CN1447463A - Nitride thin film of transition metal capable of being as anode material of batteries its preparation method - Google Patents
Nitride thin film of transition metal capable of being as anode material of batteries its preparation method Download PDFInfo
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- CN1447463A CN1447463A CN03115306A CN03115306A CN1447463A CN 1447463 A CN1447463 A CN 1447463A CN 03115306 A CN03115306 A CN 03115306A CN 03115306 A CN03115306 A CN 03115306A CN 1447463 A CN1447463 A CN 1447463A
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- film
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- transition metal
- membrane electrode
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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 invention discloses the new typed nitride Co3N, Fe3N and Ni3N thin films to be used as anode materials of lithium ion batteries. Under nitrogen atmosphere, the thin films can be obtained through the reactive deposition of pulse lasers. The particle sizes are 20-500 nm presenting the polycrystal cube structure. The discharge platforms are appeared at about 0.64V, 0.70V and 0.92V when the battery consists of the said thin films as the electrode and metal lithium. Excellent reversibility of charging and discharging cycles is maintained at 3.50-0.01 V and current density 7 micron A/cm2. The specific capacities are at about 420, 440 and 420 mAh/g. after 80 times of cycle, the loss of reversible capacity is less than about 5%.
Description
Technical field
The present invention relates to a kind of lithium ion battery anode material and preparation method thereof, particularly a kind of transition metal nitride thin-film 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.Characteristics such as because all solid state lithium-ion film cell that charges and discharge compares with other chemical cell, it is big to have specific capacity, and it is long to discharge and recharge the life-span, and security performance is good become the object that the electrochemical field primary study is developed.In this battery, the performance of electrode material will directly have influence on the performance of battery.In order to improve the performance of solid-State Thin Film Li-Ion Batteries, key is to seek the specific capacity height, has extended cycle life the electrode material that irreversible capacity loss is few.At present, the electrode material used of lithium ion battery has Sn
3N
2, and the transition metal nitride Li that contains lithium
2.6Co
0.4N, Li
2.7Fe
0.3N etc., this battery electrode material, specific capacity and Reversible Cycle etc. are still not ideal enough.Before the present invention, find no report about the preparation and the electrochemical properties test thereof of the transition metal nitride of no lithium.
Summary of the invention
It is big to the objective of the invention is to propose a kind of new specific capacity, Reversible Cycle is good, long service life can be used as transition metal nitride film of lithium ion battery anode material and preparation method thereof.
The transition metal nitride film as lithium ion battery anode material that the present invention proposes is a kind of M that is generated by reactive pulsed laser deposition
3N, M is a kind of of following metal Co, Fe, Ni here, and this thin-film material is the polycrystal cubic structure, be that 20 nanometers are formed to the nano particle of 50 nanometers by diameter, and distribution of particles is even, and the content of N is 20-30%.
The present invention finds that these thin-film materials have good electrochemical, and specific capacity is greater than 400mAh/g, and the reversible capacity loss has extraordinary Reversible Cycle, than the Sn of present use in solid-State Thin Film Li-Ion Batteries only less than 5% after 80 times and circulate
3N
2Demonstrate bigger superiority Deng anode material, can be applied to lithium ion battery.
The above-mentioned M that the present invention proposes
3The N film is to prepare by reactive pulsed laser deposition.Concrete steps are: through inciding after the lens focus on the metal M target, general M purity is greater than 99.9 ° by the laser beam of ultraviolet wavelength.The free radical that N atom and ion are arranged in the reative cell, they can be fed the nitrogen of reative cell by a noticeable degree, and through the high voltage direct current discharge generation, the pressure of control gaseous is 10～30Pa by the pair of planar discharge electrode; M
3N is deposited on and forms film on the substrate, and metal M is a kind of of Co (cobalt), Ni (nickel), Fe (iron) here, and substrate temperature is 50 ℃-200 ℃, and sedimentation time is 1-3 hour.
Among the present invention, substrate can adopt stainless steel substrates, be coated with transparent conducting glass of tin indium oxide (ITO) or glass.
Among the present invention, be deposited on the Co on the sheet glass
3N, Fe
3N, Ni
3The N film has shown different colors.Co
3N is colourless, transparent.Fe
3N is a buff, Ni
3N is light blue.
