CN1294661C - 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 PDF

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Publication number
CN1294661C
CN1294661C CNB031153062A CN03115306A CN1294661C CN 1294661 C CN1294661 C CN 1294661C CN B031153062 A CNB031153062 A CN B031153062A CN 03115306 A CN03115306 A CN 03115306A CN 1294661 C CN1294661 C CN 1294661C
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film
thin film
transition metal
discharge
preparation
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CN1447463A (en
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傅正文
秦启宗
赵胜利
岳小力
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Fudan University
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Fudan University
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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 discloses a novel thin film of transition metal nitride Co3N, Fe3N and Ni3N, which is used as positive electrode material of a lithium ion battery. The thin film material can be prepared by reactive deposition of pulsed lasers at nitrogen atmosphere. The particle dimension is from 20 to 50 nm, and the thin film material is in a polycrystal cubic structure. After a battery is composed of electrodes prepared from the thin film and lithium metal, the discharge platform presents 0.64V, 0.70V and 0.92V or so (corresponding to Li/Li [+]). When voltage range is from 3.50 to 0.01V and current density is 7 muA/cm<2>, the electrodes have favorable charge and discharge cycle reversibility, and the specific capacity is maintained at 420, 440 and 420 mAh/g or so. The reversible capacity loss is only less than 5% or so after 80 times of cycles. Compared with various kinds of existing positive electrode material of thin films, the positive electrode material of the present invention has advantages.

Description

Can be used as transition metal nitride film of battery anode material and preparation method thereof
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 includes M 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 atom percentage 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, the free radical of above-mentioned N atom and ion can be fed the nitrogen of reative cell by a noticeable degree, produces through direct-current discharge by the pair of planar discharge electrode, and the pressure of gas is 10～30Pa in the control reative cell; 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 Ni in the N film 4The 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 N ls 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 this film includes M 3N, wherein M is a kind of of following metal Co, Fe, and this film 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 atom percentage content of N is 20-30%.
2, a kind of preparation method who is used as the transition metal nitride film of Anode of lithium cell material, it is characterized in that adopting reactive pulsed laser deposition, 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, the free radical of above-mentioned N atom and ion is fed the nitrogen of reative cell by a noticeable degree, produce through direct-current discharge by the pair of planar discharge electrode, the pressure of gas is 10～30Pa in the control reative cell; 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, Fe here.
3, preparation method according to claim 2 is characterized in that, substrate adopts stainless steel substrates, is coated with the transparent conducting glass of tin indium oxide.
CNB031153062A 2003-01-30 2003-01-30 Nitride thin film of transition metal capable of being as anode material of batteries its preparation method Expired - Fee Related CN1294661C (en)

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US8080334B2 (en) * 2005-08-02 2011-12-20 Panasonic Corporation Lithium secondary battery
CN101834293B (en) * 2009-03-12 2013-10-16 复旦大学 Tungsten nitride cathode material for lithium ion battery and preparation method thereof
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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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
CN1240049A (en) * 1996-12-09 1999-12-29 尖端研究组织公司 High surface area metal nitrides or metal oxynitrides for electrical energy storage

Patent Citations (2)

* Cited by examiner, † Cited by third party
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
CN1240049A (en) * 1996-12-09 1999-12-29 尖端研究组织公司 High surface area metal nitrides or metal oxynitrides for electrical energy storage

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