CN108198698A - A kind of high power capacity transition metal nitride coating electrode material and preparation method thereof - Google Patents
A kind of high power capacity transition metal nitride coating electrode material and preparation method thereof Download PDFInfo
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- CN108198698A CN108198698A CN201810144363.0A CN201810144363A CN108198698A CN 108198698 A CN108198698 A CN 108198698A CN 201810144363 A CN201810144363 A CN 201810144363A CN 108198698 A CN108198698 A CN 108198698A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 32
- -1 transition metal nitride Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 57
- 239000002346 layers by function Substances 0.000 claims abstract description 50
- 230000007704 transition Effects 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 25
- 230000008020 evaporation Effects 0.000 claims abstract description 25
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 230000008021 deposition Effects 0.000 claims description 93
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 38
- 238000010891 electric arc Methods 0.000 claims description 20
- 238000004062 sedimentation Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 15
- 238000005137 deposition process Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 231100000719 pollutant Toxicity 0.000 claims description 6
- 238000003486 chemical etching Methods 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 80
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 46
- 239000011888 foil Substances 0.000 description 24
- 238000011068 loading method Methods 0.000 description 12
- 230000005611 electricity Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 229910052774 Proactinium Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/0641—Nitrides
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- 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
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
-
- 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
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention discloses a kind of high power capacity transition metal nitride coating electrode material, including matrix, the Cr binder courses that are deposited on described matrix surface, is deposited on the MeN transition zones of the Cr combinations layer surface and is deposited on the MeXN surface functional layers of the MeN transition layer surface；Me is at least one of Ti, Cr, Zr and Hf elements in the MeN transition zones；Me is at least one of Ti, Cr, Zr and Hf element in the MeXN surface functional layers, at least one of X Ni, Cu and Ag element.The present invention deposits transition metal nitride coating electrode material using cathodic arc evaporation deposition technique on the surface of Cu foil matrixes, the implementation cost of preparation method of the present invention is low, the coating electrode material for preparing gained has high-specific surface area and high stored energy capacitance, also there is excellent electric conductivity, chemical stability and flexibility, suitable for making electrode material for super capacitor, the application range of ultracapacitor is expanded, reduces the manufacture cost of ultracapacitor.
Description
Technical field
The present invention relates to a kind of coating electrode material more particularly to a kind of high power capacity transition metal nitride coated electrode materials
Material and preparation method thereof.
Background technology
In recent years, it is risen with the acceleration of environmental protection pressure and new-energy automobile industry, global New Energy Industry obtains
Tremendous development, New Energy Industry are forming the complete New Energy Industry chain that slave device is fabricated onto energy services.However, new
Bottleneck factor in energy industry is the storage to the energy (electric energy) and release link, and the storage and release of electric energy fast and stable are
New energy is capable of the key of Rapid Popularization and application.As the improvement to conventional batteries, ultracapacitor
(supercapacitor, ultracapacitor) has that the charging time is short, service life is long, good temp characteristic, energy saving
And the features such as environmentally protective, it is the key components and parts in New Energy Industry.But with quickly propelling for New Energy Industry, super electricity
The capacity of container and service life are increasingly difficult to meet the requirements, and cost, which remains high, also limits its popularization and application.
Currently, mainly there are three classes for making the material of ultracapacitor positive electrode：Carbon material, metal oxide materials and
Conducting polymer materials.Wherein, carbon material has large specific surface area, conductivity height, good, the electrochemical window mouth width of electrolyte wellability etc.
Advantage, but its energy density and power density are low so that its specific capacitance is relatively low.Metal oxide materials are typical counterfeit electricity
Hold electrode material, but material price is high, and its cyclical stability and self-conductive under high power work environment is poor, limit
Application of the metal oxide electrode material in ultracapacitor industrialized production is made.Conducting polymer materials are in charge and discharge
By the way that redox reaction occurs in journey, and generate n or p-type doping rapidly in electrode material film, and then make on electrode material
High Density Charge is stored, larger fake capacitance is generated and realizes electric energy storage.Ultracapacitor has made of conducting polymer materials
The features such as longevity of service, suitable temperature range are wide, environmental-friendly.However, conducting polymer poor chemical stability itself, limits it
Extensive use.