Co among the present invention
3N, Fe
3N, Ni
3The N membrane structure is determined by x-ray diffractometer (Rigata/Max-C).X-ray diffracting spectrum shows that the film that is obtained by the pulse laser reactive deposition is the polycrystal cubic structure.Fe
3Contain a spot of Fe in the N film
4N, Ni
3Contain the NiN film in the N film.Show that by ESEM mensuration the film that is made by the pulse laser reactive deposition is nano particle and forms, their diameter is respectively about 20 nanometers and 50 nanometers, and distribution of particles is even.The composition of film is characterized by x-ray photoelectron power spectrum (XPS).XPS result has shown and has consisted of nitrogen and transition metal, imitates positive divisor in conjunction with the sensitivity of element, and with integration Co, the area of Fe and Ni and N1s XPS spectrum can estimate that the content of N is about 20-30%.
Co among the present invention
3N, Fe
3N, Ni
3The electrochemical property test of N membrane electrode adopts the battery system of being made up of three electrodes, wherein Co
3N, Fe
3N, Ni
3The N 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 test that discharges and recharges of battery is carried out on blue electricity (Land) battery test system.
The Co that makes on stainless steel substrates by the pulse laser reactive deposition processes among the present invention
3N, Fe
3N, Ni
3The N membrane electrode all has charge-discharge performance.Co
3The N membrane electrode, behind lithium metal composition battery, its discharge platform appears at about 0.64V (with respect to Li/Li
+).At voltage range 3.50-0.01V and current density 7 μ A/cm
2The time, this membrane electrode specific capacity remains on about 420mAh/g.Fe
3The N membrane electrode, its discharge platform appears at about 0.70V (with respect to Li/Li
+).At voltage range 3.50-0.01V and current density 7 μ A/cm
2The time, this membrane electrode specific capacity remains on 440mAh/g.Ni
3N membrane electrode discharge platform appears at about 0.92V (with respect to Li/Li
+).At voltage range 3.50-0.01V and current density 7 μ A/cm
2The time, specific capacity remains on 420mAh/g.It is less to descend through the specific capacity that circulates more than 80 times, and capacitance loss shows that less than about 5% its cycle performance is good.Above-mentioned performance shows the Co that makes on stainless steel substrates
3N, Fe
3N, Ni
3The N membrane electrode is a kind of novel anode material, might be applied to film lithium ion battery.
Among the present invention, be coated with the Co that makes on transparent conducting glass of tin indium oxide (ITO) or the vierics
3N, Fe
3N, Ni
3The N membrane electrode has and is similar to above-mentioned characteristic.
Embodiment
Embodiment 1
Adopt reactive pulsed laser deposition respectively on stainless steel substrates, transparent conducting glass (ITO) on glass or that be coated with tin indium oxide goes up preparation Co
3The N film.The 355nm pulse laser is produced through frequency tripling by the fundamental frequency that the Nd:YAG laser produces, and laser beam is through inciding after the lens focus on the metallic cobalt target.Substrate temperature is 150 ℃, and sedimentation time is 1.5 hours, and ambient pressure is 30Pa, during direct-current discharge, and environment N
2Gas is aubergine.
Show that by X-ray diffraction mensuration the film of deposition is the Co of polycrystal cubic structure
3N.The x-ray photoelectron power spectrum has shown the peak of N and Co, and the content of N is estimated as 25%.Show the Co that makes by the pulse laser reactive deposition by stereoscan photograph mensuration
3The N film is made up of the particle that diameter is approximately 30 nanometers, and distribution of particles is even, free of pinholes.
Co
3The electrochemical property test result of N membrane electrode is as follows:
1, Co
3The N membrane electrode can be at 7 μ A/cm
2Carry out charge and discharge cycles under the charge-discharge velocity.At different voltage range 0.01-3.0V, discharge capacity can reach 421mAh/g for the first time, and nearly 80 capacity attenuations that circulate are very little, and the reversible capacity loss only is 3%.Efficiency for charge-discharge is 95%.Charge and discharge cycles time number average can reach more than 80 times.
2, Co
3The cyclic voltammetric test of N membrane electrode is presented in the discharge process first time, can observe three discharge potential peaks, respectively at 1.97V, and 1.02V, and 0.60V.After the circulation, a discharge potential peak is only arranged about 0.67V for the second time.Yet two peaks can both have been observed in all charging processes respectively at 1.8V and 2.1V.
3, Co
3After the N membrane electrode electrochemical reaction, can observe transparent Co being coated with the transparent conducting glass of tin indium oxide (ITO) film
3The N film becomes black.X-ray diffraction and x-ray photoelectron power spectrum are tested the existence of metal Co in the membrane electrode that has shown electrochemical reaction.
