex (Li that is used for cathode material for lithium ion battery of the present invention
2Se-Sb
2Se
3) film: antimony powder and selenium powder compressing tablet after 1 to 6 ground and mixed is processed the used target of pulsed laser deposition; Target surface coverage 80% high-purity lithium sheet; The distance of stainless steel substrate and target is 50mm; Substrate temperature is 300 ℃, and the 1064nm fundamental frequency that is produced by neodymium-doped yttrium pyralspite laser obtains the 355nm pulse laser behind frequency tripling, and laser beam is through inciding after the lens focus on the target; In argon gas atmosphere, on substrate, deposit 1 hour, can obtain lithium selenide of the present invention-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) film.
Embodiment 3:
Adopt reactive pulsed laser deposition to prepare the lithium selenide-antimony triselenide nano-complex (Li that is used for cathode material for lithium ion battery of the present invention
2Se-Sb
2Se
3) film: antimony powder and selenium powder compressing tablet after 1 to 3 ground and mixed is processed the used target of pulsed laser deposition; Target surface coverage 66.7% pure metal lithium sheet; The distance of stainless steel substrate and target is 40mm; Substrate temperature is 250 ℃, and the 1064nm fundamental frequency that is produced by neodymium-doped yttrium pyralspite laser obtains the 355nm pulse laser behind frequency tripling, and laser beam is through inciding after the lens focus on the target; In argon gas atmosphere, on substrate, deposit 0.5 hour, can obtain lithium selenide of the present invention-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) film.
Embodiment 4:
Transmission electron microscope(TEM) is measured lithium selenide-antimony triselenide nano-complex (Li that the foregoing description makes
2Se-Sb
2Se
3) film, the film that shows deposition is the antimony triselenide nanocrystal of polycrystalline orthohormbic structure and the composite material (Li of amorphous selenizing lithium
2Se-Sb
2Se
3) (accompanying drawing 1).The mensuration of secondary ion mass spectroscopy shows, the lithium selenide that on stainless steel substrate, deposits-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) in the film, Li, Sb, three kinds of elements of Se successively decrease to the content distribution of inside from the surface of film, the constituent content in the substrate increases progressively.(accompanying drawing 2)
To the lithium selenide on the stainless steel substrate-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) the electrochemical property test result of membrane electrode is following:
Lithium selenide-antimony triselenide nano-complex (Li
2Se-Sb
2Se
3) membrane electrode can be at 5 μ A/cm
2Carry out charge and discharge cycles under the charge-discharge velocity.In voltage range 1.7-3.5V, discharge capacity can reach 118mAh/g for the first time, and reversible capacity is 57mAh/g, and circulation back capacity tends towards stability for the second time, and 40 capacity that circulate remain on more than the 48mAh/g.
Claims (11)
1. a cathode material that is used for lithium ion battery is characterized in that described cathode material is lithium selenide-antimony triselenide, and said lithium selenide-antimony triselenide is the nano complexes material of orthohormbic structure.
2. the cathode material that is used for lithium ion battery according to claim 1 is characterized in that lithium selenide-antimony triselenide is a form of film, and its thickness is 0.2-1 μ m.
3. the preparation method who is used for the cathode material of lithium ion battery according to claim 1 and 2 is characterized in that adopting reactive pulsed laser deposition, and it comprises:
(1) antimony powder and selenium powder mixing back compressing tablet are processed the target that pulsed laser deposition is used,
Wherein, the area on the surface 50% to 80% of target covers the high-purity lithium sheet;
(2) adopting stainless steel substrates, platinized platinum or gold-plated monocrystalline silicon piece is substrate;
(3) the 1064nm fundamental frequency that is produced by laser obtains pulse laser behind frequency tripling, laser beam is through inciding after the lens focus on the above-mentioned target, and deposition obtains lithium selenide-antimony triselenide nano-complex film on substrate.
4. preparation method according to claim 3 is characterized in that the weight ratio of antimony powder and selenium powder is 1: 1~6 in the said target.
5. preparation method according to claim 4 is characterized in that the weight ratio of antimony powder and selenium powder is 1: 3~6 in the said target.
6. preparation method according to claim 3 is characterized in that the area on the surface 60%~70% of said target covers the high-purity lithium sheet.
7. preparation method according to claim 3 is characterized in that substrate temperature is 200-300 ℃.
8. preparation method according to claim 3, the distance that it is characterized in that substrate and target is 25-50mm.
9. preparation method according to claim 3 is characterized in that described laser is a neodymium-doped yttrium pyralspite laser, and pulse laser wavelength is 355nm.
10. preparation method according to claim 4 is characterized in that pulsed laser deposition is in argon gas atmosphere, to carry out.
11. preparation method according to claim 3 is characterized in that sedimentation time is 0.2-1.0 hour on substrate.
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CN104022285A (en) * | 2014-06-24 | 2014-09-03 | 武汉理工大学 | SnO2@polymer coaxial heterogeneous nano rod array structural material as well as preparation method and application thereof |
CN105185966B (en) * | 2015-10-08 | 2017-12-01 | 合肥国轩高科动力能源有限公司 | Heat sink material for lithium-ion-power cell |
CN106159239B (en) * | 2016-08-30 | 2019-06-25 | 安徽师范大学 | A kind of preparation method of manganese sulfide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery |
CN108172744B (en) * | 2017-12-27 | 2020-09-15 | 肇庆市华师大光电产业研究院 | Sb for lithium-sulfur battery diaphragm2Se3Method for preparing composite material |
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---|---|---|---|---|
JP2004047449A (en) * | 2002-05-17 | 2004-02-12 | Mitsubishi Chemicals Corp | Manufacturing method for surface modified lithium nickel composite oxide, positive electrode active material using surface modified lithium nickel composite oxide, positive electrode material, and lithium secondary battery |
WO2007055007A1 (en) * | 2005-11-10 | 2007-05-18 | Pionics Co., Ltd. | Particle of negative electrode active material for lithium secondary battery, negative electrode making use of the same and process for producing them |
CN100428536C (en) * | 2007-05-10 | 2008-10-22 | 复旦大学 | Sb2Se3 anode film material for lithium ion cell and its preparing method |
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JP2004047449A (en) * | 2002-05-17 | 2004-02-12 | Mitsubishi Chemicals Corp | Manufacturing method for surface modified lithium nickel composite oxide, positive electrode active material using surface modified lithium nickel composite oxide, positive electrode material, and lithium secondary battery |
WO2007055007A1 (en) * | 2005-11-10 | 2007-05-18 | Pionics Co., Ltd. | Particle of negative electrode active material for lithium secondary battery, negative electrode making use of the same and process for producing them |
CN100428536C (en) * | 2007-05-10 | 2008-10-22 | 复旦大学 | Sb2Se3 anode film material for lithium ion cell and its preparing method |
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