Therefore, there is an urgent need for exploitation one kind to have both high power capacity, high circulation stability, superior electrical conductivity, wide chemical window, foldable
The Novel super capacitor electrode material of (flexibility), low cost, wide, environmental-friendly etc. the characteristics of suitable temperature range, to realize super electricity
The large-scale production and extensive use of container.
Invention content
It is an object of the invention to solve the disadvantage that the above-mentioned prior art and deficiency, a kind of high power capacity transition metal nitrogen is provided
Compound coating electrode material and preparation method thereof, the transition metal nitride coating electrode material have the porous knot of surface porosity
Structure, binding force be excellent and the features such as high stored energy capacitance, suitable for making electrode material for super capacitor.
To reach its purpose, the technical solution adopted in the present invention is：A kind of high power capacity transition metal nitride coating electricity
Pole material, including matrix, the Cr binder courses that are deposited on described matrix surface, the MeN transition for being deposited on the Cr combinations layer surface
Layer and the MeXN surface functional layers for being deposited on the MeN transition layer surface；The Me of the MeN transition zones is Ti, Cr, Zr and Hf
At least one of element；The Me of the MeXN surface functional layers is at least one of Ti, Cr, Zr and Hf element, X Ni,
At least one of Cu and Ag element.
As the preferred embodiment of the present invention, described matrix is Cu foil matrixes, and the MeXN surface functional layers are equipped with through chemistry
Etch the loose and porous structure formed.
The present invention also provides a kind of preparation method of high power capacity transition metal nitride coating electrode material, including walking as follows
Suddenly：
(1) on the surface of matrix, cathodic arc evaporation deposits Cr binder courses first；
(2) and then on the Cr binder courses MeN transition zones, the Me of the MeN transition zones are deposited with cathodic arc evaporation
For at least one of Ti, Cr, Zr and Hf element；
(3) and then on the MeN transition zones cathodic arc evaporation is used, is co-deposited MeXN surface functional layers；The MeXN
The Me of surface functional layer is at least one of Ti, Cr, Zr and Hf element, at least one of X Ni, Cu and Ag element；
(4) MeXN surface functional layers described in diluting salpeter solution chemical etching are finally used, make the MeXN surface functional layers
Has loose and porous structure.
The coefficient of thermal expansion that the Cr binder courses can be alleviated between matrix and coating be excuse me, but I must be leaving now problem, and can enhance film-base junction
Close intensity.The MeN transition zones can provide support for MeXN surface functional layers, and the metallic element of MeN transition zones contains multivalent state
Ion, can be used as redox active moiety, and MeN transition zones in itself have excellent electric conductivity, chemical stability and
Mechanical property is a kind of excellent capacitor electrode material.
As the preferred embodiment of the present invention, the concrete operations of the step (1) are：Deposition chambers operating temperature is heated to
350~400 DEG C, matrix is heated to 400~450 DEG C, and extracts deposition chamber gas；When deposition chambers vacuum, to reach background true
Reciprocal of duty cycle 1.0 × 10-3After Pa, be passed through the Ar gas that gas flow is 100sccm, adjust deposition chamber environmental pressure to 1.0~
2.0Pa, by metal Cr target arc power power regulations to 2~5kW, work 10~30min；Metal Cr targets are handled through prevapourising
Afterwards, deposition chamber temperature is set as 400 DEG C, and substrate temperature is 400~450 DEG C, rotates sample stage, makes matrix face metal Cr
Target, and be 15~20cm with the distances of metal Cr targets, deposition chambers Ar atmospheric pressures are adjusted to 0.8~1.5Pa, using cathode arc
Hydatogenesis Cr binder courses.
As the preferred embodiment of the present invention, in the step (1), the Cr metals electricity of cathodic arc evaporation deposition Cr binder courses
Arc target power output is 1.5~2.5kW, and sedimentation time is 5~10min, and matrix loads the back bias voltage of -50~-150V in deposition process.
