CN100391034C - Lithium battery electrode material Li2S/Co nanometer compound film and its preparation method - Google Patents
Lithium battery electrode material Li2S/Co nanometer compound film and its preparation method Download PDFInfo
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- CN100391034C CN100391034C CNB2006100232574A CN200610023257A CN100391034C CN 100391034 C CN100391034 C CN 100391034C CN B2006100232574 A CNB2006100232574 A CN B2006100232574A CN 200610023257 A CN200610023257 A CN 200610023257A CN 100391034 C CN100391034 C CN 100391034C
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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 an electrode active material for a lithium ion battery and a preparation method of the electrode active material. The material is a nanocomposite film formed from Li2 S and a transition metal element Co, and can be prepared and obtained by a pulsed laser deposition method. The grain diameter of a Li2 S/Co nanometer compound is smaller than 50 nm, and the specific capacity of a film electrode changes within the range of different 400 to 650 mAh/g along with the difference of the transition metal element Co. The film electrode active material has the advantages of excellent stability in the repeated process of charge and discharge, high specific capacity, good cycle performance and simple preparation method; the present invention is suitable for the membrane lithium ion battery.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of with Li
2S/Co nano compound film and preparation method thereof.
Background technology
Lithium ion battery is because advantages such as its high working voltage, high-energy-density receive people's very big concern.At present lithium ion battery is on extensive use and the electronic equipments such as mobile phone, notebook computer, Digital Video, camera, and may be used for automobile and other vehicles as green energy resource.At present, the cathode material that lithium ion battery is commonly used mainly contains LiCoO
2, LiNiO
2And LiMn
2O
4Deng.Though this class cathode material has better electrochemical performance, be subjected to that price height, specific capacity are lower, the lower problem of restriction, particularly specific capacity of factor such as preparation and purge process complexity, seriously limited its better development.Although people have carried out a large amount of research, but still difficulty makes its specific capacity surpass 180mAh/g.
In the research field of lithium ion battery, sulphur has a high theoretical capacity (1672mAh/g) as a kind of, and the material of low price cost generally comes into one's own.But sulphur simple substance is because its born insulating properties, and product factor such as easily decomposes in electrolyte, is difficult to directly be used as electrode material.Recently king woods of a specified duration etc. (Jiulin Wang.et al.Adv.Funct.Mater.2003,13, No 6, June) sulfur granules embedded in the conductive organic substance, successfully obtained to have the lithium-sulfur cell that good circulation performance and capacity reach 600mAh/g.(Nobuya Machida.et al.Solid State Ionics.175 such as Nobuya Machida, 247-250 (2004)) method by ball milling is mixed and made into the powder electrode material with sulphur simple substance and metallic copper and a spot of acetylene black, and the capacity that also made surpasses the lithium-sulfur cell of 980mAh/g.And M.N.Obrovac etc. (M.N.Obrovac.et al.Electrochem.Solid-State Lett.5 (4) A70-A73 (2002)) once attempted using Li
2S and Fe ball milling mix, and discharge and recharge then, but its reversible capacity only is about 170mAh/g, and decay are very fast.Up to the present, research report Li is not also arranged
2The S/Co mixture is as the electrode material of lithium ion battery.
The present invention proposes to use Li
2The nanoscale mixture of S and metal Co is made thin-film electrode material by pulsed laser deposition, provides a kind of and not only contains the electro-chemical activity lithium, and have the high-capacity electrode material of good charge-discharge performance.Cardinal principle is: adopt pulsed laser deposition technique to make Li
2S and Co high degree of dispersion are mixed, and obtain the nano-complex film on substrate.Wherein the film particle diameter is preferably in below the 20nm less than 50nm, can reduce the electrochemistry internal resistance of reaction system so greatly, improves the utilance of active material in the reaction system, finally improves the electrochemistry capacitance and the cycle performance of system.
Summary of the invention
The object of the present invention is to provide a kind of charge-discharge performance good, utmost point material of the lithium ion battery that electrochemistry capacitance is high and preparation method thereof.
The electrode active material of the lithium ion battery that the present invention proposes.Be by Li
2S evenly mixes the nano compound film that the back adopts pulsed laser deposition to be prepared from transition metal Co, wherein, and Li
2The mol ratio of S and transition metal Co is 1: x, 2＞x＞0.5.
In the above-mentioned electrode material, the particle diameter of Co preferably reaches below the 20nm less than 50nm; Li
2The particle diameter of S is less than 50nm, and representative value is less than 20nm.
The invention has the advantages that and directly utilize Li
2The nano-mixture of S and transition metal Co forms the electrode material with electro-chemical activity, and this material not only can provide the lithium source when discharging and recharging, and has favorable charge-discharge cycle performance and very high specific capacity (reaching 400-650mAh/g); The preparation process of mixture does not need the pyroreaction or the high-energy ball milling process of traditional electrode material, only needs to take certain method to make compound reach the following mixing of nanoscale (50nm) and gets final product.Therefore has the remarkable advantage that preparation process is simple, chemical property is good.
Narrate the preparation process of electrode active material among the present invention below:
Pulsed laser deposition prepares thin-film material---and with mol ratio is 1: the Li of x (2＞x＞0.5)
2S be pressed into target material after transition metal Co evenly mixes, the method by pulsed laser deposition is prepared into composite Nano mixture electrode film material.Preparation condition is: substrate is selected stainless steel substrates for use, and the distance of substrate and target is 35-45mm; Deposition atmosphere is an argon gas, keeps pressure at 8-10Pa; Depositing temperature is a room temperature; Laser is the 355nm pulse laser that is produced through frequency tripling by the fundamental frequency that the Nd:YAG laser produces, pulse frequency 10Hz, and pulse duration 10ns, energy density is 1.5-2.5J/cm
-2Sedimentation time 0.5-1h.
