CN105779954A - Method for preparing GaN/electric conducting substrate composite material by magnetron sputtering method and application thereof to sodium ion battery - Google Patents

Method for preparing GaN/electric conducting substrate composite material by magnetron sputtering method and application thereof to sodium ion battery Download PDF

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Publication number
CN105779954A
CN105779954A CN201610119485.5A CN201610119485A CN105779954A CN 105779954 A CN105779954 A CN 105779954A CN 201610119485 A CN201610119485 A CN 201610119485A CN 105779954 A CN105779954 A CN 105779954A
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gan
substrate
magnetron sputtering
ion battery
target
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CN201610119485.5A
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倪世兵
黄鹏
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China Three Gorges University CTGU
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China Three Gorges University CTGU
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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 relates to a method for preparing a GaN/electric conducting substrate composite material by a magnetron sputtering method. The composite material is GaN; and the preparation method specifically comprises the following steps: a GaN target with a purity of 99.99% and a metal substrate are respectively put in a sputtering cavity, and the distance D from the target to the substrate is 7 cm; the cavity is vacuumized, and V is not less than 1*10-7 Torr; the substrate is heated to keep at 25-700 DEG C; the target is bombarded by using magnetron sputtering; and GaN is deposited and grown on the metal substrate. The prepared GaN directly grows on an electric conducting substrate, and is tightly combined with the substrate; the growing thickness of the GaN material can be controlled through adjusting the time; the GaN in prepared samples is uniform nanometer particles with an average size of 40 nm; and the prepared GaN can serve as a sodium ion battery negative pole material, and has higher charging and discharging volumes and lower charging and discharging platforms.