As the preferred embodiment of the present invention, in the step (1), before deposition chambers are passed through Ar gas, also to deposition chamber
Heated baking is carried out, to remove the pollutant of deposition chamber inner wall absorption.
As the preferred embodiment of the present invention, the concrete operations of the step (2) are：After Cr binder courses deposition is completed,
It maintains the temperature of deposition chamber in 400 DEG C, the temperature of matrix at 400~450 DEG C, is passed through N2Gas, adjust flow so that Ar gas with
N2The total flow of gas is 150~300sccm, N2Intrinsic standoff ratio is 40~60%, and MeN transition zones are deposited using cathodic arc evaporation.
As the preferred embodiment of the present invention, in the step (2), cathodic arc evaporation deposits the Me metals of MeN transition zones
Electric arc target power output is 1.5~2.5kW, and sedimentation time is 5~10min, and matrix loads the negative bias of -50~-150V in deposition process
Pressure.
As the preferred embodiment of the present invention, the concrete operations of the step (3) are：After MeN transition zones deposition is completed,
It maintains the temperature of deposition chamber in 400 DEG C, the temperature of matrix at 400~450 DEG C, rotates sample stage, matrix is made to be located at metal Me
The centre position of target and metal X targets, and be 15~20cm with the spacing of two target, it is passed through N2Gas adjusts flow so that Ar gas
With N2The total flow of gas is 150~300sccm, N2Qi leel pressure ratio is 40~60%, adjusting deposition chambers pressure to 0.8~
1.5Pa, while Me electric arc targets and X electric arc targets are opened, deposition obtains MeXN surface functional layers.
As the preferred embodiment of the present invention, in the step (3), the Me electric arc target power outputs of deposition MeXN surface functional layers are
2.0~2.5kW, X electric arcs target power output are 0~2.0kW, and sedimentation time is 10~30min, matrix loading -50 in deposition process~-
The back bias voltage of 150V, matrix pivoted frame rotating speed are 1~4rpm.
As the preferred embodiment of the present invention, the content of Me, X and N element is followed successively by respectively in the MeXN surface functional layers
20~50at.%, 0~30at.% and 45~55at.%；The thickness of the MeXN surface functional layers is 50~1000nm.
As the preferred embodiment of the present invention, the concrete operations of the step (4) are：With the dilution nitre of 0.01~0.2mol/L
Acid solution corrodes MeXN surface functional layers, and the time is 5min~5h, obtain surface with loose and porous structure, binding force it is excellent and
The transition metal nitride coating electrode material of high stored energy capacitance.
As present invention further optimization scheme, the concrete operations of the step (4) are：With 0.01~0.2mol/L's
It dilutes salpeter solution and corrodes MeXN surface functional layers, the time is 1h~5h, and it is excellent with loose and porous structure, binding force to obtain surface
The transition metal nitride coating electrode material of good and high stored energy capacitance.
Beneficial effects of the present invention are：The present invention is deposited using cathodic arc evaporation deposition technique on the surface of Cu foil matrixes
Transition metal nitride coating electrode material, the implementation cost of preparation method of the present invention is low, prepares the coating electrode material of gained
It is super suitable for making also with excellent electric conductivity, chemical stability and flexibility with high-specific surface area and high stored energy capacitance
Capacitor electrode material expands the application range of ultracapacitor, reduces the manufacture cost of ultracapacitor.
Description of the drawings
Fig. 1 is the structure diagram of the high power capacity transition metal nitride coating electrode material of the present invention；
Fig. 2 is the XRD spectrum of the high power capacity transition metal nitride coating electrode material of the present invention；
Fig. 3 is the SEM surfaces of the high power capacity transition metal nitride coating electrode material of the present invention, Cross Section Morphology figure；
Dilution nitric acid of the high power capacity transition metal nitride coating electrode material through 0.01mol/L that Fig. 4 is the present invention is molten
Surface topography map after liquid erosion；
Fig. 5 is dilution salpeter solution of the high power capacity transition metal nitride coating electrode material through 0.2mol/L of the present invention
Surface topography map after erosion；
Fig. 6 is dilution salpeter solution of the high power capacity transition metal nitride coating electrode material through 0.2mol/L of the present invention
XRD spectrum after erosion.