4, Co
3When N membrane electrode electrochemical reaction recharged, the transmissivity of membrane electrode more slightly improved, and still observed the membrane electrode of black with eye.X-ray diffraction and the test of x-ray photoelectron power spectrum have shown the disappearance of metal Co, but do not observe Co
3The polycrystalline of N.
Therefore, in nano Co
3The N film can be used as the anode material of lithium ion battery.
Embodiment 2
Adopt reactive pulsed laser deposition, respectively on stainless steel substrates, on glass, the transparent conducting glass (ITO) that is coated with tin indium oxide goes up preparation Fe
3The N film.The 355nm pulse laser is produced through frequency tripling by the fundamental frequency that the Nd:YAG laser produces, and laser beam is through inciding after the lens focus on the metallic iron target.Substrate temperature is 100 ℃, and sedimentation time is 1.5 hours, and ambient pressure is 25Pa, during direct-current discharge, and environment N
2Gas is aubergine.
Show that by X-ray diffraction mensuration the film of deposition is the Fe of polycrystal cubic structure
3N, and contain a spot of Fe
4N.The x-ray photoelectron power spectrum has shown the peak of N and Fe, and the content of N is estimated as 23%.Show the Fe that makes by the pulse laser reactive deposition by stereoscan photograph mensuration
3The N film is made up of the particle that diameter is approximately 30 nanometers, and distribution of particles is even, free of pinholes.
Fe
3The electrochemical property test result of N membrane electrode is as follows:
1, Fe
3The N membrane electrode can be at 7 μ A/cm
2Carry out charge and discharge cycles under the charge-discharge velocity.At different voltage range 0.01-3.0V, discharge capacity can reach 440mAh/g for the first time, and nearly 80 capacity attenuations that circulate are very little, and reversible capacity loses less than 1%.Efficiency for charge-discharge is 95%.Charge and discharge cycles time number average can reach more than 80 times.
2, Fe
3The test of the cyclic voltammetric of N membrane electrode is presented at for the first time in the discharge process, can observe two irreversible discharge potential peaks at 2.87V and 1.70V, with a reversible discharge potential peak about 0.70V.Yet can both observe a peak in all charging processes about 1.70V.
3, Fe
3After the N membrane electrode electrochemical reaction, can observe the Fe of buff being coated with the transparent conducting glass of tin indium oxide (ITO) film
3The N film becomes black.X-ray diffraction and x-ray photoelectron power spectrum are tested the existence of metal Fe in the membrane electrode that has shown electrochemical reaction.
4, Fe
3When N membrane electrode electrochemical reaction recharged, the transmissivity of membrane electrode more slightly improved, and still observed the membrane electrode of black with eye.X-ray diffraction and the test of x-ray photoelectron power spectrum have shown the disappearance of metal Fe, but do not observe Fe
3The polycrystalline of N.
Therefore, in nanometer Fe
3The N film can be used as the anode material of lithium ion battery.
Embodiment 3
Adopt reactive pulsed laser deposition respectively at the preparation Ni on the stainless steel substrates, on glass, the transparent conducting glass (ITO) that is coated with tin indium oxide
3The N film.The 355nm pulse laser is produced through frequency tripling by the fundamental frequency that the Nd:YAG laser produces, and laser beam is through inciding after the lens focus on the metallic nickel target.Substrate temperature is 100 ℃, and sedimentation time is 2 hours, and ambient pressure is 10Pa, during direct-current discharge, and environment N
2Gas is aubergine.
Show that by X-ray diffraction mensuration the film of deposition is the Ni of polycrystal cubic structure
3N contains small amount of N i
4N.The x-ray photoelectron power spectrum has shown the peak of N and Ni, and the content of N is estimated as 21%.Show the Ni that makes by the pulse laser reactive deposition by stereoscan photograph mensuration
3The N film is made up of the particle that diameter is approximately 30 nanometers, and distribution of particles is even, free of pinholes.
Ni
3The electrochemical property test result of N membrane electrode is as follows:
1, Ni
3The N membrane electrode can be at 7 μ A/cm
2Carry out charge and discharge cycles under the charge-discharge velocity.At different voltage range 0.01-3.0V, discharge capacity can reach 420mAh/g for the first time, and specific capacity decays to 96%.Circulating, the reversible capacity loss only is 4% after 50 times.Efficiency for charge-discharge is 95%.Charge and discharge cycles time number average can reach more than 50 times.
2, Ni
3The cyclic voltammetric test of N membrane electrode is presented in the discharge process first time, can observe two discharge potential peaks, respectively at 1.73V and 0.46V.After the circulation, a discharge potential peak is only arranged about 0.90V for the second time.Yet two peaks can both have been observed in all charging processes respectively at 1.5V and 2.2V.
