CN207909719U - A kind of high power capacity transition metal nitride coated electrode - Google Patents
A kind of high power capacity transition metal nitride coated electrode Download PDFInfo
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- CN207909719U CN207909719U CN201820249632.5U CN201820249632U CN207909719U CN 207909719 U CN207909719 U CN 207909719U CN 201820249632 U CN201820249632 U CN 201820249632U CN 207909719 U CN207909719 U CN 207909719U
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- -1 transition metal nitride Chemical class 0.000 title claims abstract description 35
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 31
- 239000002346 layers by function Substances 0.000 claims abstract description 42
- 230000007704 transition Effects 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- 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 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000011888 foil Substances 0.000 claims description 12
- 238000003486 chemical etching Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 46
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000007772 electrode material Substances 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 description 70
- 239000007789 gas Substances 0.000 description 46
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 34
- 238000010891 electric arc Methods 0.000 description 18
- 238000005137 deposition process Methods 0.000 description 15
- 238000004062 sedimentation Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000007788 liquid Substances 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
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 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
- 150000001875 compounds Chemical class 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 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
- 150000003624 transition metals Chemical class 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
-
- 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
Abstract
The utility model discloses a kind of high power capacity transition metal nitride coated electrode, including matrix, be deposited on described matrix surface Cr binder courses, be deposited on the MeN transition zones of the Cr combinations layer surface and be deposited on the MeXN surface functional layers of the MeN transition layer surface；Me is Ti, Cr, Zr or Hf in the MeN transition zones；Me is Ti, Cr, Zr or Hf, X Ni, Cu or Ag in the MeXN surface functional layers.The utility model deposits transition metal nitride coating electrode material using cathodic arc evaporation deposition technique on the surface of Cu foil matrixes, the preparation method implementation cost of the utility model is low, the coated electrode 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 of super capacitor, the application range for expanding ultracapacitor reduces the manufacturing cost of ultracapacitor.
Description
Technical field
The utility model is related to a kind of coated electrode more particularly to a kind of high power capacity transition metal nitride coated electrodes.
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 from device fabrication to 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 is high to also limit its popularization and application.
Currently, the material for making ultracapacitor positive electrode mainly has three classes：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
It by the way that redox reaction occurs in journey, and generates n or p-type doping rapidly in electrode material film, and then makes on electrode material
High Density Charge is stored, larger fake capacitance is generated and realizes electric energy storage.Ultracapacitor made of conducting polymer materials has
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 develop one kind having both high power capacity, high circulation stability, superior electrical conductivity, wide chemical window, foldable
The Novel super capacitor electrode of (flexibility), low cost, wide, environmental-friendly etc. the characteristics of suitable temperature range, to realize ultracapacitor
Large-scale production and extensive use.
Utility model content
The shortcomings that utility model aims to solve the above-mentioned prior arts and deficiency provide a kind of high power capacity transition gold
Belong to nitride coatings electrode, the surface of the transition metal nitride coated electrode has a loose and porous structure, binding force it is excellent and
Have the features such as high stored energy capacitance, is suitable for making electrode of super capacitor.
To reach its purpose, technical solution is used by the utility model：A kind of high power capacity transition metal nitride painting
Layer electrode, including matrix, be deposited on described matrix surface Cr binder courses, be deposited on the MeN transition of 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 be Ti, Cr, Zr or
Hf；The Me of the MeXN surface functional layers is Ti, Cr, Zr or Hf, X Ni, Cu or Ag.
Preferably, described matrix is Cu foil matrixes.
Further, the MeXN surface functional layers are equipped with through loose and porous structure made of chemical etching.
Preferably, the thickness of the MeXN surface functional layers is 50~1000nm.
Preferably, in the MeXN surface functional layers content of Me, X and N element be followed successively by respectively 20~50at.%, 0~
30at.% and 45~55at.%.
Further, the Cr binder courses and the MeN transition zones are to be deposited using cathodic arc evaporation.
Further, the MeXN surface functional layers are to be co-deposited using cathodic arc evaporation.
Preferably, the preparation method of the high power capacity transition metal nitride coated electrode, includes the following steps：
(1) Cr binder courses are deposited with cathodic arc evaporation on the surface of matrix 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 Ti, Cr, Zr or Hf；
(3) and then on the MeN transition zones cathodic arc evaporation is used, MeXN surface functional layers are co-deposited；The MeXN
The Me of surface functional layer is Ti, Cr, Zr or Hf, X Ni, Cu or Ag；
(4) finally make the MeXN surface functional layers with MeXN surface functional layers described in salpeter solution chemical etching are diluted
Has loose and porous structure.