Specific embodiment
It more clearly to state technical scheme of the present invention, further illustrates, but cannot use with reference to specific embodiment
In the limitation present invention, this is only the section Example of the present invention.Matrix used in following embodiment of the present invention is Cu foil bases
Body.
Embodiment 1
The present embodiment 1 provides a kind of high power capacity transition metal nitride coating electrode material, as shown in Figure 1, including Cu foils
Matrix 1, the Cr binder courses 2 for being deposited on 1 surface of Cu foils matrix, the MeN transition zones 3 for being deposited on 2 surface of Cr binder courses and deposition
MeXN surface functional layers 4 in 3 surface of MeN transition zones.Specifically, in MeN transition zones 3 Me in Ti, Cr, Zr and Hf at least
A kind of element；Me is at least one of Ti, Cr, Zr and Hf element in MeXN surface functional layers 4, in X Ni, Cu and Ag extremely
A kind of few element.MeXN surface functional layers 4 are equipped with the loose and porous structure formed through chemical etching.
Embodiment 2
The present embodiment 2 provides a kind of preparation method of high power capacity transition metal nitride coating electrode material, including as follows
Step：
(1) Cu foils substrate pretreated：
After Cu foils matrix is carried out mechanical lapping and polishing treatment, started the cleaning processing with solvent：First with isopropanol ultrasound
10min is cleaned, the alcoholic solution for reusing a concentration of 98% is cleaned by ultrasonic 10min, is cleaned by ultrasonic again with ultra-pure water after taking-up
3min；Then ion source Bombardment and cleaning processing is carried out：Using Ar+Ion source carries out Cu foils matrix cleaning 5min, and ion source is banged
The environmental pressure for hitting cleaning treatment is 2.2 × 10-2Pa, Ar throughput are 50sccm, and Cu foils substrate bias is -150V；It obtains pre-
Treated Cu foil matrixes.
(2) Cr binder courses are deposited in pretreated Cu foils matrix surface cathodic arc evaporation, to alleviate Cu foil matrixes
Excuse me, but I must be leaving now with coating coefficient of thermal expansion problem and enhances film-film-substrate binding strength：
Deposition chambers operating temperature is heated to 350 DEG C, Cu foil matrixes are heated to 400 DEG C, and extract deposition chamber gas
Body.Long-time heating toasts deposition chamber, to remove the pollutants such as the steam of deposition chamber inner wall absorption and oxygen.Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, Ar gas is passed through, sets gas flow as 100sccm, adjusts deposition chamber
Environmental pressure is to 1.0Pa, and by metal Cr target arc power power regulations to 2kW, work 30min.Metal Cr targets are through prevapourising
After processing, deposition chamber temperature is set as 400 DEG C, Cu foils substrate temperature is 400 DEG C, rotates sample stage, makes Cu foil matrix faces
Metal Cr targets, and be 15cm with the distances of metal Cr targets, deposition chambers Ar atmospheric pressures are adjusted to 0.8Pa, are steamed using cathode arc
Hair deposition Cr binder courses, Cr metal arcs target power output is 1.5kW, sedimentation time 10min, and Cu foil matrixes add in deposition process
The back bias voltage of load -50V.
(3) on the Cr binder courses with cathodic arc evaporation depositing TiN transition zone support is provided for surface functional layer：
After Cr binder courses deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 400
DEG C, it is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 150sccm, N2Intrinsic standoff ratio is 40%, using cathode electricity
Arc hydatogenesis TiN transition zones, Ti metal arcs target power output are 1.5kW, sedimentation time 10min, Cu foil bases in deposition process
The back bias voltage of body loading -50V.