3, Ni
3After the N membrane electrode electrochemical reaction, can observe Ni being coated with the transparent conducting glass of tin indium oxide (ITO) film
3The N film becomes black.X-ray diffraction and x-ray photoelectron power spectrum are tested the existence of metal Ni in the membrane electrode that has shown electrochemical reaction.
4, Ni
3When N membrane electrode electrochemical reaction recharged, the transmissivity of membrane electrode more slightly improved, and still observed the membrane electrode of black with eye.X-ray diffraction and the test of x-ray photoelectron power spectrum have shown the disappearance of metal Ni, but do not observe Ni
3The polycrystalline of N.
Therefore, at nanometer Ni
3The N film can be used as the anode material of lithium ion battery.
Claims (3)
1, a kind of transition metal nitride film as the Anode of lithium cell material is characterized in that it being the M that is generated by reactive pulsed laser deposition
3N, M is a kind of of following metal Co, Fe, Ni here, and this thin-film material is the polycrystal cubic structure, be that 20 nanometers are formed to the nano particle of 50 nanometers by diameter, and distribution of particles is even, and the content of N is 20-30%.
2, a kind of preparation method as the said transition metal nitride film of claim 1 is characterized in that adopting reactive pulsed laser deposition, and concrete steps are: by the laser beam of ultraviolet wavelength through inciding after the lens focus on the metal M target; The free radical that N atom and ion are arranged in the reative cell, they are by the nitrogen of noticeable degree feeding reative cell, and through the high voltage direct current discharge generation, the pressure of control gaseous is 10～30Pa by the pair of planar discharge electrode; M
3N is deposited on and forms film on the substrate, and substrate temperature is 50 ℃-200 ℃, and sedimentation time is 1-3 hour, and metal M is a kind of of Co, Ni, Fe here.
3, preparation method according to claim 2 is characterized in that, substrate adopts stainless steel substrates, the transparent conducting glass that is coated with tin indium oxide or glass.
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|---|---|---|---|
| CNB031153062A CN1294661C (en) | 2003-01-30 | 2003-01-30 | Nitride thin film of transition metal capable of being as anode material of batteries its preparation method |
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|---|---|---|---|
| CNB031153062A CN1294661C (en) | 2003-01-30 | 2003-01-30 | Nitride thin film of transition metal capable of being as anode material of batteries its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1447463A true CN1447463A (en) | 2003-10-08 |
| CN1294661C CN1294661C (en) | 2007-01-10 |
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ID=28050417
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101233629B (en) * | 2005-08-02 | 2010-06-02 | 松下电器产业株式会社 | Negative electrode for lithium secondary battery and method for producing same |
| CN102623696A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Preparation method for core-shell type carbon-coated iron nitride nano-composite particles and application of core-shell type carbon-coated iron nitride nano-composite particles |
| CN101834293B (en) * | 2009-03-12 | 2013-10-16 | 复旦大学 | Tungsten nitride cathode material for lithium ion battery and preparation method thereof |
| CN105845444A (en) * | 2016-05-25 | 2016-08-10 | 东南大学 | Preparation and application for transition metal sulfide-based counter electrode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06290782A (en) * | 1993-03-30 | 1994-10-18 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery |
| US5980977A (en) * | 1996-12-09 | 1999-11-09 | Pinnacle Research Institute, Inc. | Method of producing high surface area metal oxynitrides as substrates in electrical energy storage |
-
2003
- 2003-01-30 CN CNB031153062A patent/CN1294661C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101233629B (en) * | 2005-08-02 | 2010-06-02 | 松下电器产业株式会社 | Negative electrode for lithium secondary battery and method for producing same |
| CN101834293B (en) * | 2009-03-12 | 2013-10-16 | 复旦大学 | Tungsten nitride cathode material for lithium ion battery and preparation method thereof |
| CN102623696A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Preparation method for core-shell type carbon-coated iron nitride nano-composite particles and application of core-shell type carbon-coated iron nitride nano-composite particles |
| CN102623696B (en) * | 2012-03-31 | 2014-06-25 | 大连理工大学 | Preparation method for core-shell type carbon-coated iron nitride nano-composite particles and application of core-shell type carbon-coated iron nitride nano-composite particles |
| CN105845444A (en) * | 2016-05-25 | 2016-08-10 | 东南大学 | Preparation and application for transition metal sulfide-based counter electrode |
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| CN1294661C (en) | 2007-01-10 |
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