The Cr binder courses can alleviate the coefficient of thermal expansion between matrix and coating and 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 itself have excellent electric conductivity, chemical stability and
Mechanical property is a kind of excellent capacitor electrode material.
Preferably, the concrete operations of the step (1) are：Deposition chambers operating temperature is heated to 350~400 DEG C, base
Body is heated to 400~450 DEG C, and extracts deposition chamber gas；When deposition chambers vacuum reaches background vacuum 1.0 × 10- 3After Pa, it is passed through the Ar gas that gas flow is 100sccm, adjusts deposition chamber environmental pressure to 1.0~2.0Pa, by metal Cr
Target arc power power regulation is to 2~5kW, and work 10~30min；Metal Cr targets set deposit cavity after prevapourising is handled
Temperature is 400 DEG C, and substrate temperature is 400~450 DEG C, rotates sample stage, makes matrix face metal Cr targets, and with metal Cr targets
Distance be 15~20cm, adjust deposition chambers Ar atmospheric pressures to 0.8~1.5Pa, combined using cathodic arc evaporation deposition Cr
Layer.
Preferably, in the step (1), the Cr metal arc target power outputs that cathodic arc evaporation deposits Cr binder courses are 1.5
~2.5kW, sedimentation time are 5~10min, and matrix loads the back bias voltage of -50~-150V in deposition process.
Preferably, in the step (1), before being passed through Ar gas to deposition chambers, heated baking also is carried out to deposition chamber, with
Remove the pollutant of deposition chamber inner wall absorption.
Preferably, the concrete operations of the step (2) are：After Cr binder courses deposition is completed, deposition chamber is maintained
Temperature, at 400~450 DEG C, is passed through N in 400 DEG C, the temperature of matrix2Gas adjusts flow so that Ar gas and N2The total flow of gas is
150~300sccm, N2Intrinsic standoff ratio is 40~60%, and MeN transition zones are deposited using cathodic arc evaporation.
Preferably, in the step (2), the Me metal arc target power outputs that cathodic arc evaporation deposits MeN transition zones are 1.5
~2.5kW, sedimentation time are 5~10min, and matrix loads the back bias voltage of -50~-150V in deposition process.
Preferably, the concrete operations of the step (3) are：After MeN transition zones deposition is completed, deposition chamber is maintained
Temperature in 400 DEG C, the temperature of matrix at 400~450 DEG C, rotate sample stage, matrix made to be located at metal Me targets and metal X targets
Centre position, and be 15~20cm with the spacing of two target, it is passed through N2Gas adjusts flow so that Ar gas and N2The total flow of gas
For 150~300sccm, N2Qi leel pressure ratio is 40~60%, adjusts deposition chambers pressure to 0.8~1.5Pa, while opening Me electricity
Arc target and X electric arc targets, deposition obtain MeXN surface functional layers.
Preferably, in the step (3), the Me electric arc target power outputs of deposition MeXN surface functional layers are 2.0~2.5kW, X electricity
Arc target power output is 0~2.0kW, and sedimentation time is 10~30min, and matrix loads the back bias voltage of -50~-150V in deposition process,
Matrix pivoted frame rotating speed is 1~4rpm.
Preferably, the concrete operations of the step (4) are：MeXN is corroded with the dilution salpeter solution of 0.01~0.2mol/L
Surface functional layer, time are 5min~5h, obtain surface with loose and porous structure, binding force is excellent and the mistake of high stored energy capacitance
Cross metal nitride coatings electrode material.
Preferably, the concrete operations of the step (4) are：MeXN is corroded with the dilution salpeter solution of 0.01~0.2mol/L
Surface functional layer, time are 1h~5h, obtain surface with loose and porous structure, binding force is excellent and the transition of high stored energy capacitance
Metal nitride coatings electrode material.
The beneficial effects of the utility model are：The utility model is using cathodic arc evaporation deposition technique in Cu foil matrixes
Surface deposits transition metal nitride coating electrode material, and the preparation method implementation cost of the utility model is low, prepares gained
Coated electrode has high-specific surface area and high stored energy capacitance, also has excellent electric conductivity, chemical stability and flexibility, is suitable for
Electrode of super capacitor is made, the application range of ultracapacitor is expanded, reduces the manufacturing cost of ultracapacitor.
Description of the drawings
Fig. 1 is the structural schematic diagram of the high power capacity transition metal nitride coated electrode of the utility model；
Fig. 2 is the XRD spectrum of the high power capacity transition metal nitride coated electrode of the utility model；
Fig. 3 is the surfaces SEM of the high power capacity transition metal nitride coated electrode of the utility model, Cross Section Morphology figure；
Fig. 4 is that the dilution nitric acid of the high power capacity transition metal nitride coated electrode through 0.01mol/L of the utility model is molten
Surface topography map after liquid erosion；
Fig. 5 is that the dilution nitric acid of the high power capacity transition metal nitride coated electrode through 0.2mol/L of the utility model is molten
Surface topography map after liquid erosion；
Fig. 6 is the dilution salpeter solution of the high power capacity transition metal nitride coated electrode through 0.2mol/L of the utility model
XRD spectrum after erosion.