(4) TiNiN surface functional layers are co-deposited with cathodic arc evaporation on the TiN transition zones：
After TiN transition zones deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 400
DEG C, sample stage is rotated, Cu foils matrix is made to be located at the centre position of metal Ti targets and W metal target, and be with the spacing of two target
15cm is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 150sccm, N2Qi leel pressure ratio is 40%.It is heavy to adjust
Product chamber pressure opens Ti electric arc targets and Ni electric arc targets to 0.8Pa, and Ti electric arcs target power output is 2.5kW, Ni electric arc target power output
For 0kW, the back bias voltage of Cu foil matrix loadings -50V in deposition process, matrix pivoted frame rotating speed is 1rpm, sedimentation time 30min,
Deposition obtains TiNiN surface functional layers.In TiNiN surface functional layers the content of Ti, Ni and N element be followed successively by respectively 50at.%,
0at.% and 50at.%；The thickness of the TiNiN surface functional layers is 50nm.
Embodiment 3
The present embodiment 3 provides a kind of preparation method of high power capacity transition metal nitride coating electrode material, including as follows
Step：
(1) Cu foils substrate pretreated：With embodiment 2.
(2) Cr binder courses are deposited in pretreated Cu foils matrix surface cathodic arc evaporation, to alleviate Cu foil matrixes
Excuse me, but I must be leaving now with coating coefficient of thermal expansion problem and enhances film-film-substrate binding strength：
Deposition chambers operating temperature is heated to 400 DEG C, Cu foil matrixes are heated to 450 DEG C, and extract deposition chamber gas
Body.Long-time heating toasts deposition chamber, to remove the pollutants such as the steam of deposition chamber inner wall absorption and oxygen.Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, Ar gas is passed through, sets gas flow as 100sccm, adjusts deposition chamber
Environmental pressure is to 2.0Pa, and by metal Cr target arc power power regulations to 5kW, work 10min.Metal Cr targets are through prevapourising
After processing, deposition chamber temperature is set as 400 DEG C, Cu foils substrate temperature is 450 DEG C, rotates sample stage, makes Cu foil matrix faces
Metal Cr targets, and be 20cm with the distances of metal Cr targets, deposition chambers Ar atmospheric pressures are adjusted to 1.5Pa, are steamed using cathode arc
Hair deposition Cr binder courses, Cr metal arcs target power output is 2.5kW, sedimentation time 5min, Cu foils matrix loading in deposition process-
The back bias voltage of 150V.
(3) CrN transition zones are deposited with cathodic arc evaporation on the Cr binder courses, support is provided for surface functional layer：
After Cr binder courses deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 450
DEG C, it is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 300sccm, N2Intrinsic standoff ratio is 60%, using cathode electricity
Arc hydatogenesis CrN transition zones, Cr metal arcs target power output are 2.5kW, sedimentation time 5min, Cu foil matrixes in deposition process
The back bias voltage of loading -150V.
(4) CrCuN surface functional layers are co-deposited with cathodic arc evaporation on the CrN transition zones：
After CrN transition zones deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 450
DEG C, sample stage is rotated, Cu foils matrix is made to be located at the centre position of metal Cr targets and Ni metal target, and be with the spacing of two target
20cm is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 300sccm, N2Qi leel pressure ratio is 60%.It is heavy to adjust
Product chamber pressure opens Cr electric arc targets and Cu electric arc targets to 1.5Pa, and Cr electric arcs target power output is 2.0kW, Cu electric arc target power output
For 2.0kW, the back bias voltage of Cu foil matrix loadings -150V in deposition process, matrix pivoted frame rotating speed is 4rpm, and sedimentation time is
10min, deposition obtain CrCuN surface functional layers.The content of Cr, Cu and N element is followed successively by respectively in CrCuN surface functional layers
20at.%, 25at.% and 55at.%；The thickness of the CrCuN surface functional layers is 1000nm.
Embodiment 4
The present embodiment 4 provides a kind of preparation method of high power capacity transition metal nitride coating electrode material, including as follows
Step：
(1) Cu foils substrate pretreated：With embodiment 2.