Description

A kind of magnetron sputtering method prepares the method for GaN/ conducting base composite and the application on sodium-ion battery thereof
Technical field
The present invention relates to a kind of method that magnetron sputtering method prepares GaN/ conducting base composite, and be applied on sodium-ion battery, belong to energy storage material and field of electrochemical power source.
Technical background
Lithium ion battery has the remarkable advantages such as high, big, the environmental friendliness of specific energy of running voltage, is the energy storage device of a kind of rationality.It is not only widely used in the portable electric appts such as mobile phone, laptop computer, is also regarded as the ideal source of the power supply of following electric vehicle and large-scale energy-accumulating power station.But, lithium resource reserves are limited, are difficult to meet the heavy demand in following energy storage market.Along with the continuous exploitation of lithium resource, its cost is just gradually increasing, and this defines huge challenge for lithium ion battery scale application in electric automobile and large-scale energy-accumulating power station.It is extremely urgent that searching can substitute the low cost of lithium ion battery, Novel energy storage apparatus.Sodium and lithium are in same main group, have similar physicochemical properties, and the sodium-ion battery with sodium as core has the operation principle similar with lithium ion battery and close chemical property, is the ideal substitute of lithium ion battery.And, sodium element is widely distributed, refines simple, and with low cost, this is conducive to its large-scale application in electric automobile and large-scale energy-accumulating power station.But, the performance of sodium-ion battery the most still can not show a candle to lithium ion battery, and the principal element restricting its development is electrode material.The initial Research Thinking of sodium ion battery electrode material is also similar to that lithium ion battery electrode material.But, follow-up study finds, sodium ion battery electrode material can not be analogized completely in lithium ion battery material system.A lot of materials in lithium ion battery with premium properties, when being applied in sodium-ion battery, it may appear that the problems such as capacity is low, poorly reversible, even without electro-chemical activity.At present, sodium-ion battery positive material is mainly by deriving in original anode material for lithium-ion batteries system, kind relative abundance.And the kind of anode material of lithium-ion battery is the deficientest, need extension badly.Explore novel anode material of lithium-ion battery for sodium-ion battery development have be of great significance.
Summary of the invention
Based on background above, this project development one sputtering method prepares GaN/ conducting base composite construction, shows higher reversible capacity using it as binder free sodium-ion battery negative pole.Result shows, GaN can be as the preferable novel anode material of lithium-ion battery of one.Concrete preparation method is as follows:
(1) purity is 99.99%GaN target and metal substrate is placed in sputtering chamber respectively, target and substrate distance D=7cm；
(2) cavity is carried out evacuation, V >=1 × 10-7Torr；
(3) substrate is heated, and its temperature is maintained at 25～700 DEG C；
(4) utilize magnetron sputtering that target is bombarded, on the metallic substrate deposition growing GaN.
Step (4) is at reacting gas N2Flow F=20sccm, operating air pressure P=100mTorr；Obtain after sedimentation time 20～200min under conditions of sputtering power W=200w.
Described metal substrate is any one in Copper Foil, nickel foil, foam copper, nickel foam, the Copper Foil of pre-deposition graphene buffer layers, nickel foil, foam copper or nickel foam.
The GaN/ conducting base composite that described magnetron sputtering method is prepared by present invention application on sodium-ion battery
GaN material involved in the present invention and preparation method have a following distinguishing feature:
(1) GaN prepared by is grown directly upon on conducting base, is tightly combined with matrix；
(2) growth thickness of GaN material can be controlled by the adjustment time；
(3) in sample prepared by, GaN is uniform nano-particle, and average-size is at 40nm；
(4) GaN prepared by can have higher charge and discharge capacity and relatively low charge and discharge platform as anode material of lithium-ion battery.
Accompanying drawing explanation
The SEM figure of sample prepared by Fig. 1 embodiment 1；
The charge and discharge curve first of sample prepared by Fig. 2 embodiment 1；
The charge and discharge curve first of sample prepared by Fig. 3 embodiment 2；
The charge and discharge curve first of sample prepared by Fig. 4 embodiment 3.
Detailed description of the invention
Embodiment 1
Purity is 99.99%GaN target and Copper Foil is placed in sputtering chamber respectively, target and substrate distance D=7cm；Cavity is evacuated to V >=1 × 10-7Torr is also heated to 500oC to substrate；Utilize magnetron sputtering that target is bombarded, on the metallic substrate deposition growing GaN.Utilize magnetron sputtering that target is bombarded, reacting gas N during deposition growing GaN is constituted on the metallic substrate2Flow F=20sccm, operating air pressure P=100mTorr；Sputtering power W=200w, sedimentation time 120mins.Prepared sample is through characterizing through SEM, and as seen from Figure 1, sample is nano-particle, average-size about 40nm.The material of embodiment 1 gained is made button cell as follows: prepared GaN/Cu is cut into the disk of diameter 14mm, at 120 DEG C, be vacuum dried 12h.With metallic sodium sheet for electrode, Grade GF/D is barrier film, is dissolved with NaPF6(1mol/L) solution of EC+DEC (volume ratio is 1:1) is electrolyte, is assembled into CR2025 type battery in the glove box of argon shield.Set of cells stands 10h after installing, then carries out constant current charge-discharge test with CT2001A battery test system, and test voltage is 3～0.02V.Fig. 2 shows, the GaN prepared by embodiment 1 is respectively 836 and 887mAh/g as sodium-ion battery negative pole charge and discharge capacity first, and discharge platform is mainly between 1.0～0.02V, and charging platform is mainly between 0.2～2.0V.
Embodiment 2
Purity is 99.99%GaN target and nickel foam is placed in sputtering chamber respectively, target and substrate distance D=7cm；Cavity is evacuated to V >=1 × 10-7Torr is also heated to 500oC to substrate；Utilize magnetron sputtering that target is bombarded, on the metallic substrate deposition growing GaN.Reacting gas N2Flow F=20sccm, operating air pressure P=100mTorr；Sputtering power W=200w, sedimentation time 80mins.The material of embodiment 2 gained is prepared as button cell by step in embodiment 1 and its chemical property is studied.As it is shown on figure 3, the GaN prepared by embodiment 2 is respectively 901 and 948mAh/g as sodium-ion battery negative pole charge and discharge capacity first.
Embodiment 3
The Copper Foil that purity is 99.99%GaN target and pre-deposition Graphene is placed in sputtering chamber respectively, target and substrate distance D=7cm；Cavity is evacuated to V >=1 × 10-7Torr is also heated to 500oC to substrate；Utilize magnetron sputtering that target is bombarded, on the metallic substrate deposition growing GaN.Reacting gas N2Flow F=20sccm, operating air pressure P=100mTorr；Sputtering power W=30w, sedimentation time 30mins.The material of embodiment 2 gained is prepared as button cell by step in embodiment 1 and its chemical property is studied.As it is shown on figure 3, the GaN prepared by embodiment 2 is respectively 873 and 934mAh/g as sodium-ion battery negative pole charge and discharge capacity first.