Specific implementation mode
It more clearly to state the technical solution of the utility model, is further illustrated with reference to specific embodiment, but not
It can be used to limit the utility model, this is only the section Example of the utility model.
Embodiment 1
The present embodiment 1 provides a kind of high power capacity transition metal nitride coated electrode, as shown in Figure 1, including Cu foil matrixes
1, the Cr binder courses 2 on 1 surface of Cu foils matrix are deposited on, the MeN transition zones 3 on 2 surface of Cr binder courses is deposited on and is deposited on MeN
The MeXN surface functional layers 4 on 3 surface of transition zone.Specifically, Me is Ti, Cr, Zr or Hf in MeN transition zones 3；MeXN functions of surface
Me is Ti, Cr, Zr or Hf, X Ni, Cu or Ag in layer 4；MeXN surface functional layers 4 are equipped with through loose more made of chemical etching
Pore structure.
Embodiment 2
The present embodiment 2 provides a kind of preparation method of high power capacity transition metal nitride coated electrode, includes the following steps：
(1) Cu foils substrate pretreated：
After Cu foil matrixes are carried out mechanical lapping and polishing treatment, started the cleaning processing with solvent：First use 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 cleaning 5min to Cu foils matrix, and ion source is banged
The environmental pressure for hitting cleaning treatment is 2.2 × 10-2Pa, Ar throughput are 50sccm, and Cu foil 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 steam and the pollutants such as oxygen of the absorption of deposition chamber inner wall.Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, it is passed through Ar gas, gas flow is set 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 foil substrate temperatures are 400 DEG C, rotate sample stage, make Cu foil matrix faces
Metal Cr targets, and be 15cm at a distance from 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 arc target power outputs are 1.5kW, sedimentation time 10min, and Cu foil matrixes add in deposition process
The back bias voltage of load -50V.
(3) cathodic arc evaporation depositing TiN transition zone is used on the Cr binder courses, and 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 arc target power outputs are 1.5kW, sedimentation time 10min, Cu foil bases in deposition process
The back bias voltage of body load -50V.
(4) cathodic arc evaporation is used on the TiN transition zones, is co-deposited TiNiN surface functional layers：
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, so that Cu foil matrixes is 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 arc target power outputs are 2.5kW, Ni electric arc target power output
For 0kW, the back bias voltage of Cu foil matrix loads -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 coated electrode, includes the following steps：
(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 steam and the pollutants such as oxygen of the absorption of deposition chamber inner wall.Work as deposit cavity
Room vacuum reaches background vacuum 1.0 × 10-3After Pa, it is passed through Ar gas, gas flow is set as 100sccm, adjusts deposition chambers
Interior environmental pressure is to 2.0Pa, and by metal Cr target arc power power regulations to 5kW, work 10min.Metal Cr targets are steamed through pre-
After hair processing, deposition chamber temperature is set as 400 DEG C, Cu foil substrate temperatures are 450 DEG C, rotate sample stage, make Cu foils matrix just
It is 20cm to metal Cr targets, and at a distance from metal Cr targets, adjusts deposition chambers Ar atmospheric pressures to 1.5Pa, using cathode arc
Hydatogenesis Cr binder courses, Cr metal arc target power outputs are 2.5kW, sedimentation time 5min, and Cu foil matrixes add in deposition process
The back bias voltage of load -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 arc target power outputs are 2.5kW, sedimentation time 5min, Cu foil matrixes in deposition process
The back bias voltage of load -150V.
(4) cathodic arc evaporation is used on the CrN transition zones, is co-deposited CrCuN surface functional layers：
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, so that Cu foil matrixes is 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 arc target power outputs are 2.0kW, Cu electric arc target power output
For 2.0kW, the back bias voltage of Cu foil matrix loads -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 coated electrode, includes the following steps：
(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 steam and the pollutants such as oxygen of the absorption of deposition chamber inner wall.Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, it is passed through Ar gas, gas flow is set 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 foil substrate temperatures are 420 DEG C, rotate sample stage, make Cu foil matrix faces
Metal Cr targets, and be 18cm at a distance from 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 arc target power outputs are 2.0kW, sedimentation time 8min, Cu foil matrixes load-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 arc target power outputs are 2.0kW, sedimentation time 8min, Cu foil matrixes in deposition process
The back bias voltage of load -100V.