(2) Cr binder courses are deposited in pretreated Cu foils matrix surface cathodic arc evaporation, to alleviate Cu foil matrixes
Excuse me, but I must be leaving now with coating coefficient of thermal expansion problem and enhances film-film-substrate binding strength：
Deposition chambers operating temperature is heated to 380 DEG C, Cu foil matrixes are heated to 420 DEG C, and extract deposition chamber gas
Body.Long-time heating toasts deposition chamber, to remove the pollutants such as the steam of deposition chamber inner wall absorption and oxygen.Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, Ar gas is passed through, sets gas flow as 100sccm, adjusts deposition chamber
Environmental pressure is to 1.5Pa, and by metal Cr target arc power power regulations to 3kW, work 20min.Metal Cr targets are through prevapourising
After processing, deposition chamber temperature is set as 400 DEG C, Cu foils substrate temperature is 420 DEG C, rotates sample stage, makes Cu foil matrix faces
Metal Cr targets, and be 18cm with the distances of metal Cr targets, deposition chambers Ar atmospheric pressures are adjusted to 1.2Pa, are steamed using cathode arc
Hair deposition Cr binder courses, Cr metal arcs target power output is 2.0kW, sedimentation time 8min, Cu foils matrix loading in deposition process-
The back bias voltage of 100V.
(3) ZrN transition zones are deposited with cathodic arc evaporation on the Cr binder courses, support is provided for surface functional layer：
After Cr binder courses deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 420
DEG C, it is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 230sccm, N2Intrinsic standoff ratio is 50%, using cathode electricity
Arc hydatogenesis ZrN transition zones, Zr metal arcs target power output are 2.0kW, sedimentation time 8min, Cu foil matrixes in deposition process
The back bias voltage of loading -100V.
(4) ZrAg N surface functional layers are co-deposited with cathodic arc evaporation on the ZrN transition zones：
After ZrN transition zones deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 420
DEG C, sample stage is rotated, Cu foils matrix is made to be located at the centre position of metal Zr targets and metal Ag targets, and be with the spacing of two target
18cm is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 230sccm, N2Qi leel pressure ratio is 50%.It is heavy to adjust
Product chamber pressure opens Zr electric arc targets and Ag electric arc targets to 1.2Pa, and Zr electric arcs target power output is 2.2kW, Ag electric arc target power output
For 1.0kW, the back bias voltage of Cu foil matrix loadings -100V in deposition process, matrix pivoted frame rotating speed is 2.5rpm, and sedimentation time is
20min, deposition obtain ZrAgN surface functional layers.The content of Zr, Ag and N element is followed successively by respectively in ZrAgN surface functional layers
35at.%, 13at.% and 52at.%；The thickness of the ZrAgN surface functional layers is 500nm.
Embodiment 5
The present embodiment 5 provides a kind of preparation method of high power capacity transition metal nitride coating electrode material, including as follows
Step：
(1) Cu foils substrate pretreated：With embodiment 2.
(2) Cr binder courses are deposited in pretreated Cu foils matrix surface cathodic arc evaporation, to alleviate Cu foil matrixes
Excuse me, but I must be leaving now with coating coefficient of thermal expansion problem and enhances film-film-substrate binding strength：
Deposition chambers operating temperature is heated to 360 DEG C, Cu foil matrixes are heated to 430 DEG C, and extract deposition chamber gas
Body.Long-time heating toasts deposition chamber, to remove the pollutants such as the steam of deposition chamber inner wall absorption and oxygen.Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, Ar gas is passed through, sets gas flow as 100sccm, adjusts deposition chamber
Environmental pressure is to 1.8Pa, and by metal Cr target arc power power regulations to 4kW, work 15min.Metal Cr targets are through prevapourising
After processing, deposition chamber temperature is set as 400 DEG C, Cu foils substrate temperature is 430 DEG C, rotates sample stage, makes Cu foil matrix faces
Metal Cr targets, and be 17cm with the distances of metal Cr targets, deposition chambers Ar atmospheric pressures are adjusted to 1.3Pa, are steamed using cathode arc
Hair deposition Cr binder courses, Cr metal arcs target power output is 2.2kW, sedimentation time 7min, Cu foils matrix loading in deposition process-
The back bias voltage of 120V.