Claims (4)

1. the method that a magnetron sputtering method prepares GaN/ conducting base composite, it is characterised in that this composite is GaN, Concrete preparation method is:
(1) my 99.99%GaN target of purity and metal substrate are placed in sputtering chamber respectively, target and substrate distance D=7cm；
(2) cavity is carried out evacuation, V >=1 × 10-7Torr；
(3) substrate is heated, and its temperature is maintained at 25～700 DEG C；
(4) utilize magnetron sputtering that target is bombarded, on the metallic substrate deposition growing GaN.
2. the method that the magnetron sputtering method described in claim 1 prepares GaN/ conducting base composite, it is characterised in that step (4) It is at reacting gas N2Flow F=20sccm, operating air pressure P=100mTorr；Under conditions of sputtering power W=200w Obtain after sedimentation time 20～200min.
3. the method that magnetron sputtering method described in claim 1 prepares GaN/ conducting base composite, it is characterised in that described gold Genus substrate is Copper Foil, nickel foil, foam copper, nickel foam, the Copper Foil of pre-deposition graphene buffer layers, nickel foil, foam copper or foam Any one in nickel.
4. the GaN/ conducting base composite that prepared by the magnetron sputtering method described in any one of claim 1-3 is on sodium-ion battery Application.
CN201610119485.5A 2016-03-02 2016-03-02 Method for preparing GaN/electric conducting substrate composite material by magnetron sputtering method and application thereof to sodium ion battery Withdrawn CN105779954A (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN106935852A (en) * 2017-04-14 2017-07-07 中国科学院半导体研究所 Si doped gallium nitrides/metal negative electrode battery material and preparation method thereof, lithium battery
CN110137441A (en) * 2019-02-28 2019-08-16 厦门理工学院 A kind of carbon fiber load gallium nitride negative electrode material, preparation method and lithium ion battery in situ
CN112309723A (en) * 2020-10-29 2021-02-02 齐鲁工业大学 Working electrode based on carbon cloth/gallium oxynitride and super capacitor
CN113113237A (en) * 2020-10-29 2021-07-13 齐鲁工业大学 Carbon cloth/gallium oxynitride and application thereof
CN113113239A (en) * 2020-10-29 2021-07-13 齐鲁工业大学 Carbon cloth/gallium oxynitride supercapacitor electrode material and preparation method thereof
EP4044281A1 (en) * 2021-02-15 2022-08-17 Epinovatech AB Battery cell with an anode comprising gallium nitride nanocrystals

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CN103996611A (en) * 2014-05-30 2014-08-20 广州市众拓光电科技有限公司 GaN thin film growing on metal Al substrate and preparing method and application thereof

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CN103996611A (en) * 2014-05-30 2014-08-20 广州市众拓光电科技有限公司 GaN thin film growing on metal Al substrate and preparing method and application thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106935852A (en) * 2017-04-14 2017-07-07 中国科学院半导体研究所 Si doped gallium nitrides/metal negative electrode battery material and preparation method thereof, lithium battery
CN110137441A (en) * 2019-02-28 2019-08-16 厦门理工学院 A kind of carbon fiber load gallium nitride negative electrode material, preparation method and lithium ion battery in situ
CN112309723A (en) * 2020-10-29 2021-02-02 齐鲁工业大学 Working electrode based on carbon cloth/gallium oxynitride and super capacitor
CN113113237A (en) * 2020-10-29 2021-07-13 齐鲁工业大学 Carbon cloth/gallium oxynitride and application thereof
CN113113239A (en) * 2020-10-29 2021-07-13 齐鲁工业大学 Carbon cloth/gallium oxynitride supercapacitor electrode material and preparation method thereof
CN112309723B (en) * 2020-10-29 2021-09-21 齐鲁工业大学 Working electrode based on carbon cloth/gallium oxynitride and super capacitor
CN113113239B (en) * 2020-10-29 2022-04-29 齐鲁工业大学 Carbon cloth/gallium oxynitride supercapacitor electrode material and preparation method thereof
CN113113237B (en) * 2020-10-29 2022-04-29 齐鲁工业大学 Carbon cloth/gallium oxynitride and application thereof
EP4044281A1 (en) * 2021-02-15 2022-08-17 Epinovatech AB Battery cell with an anode comprising gallium nitride nanocrystals

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