(4) cathodic arc evaporation is used on the ZrN transition zones, is co-deposited ZrAg N surface functional layers：
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, so that Cu foil matrixes is 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 arc target power outputs are 2.2kW, Ag electric arc target power output
For 1.0kW, the back bias voltage of Cu foil matrix loads -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 coated electrode, includes the following steps：
(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 steam and the pollutants such as oxygen of the absorption of deposition chamber inner wall.Work as deposition chambers
Vacuum reaches background vacuum 1.0 × 10-3After Pa, it is passed through Ar gas, gas flow is set 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 foil substrate temperatures are 430 DEG C, rotate sample stage, make Cu foil matrix faces
Metal Cr targets, and be 17cm at a distance from 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 arc target power outputs are 2.2kW, sedimentation time 7min, Cu foil matrixes load-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 arc target power outputs are 2.2kW, sedimentation time 7min, Cu foil matrixes in deposition process
The back bias voltage of load -120V.
(4) cathodic arc evaporation is used on the HfN transition zones, is co-deposited HfNiN surface functional layers：
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, so that Cu foil matrixes is 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 arc target power outputs are 2.0kW, Ni electric arc target power output
For 2.0kW, the back bias voltage of Cu foil matrix loads -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. the transition metal nitride coated electrode of pair the utility model carries out XRD and sem analysis respectively, such as Fig. 2~figure
Shown in 6.It is seen that the coated electrode of the utility model has high-specific surface area.
2. using the dilution salpeter solution of 0.01mol/L and 0.2mol/L to transition metal nitrogen made from embodiment 2~5 respectively
Compound coated electrode carries out chemical etching, and detects its capability value.
It is as shown in Table 1 and Table 2 to survey result：
Capability value of the 1 transition metal nitride coated electrode of table after the dilution salpeter solution of 0.01mol/L corrodes
Capability value of the 2 transition metal nitride coated electrode of table after the dilution salpeter solution of 0.2mol/L corrodes
It can be seen that from Tables 1 and 2, dilution nitric acid of the coated electrode through 0.01mol/L or 0.2mol/L of embodiment 2~5
After solution corrodes, it can reach higher stored energy capacitance value, further illustrate the transition metal nitride coating of the utility model
Electrode has high stored energy capacitance.
Finally it should be noted that above example is only to illustrate the technical solution of the utility model rather than limits it
System.Although the utility model is described in detail with reference to above-described embodiment, those of ordinary skill in the art should
Understand：Specific embodiment of the present utility model can be still modified or replaced equivalently, and it is new without departing from this practicality
Any modification of type spirit and scope or equivalent replacement should all cover in the right of the utility model.
Claims (6)
1. a kind of high power capacity transition metal nitride coated electrode, it is characterised in that：Including matrix, it is deposited on described matrix surface
Cr binder courses, be deposited on the MeN transition zones of the Cr combinations layer surface and be deposited on the MeXN of the MeN transition layer surface
Surface functional layer；The Me of the MeN transition zones is Ti, Cr, Zr or Hf；The Me of the MeXN surface functional layers be Ti, Cr, Zr or
Hf, X Ni, Cu or Ag.
2. high power capacity transition metal nitride coated electrode as described in claim 1, it is characterised in that：Described matrix is Cu foils
Matrix.
3. high power capacity transition metal nitride coated electrode as claimed in claim 1 or 2, it is characterised in that：The MeXN tables
Face functional layer is equipped with through loose and porous structure made of chemical etching.
4. high power capacity transition metal nitride coated electrode as claimed in claim 3, it is characterised in that：The MeXN surface works
The thickness of ergosphere is 50~1000nm.
5. high power capacity transition metal nitride coated electrode as described in claim 1, it is characterised in that：The Cr binder courses and
The MeN transition zones are to be deposited using cathodic arc evaporation.
6. high power capacity transition metal nitride coated electrode as described in claim 1, it is characterised in that：The MeXN surface works
Ergosphere is to be co-deposited using cathodic arc evaporation.
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| CN108198698A (en) * | 2018-02-11 | 2018-06-22 | 广州大学 | A kind of high power capacity transition metal nitride coating electrode material and preparation method thereof |
| CN113122843A (en) * | 2021-04-05 | 2021-07-16 | 莫日根 | Preparation method of aluminum alloy composite board |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108198698A (en) * | 2018-02-11 | 2018-06-22 | 广州大学 | A kind of high power capacity transition metal nitride coating electrode material and preparation method thereof |
| CN108198698B (en) * | 2018-02-11 | 2024-04-09 | 广州大学 | High-capacity transition metal nitride coating electrode material and preparation method thereof |
| CN113122843A (en) * | 2021-04-05 | 2021-07-16 | 莫日根 | Preparation method of aluminum alloy composite board |
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