(3) HfN transition zones are deposited with cathodic arc evaporation on the Cr binder courses, support is provided for surface functional layer：
After Cr binder courses deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 430
DEG C, it is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 200sccm, N2Intrinsic standoff ratio is 45%, using cathode electricity
Arc hydatogenesis HfN transition zones, Hf metal arcs target power output are 2.2kW, sedimentation time 7min, Cu foil matrixes in deposition process
The back bias voltage of loading -120V.
(4) HfNiN surface functional layers are co-deposited with cathodic arc evaporation on the HfN transition zones：
After HfN transition zones deposition is completed, maintain the temperature of deposition chamber in 400 DEG C, the temperature of Cu foil matrixes 430
DEG C, sample stage is rotated, Cu foils matrix is made to be located at the centre position of metal Hf targets and W metal target, and be with the spacing of two target
17cm is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas is 200sccm, N2Qi leel pressure ratio is 45%.It is heavy to adjust
Product chamber pressure opens Hf electric arc targets and Ni electric arc targets to 1.3Pa, and Hf electric arcs target power output is 2.0kW, Ni electric arc target power output
For 2.0kW, the back bias voltage of Cu foil matrix loadings -120V in deposition process, matrix pivoted frame rotating speed is 3rpm, and sedimentation time is
15min, deposition obtain HfNiN surface functional layers.The content of Hf, Ni and N element is followed successively by respectively in HfNiN surface functional layers
25at.%, 30at.% and 45at.%；The thickness of the HfNiN surface functional layers is 200nm.
Embodiment 6
1. a pair transition metal nitride coating electrode material of the invention carries out XRD and sem analysis respectively, such as Fig. 2~Fig. 6
It is shown.It is seen that the coating electrode material of the present invention has high-specific surface area.
2. respectively with the dilution salpeter solution of 0.01mol/L and 0.2mol/L to transition metal nitrogen made from embodiment 2~5
Compound coating electrode material carries out chemical etching, and detects its capability value.
Survey result as shown in Table 1 and Table 2：
Capability value of the 1 transition metal nitride coating electrode material of table after the dilution salpeter solution of 0.01mol/L corrodes
Capability value of the 2 transition metal nitride coating electrode material of table after the dilution salpeter solution of 0.2mol/L corrodes
It can be seen that from Tables 1 and 2, dilution of the coating electrode material of embodiment 2~5 through 0.01mol/L or 0.2mol/L
After salpeter solution corrodes, it can reach higher stored energy capacitance value, the transition metal nitride coating further illustrated the present invention
Electrode material has high stored energy capacitance.
Finally it should be noted that the above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof.To the greatest extent
Pipe is described in detail the present invention with reference to above-described embodiment, those of ordinary skills in the art should understand that：Still
The specific embodiment of the present invention can be modified or replaced equivalently, and without departing from any of spirit and scope of the invention
Modification or equivalent replacement, are intended to be within the scope of the claims of the invention.
Claims (10)
1. a kind of high power capacity transition metal nitride coating electrode material, it is characterised in that：Including matrix, it is deposited on described matrix
The Cr binder courses on surface, the MeN transition zones for being deposited on the Cr combinations layer surface and it is deposited on the MeN transition layer surface
MeXN surface functional layers；The Me of the MeN transition zones is at least one of Ti, Cr, Zr and Hf elements；The MeXN surface works
The Me of ergosphere is at least one of Ti, Cr, Zr and Hf element, at least one of X Ni, Cu and Ag element.
2. high power capacity transition metal nitride coating electrode material as described in claim 1, it is characterised in that：Described matrix is
Cu foil matrixes, the MeXN surface functional layers are equipped with the loose and porous structure formed through chemical etching.