Description of drawings
Fig. 1 is Li
2S/Co nano compound film charging and discharging curve.
Embodiment
Embodiment 1
With mol ratio is 1: 1 chemical pure Li
2S fully mixes with the Co powder; Then the mixture powder is pressed into the target material of pulsed laser deposition, is prepared into composite Nano mixture electrode film material by pulsed laser deposition.Preparation condition: substrate is a stainless steel substrates, and the distance of substrate and target is 40mm; Deposition process is carried out in argon gas, keeps pressure at 10Pa; Depositing temperature is a room temperature; Optical maser wavelength is 355nm, pulse frequency 10Hz, and pulse duration 10ns, energy density is 2J/cm
-2Sedimentation time is 0.5 hour.
Show that by SEM grain diameter is about about 20nm in the deposit film.The film that shows deposition is Li
2The S/Co nano complexes material constitutes.Show that by TEM electronic diffraction mensuration deposit film is Li
2S/Co nano-mixture, wherein Li
2S is a face-centred cubic structure, and Co is a hexagonal structure, wherein contains a spot of CoS
xCompound, this is inevitable in the deposition process.With this film as work electrode, with the high purity lithium sheet as electrode is assembled into simulated battery.Wherein electrolyte is 1MLiPF
6+ EC+DMC (volume ratio of EC and DMC is 1/1), battery are assemblied in the drying box of applying argon gas and carry out.Discharging and recharging on the Land battery test system of battery carried out.The mixture film electrode has shown good electrochemical.The battery discharge platform is about 1.5V, and capacity reaches (accompanying drawing) about 600mAh/g.
For Li
2Have the related parameter condition in aforementioned range, to change in the S/Co nano compound film preparation process, all can obtain with embodiment 1 in the Li of identical or close chemical property
2The S/Co film all can be used as the electrode material of lithium ion battery, does not enumerate one by one here.
Claims (2)
1. an electrode active material that is used for lithium ion battery is characterized in that by mol ratio be 1: x, the Li of 2＞x＞0.5
2After S and transition metal Co evenly mix, the composite Nano mixture film that adopts pulsed laser deposition to be prepared from, Li in the film
2The S particle diameter is less than 50nm, and the Co particle diameter is less than 50nm.
2. a preparation method who is used for the electrode active material of lithium ion battery as claimed in claim 1 is characterized in that with mol ratio be 1: x, the Li of 2＞x＞0.5
2S be pressed into target material after Co evenly mixes, the method by pulsed laser deposition is prepared into composite Nano mixture electrode film material; Its preparation condition is: substrate adopts stainless steel substrates, and the distance of substrate and target is 35-45mm; Deposition atmosphere is an argon gas, keeps pressure 8-10Pa; Depositing temperature is a room temperature; Laser energy density is 1.5-2.5J/cm
-2, sedimentation time is 0.5-1 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100232574A CN100391034C (en) | 2006-01-12 | 2006-01-12 | Lithium battery electrode material Li2S/Co nanometer compound film and its preparation method |
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|---|---|---|---|
| CNB2006100232574A CN100391034C (en) | 2006-01-12 | 2006-01-12 | Lithium battery electrode material Li2S/Co nanometer compound film and its preparation method |
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| CN1794495A CN1794495A (en) | 2006-06-28 |
| CN100391034C true CN100391034C (en) | 2008-05-28 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101997145B (en) * | 2009-08-25 | 2013-06-05 | 苏州宝时得电动工具有限公司 | Lithium sulfur battery |
| CN103151554B (en) * | 2009-08-25 | 2016-08-03 | 苏州宝时得电动工具有限公司 | Lithium-sulfur cell |
| CN101794877A (en) * | 2010-03-25 | 2010-08-04 | 复旦大学 | Copper fluoride-selenium nanometer composite cathode material for lithium ion battery and preparation method thereof |
| WO2013057023A1 (en) | 2011-10-17 | 2013-04-25 | Volkswagen Ag | Active material for batteries |
| FI126759B (en) | 2014-12-05 | 2017-05-15 | Picodeon Ltd Oy | Method for making thin films using short laser pulses and composite target materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1134080C (en) * | 1999-04-26 | 2004-01-07 | 松下电器产业株式会社 | Anode, its manufacturing method and lithium battery using said anode |
| CN1189962C (en) * | 2002-07-30 | 2005-02-16 | 复旦大学 | Nano anode material for Li-ion battery and its preparing process |
| CN1191655C (en) * | 2003-03-06 | 2005-03-02 | 复旦大学 | Method for preparing lithium ion solid electrolyte film with high deposition rate |
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2006
- 2006-01-12 CN CNB2006100232574A patent/CN100391034C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1134080C (en) * | 1999-04-26 | 2004-01-07 | 松下电器产业株式会社 | Anode, its manufacturing method and lithium battery using said anode |
| CN1189962C (en) * | 2002-07-30 | 2005-02-16 | 复旦大学 | Nano anode material for Li-ion battery and its preparing process |
| CN1191655C (en) * | 2003-03-06 | 2005-03-02 | 复旦大学 | Method for preparing lithium ion solid electrolyte film with high deposition rate |
Non-Patent Citations (2)
| Title |
|---|
| Electrochemically active lithia/metalandlithiumsulfide/metalcomposites. M.N.Obrovac,etc.Electrochemical and Solid-state letters,Vol.5 No.4. 2002 |
| Electrochemically active lithia/metalandlithiumsulfide/metalcomposites. M.N.Obrovac,etc.Electrochemical and Solid-state letters,Vol.5 No.4. 2002 * |
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