3. a kind of preparation method of high power capacity transition metal nitride coating electrode material, which is characterized in that include the following steps：
(1) on the surface of matrix, cathodic arc evaporation deposits Cr binder courses first；
(2) MeN transition zones are deposited with cathodic arc evaporation and then on the Cr binder courses, the Me of the MeN transition zones is Ti,
At least one of Cr, Zr and Hf element；
(3) and then on the MeN transition zones cathodic arc evaporation is used, is co-deposited MeXN surface functional layers；The MeXN surfaces
The Me of functional layer is at least one of Ti, Cr, Zr and Hf element, at least one of X Ni, Cu and Ag element；
(4) MeXN surface functional layers described in diluting salpeter solution chemical etching are finally used, have the MeXN surface functional layers
Loose and porous structure.
4. preparation method as claimed in claim 3, which is characterized in that the concrete operations of the step (1) are：By deposition chambers
Operating temperature is heated to 350~400 DEG C, and matrix is heated to 400~450 DEG C, and extracts deposition chamber gas；Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, the Ar gas that gas flow is 100sccm is passed through, adjusts deposition chamber environment
Pressure is to 1.0~2.0Pa, and by metal Cr target arc power power regulations to 2~5kW, work 10~30min；Metal Cr targets
After prevapourising is handled, deposition chamber temperature is set as 400 DEG C, substrate temperature is 400~450 DEG C, rotates sample stage, makes matrix
Face metal Cr targets, and be 15~20cm with the distances of metal Cr targets, deposition chambers Ar atmospheric pressures are adjusted to 0.8~1.5Pa, are adopted
Cr binder courses are deposited with cathodic arc evaporation, Cr metal arcs target power output is 1.5~2.5kW, and sedimentation time is 5~10min, is sunk
Matrix loads the back bias voltage of -50~-150V during product.
5. preparation method as claimed in claim 4, which is characterized in that in the step (1), Ar gas is passed through to deposition chambers
Before, heated baking also is carried out to deposition chamber, to remove the pollutant of deposition chamber inner wall absorption.
6. preparation method as claimed in claim 3, which is characterized in that the concrete operations of the step (2) are：In Cr binder courses
After deposition is completed, the temperature of deposition chamber is maintained, at 400~450 DEG C, to be passed through N in 400 DEG C, the temperature of matrix2Gas adjusts stream
Amount so that Ar gas and N2The total flow of gas is 150~300sccm, N2Intrinsic standoff ratio is 40~60%, is sunk using cathodic arc evaporation
Product MeN transition zones, Me metal arcs target power output are 1.5~2.5kW, and sedimentation time is 5~10min, and matrix adds in deposition process
Carry the back bias voltage of -50~-150V.
7. preparation method as claimed in claim 3, which is characterized in that the concrete operations of the step (3) are：In MeN transition
After layer deposition is completed, the temperature of deposition chamber is maintained, at 400~450 DEG C, to rotate sample stage in 400 DEG C, the temperature of matrix, make
Matrix is located at the centre position of metal Me targets and metal X targets, and is 15~20cm with the spacing of two target, is passed through N2Gas is adjusted
Amount of restriction so that Ar gas and N2The total flow of gas is 150~300sccm, N2Qi leel pressure ratio is 40~60%, adjusts deposition chambers
Pressure opens Me electric arc targets and X electric arc targets to 0.8~1.5Pa, and deposition obtains MeXN surface functional layers.
8. preparation method as claimed in claim 7, which is characterized in that in the step (3), deposition MeXN surface functional layers
Me electric arc target power outputs are 2.0~2.5kW, X electric arc target power outputs are 0~2.0kW, and sedimentation time is 10~30min, in deposition process
Matrix loads the back bias voltage of -50~-150V, and matrix pivoted frame rotating speed is 1~4rpm.
9. preparation method as claimed in claim 7 or 8, which is characterized in that Me, X and N element in the MeXN surface functional layers
Content be followed successively by 20~50at.%, 0~30at.% and 45~55at.% respectively；The thickness of the MeXN surface functional layers
For 50~1000nm.
10. preparation method as claimed in claim 3, which is characterized in that the concrete operations of the step (4) are：With 0.01~
The dilution salpeter solution of 0.2mol/L corrodes MeXN surface functional layers, and the time is 5min~5h, obtains surface with loose porous
The transition metal nitride coating electrode material of structure.
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