CN102201456A - Flexible metal substrate connected with back electrode of solar battery and fabrication method thereof - Google Patents
Flexible metal substrate connected with back electrode of solar battery and fabrication method thereof Download PDFInfo
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Abstract
The invention discloses a flexible metal substrate connected with a back electrode of a solar battery and a fabrication method thereof. The flexible metal substrate has a structure made of stainless steel strip/copper/nickel/nickel-molybdenum alloy, wherein a nickel layer and a nickel-molybdenum alloy coating layer serve as diffusion barrier layers which are both multi-layer coating layers; and the mass content of molybdenum in the nickel-molybdenum alloy coating layer in the diffusion barrier layers is gradually increased from 10% to 80% layer by layer along the growth direction of the coating layer. Therefore, the diffusion of copper and Fe element in the steel strip can be effectively prevented, no new harmful elements are introduced, and the nickel-molybdenum alloy with high molybdenum content can enhance the bonding force between the substrate and a back electrode (Mo layer). Meanwhile, a Cu layer serves as a main current conduction layer, so that the Mo layer is only used as the back contact layer capable of forming good ohmic contact with an absorption layer. The flexible metal substrate used as the substrate of a CIGS (copper indium gallium selenide) solar battery can greatly lower the requirement on the thickness of the Mo layer, and the flexible substrate described in the invention can be manufactured continuously with low cost and high efficiency on a continuous electroplating production line.
Description
Technical field
The present invention relates to the flexible metal substrate that links to each other with back electrode of solar cell and the preparation method who on metallic substrates, prepares electric current master conducting shell and multilayer diffusion impervious layer with low-cost coil type technology successively.
Background technology
Under the background of energy crisis, solar cell becomes the focus that replaces in the energy research.The thin-film solar cells that wherein has the chalcopyrite phase (comprises solar cells such as copper indium diselenide, copper indium sulphur, Copper Indium Gallium Selenide, hereinafter to be referred as CIGS) thin-film solar cells stable performance, capability of resistance to radiation be strong, its photoelectric conversion efficiency is first of the various thin film solar cells at present, spectral response range is wide, power output is higher than other any kind of solar cell under overcast and rainy light intensity, be called next epoch one of the most promising cheap solar cell in the world, might be become one of main product of following photovoltaic cell.Compare with conventional energy resource, the realization of solar cell commercial competitiveness is the reduction of cost.The maximum bottleneck of present stage restriction solar cell development is the too high cost of raw material and production cost.
The typical structure of CIGS battery is: glass substrate, (Mo layer) dorsum electrode layer, (CIGS) absorbed layer, (CdS) resilient coating, double-deck ZnO Window layer: intrinsic ZnO (i.ZnO) layer and mix Al low-resistance transparent ZnO (AI:ZnO) layer, aluminium electrode.
Though the infiltration of the Na element in the hard soda-lime glass helps improving the efficient of battery, excessive N a can cause absorbed layer to come off at the interface of metal back electrode layer, influences the useful life of battery.Simultaneously, the hard soda-lime glass is that the solar cell of substrate can only adopt batch-wise prepared, and cost is very high.Producing all technologies based on batch-type also always can increase cost, so the explained hereafter of coil type is vital for reducing cost.Flexible substrate can satisfy the large tracts of land coiling of solar cell and produce.Compare polyimides, the sheet metal strip substrate more can stand the used high-temperature of high-quality CIGS material preparation, and still, the harmful element of metal substrate can be diffused into absorbed layer in the absorbed layer preparation process, influences the quality of forming film of absorbed layer.Therefore, it is very necessary preparing one deck diffusion impervious layer between metal substrate and back electrode.
In Thin Solid Films 431-432 (2003) 392-397, shown " Diffusion barriers forCIGS solar cells on metallic substrates " and disclosed a kind of diffusion impervious layer and preparation method thereof by people such as K.Herz.Adopt the method for rf magnetron sputtering on metal substrate, to prepare Al in the literary composition
2O
3, can effectively keep off the diffusion of base metals.Adopt the method for electron beam evaporation to prepare Al among the patent CN 1836338A
2O
3, metallic element Na has simultaneously also mixed in the barrier layer.Preparation ZrO is used as the barrier layer among the patent CN 1875127A.
Though above-mentioned barrier layer is barrier metal substrate elemental diffusion well, required aborning instrument cost height, and prepare consuming time longer; Phenomenons such as coming off appears in while diffusion impervious layer in the battery subsequent preparation process easily, cracking cause the battery production rate of finished products to reduce, and then increase cost.
The back electrode of battery, 1) and form good Ohmic contact between the absorbed layer role mainly contains 3 points in battery:, mainly contain the character decision of material; 2) use the effect of playing the conduction of current layer at battery, by the character and the thickness decision of material; 3) connect substrate and battery main body, prevent the battery cracking, come off.Vertical many metal materials comprise that quilts such as Mo, Pt, Au, Al, Ni, Ag, Cu try to be used for the back electrode material, but except Mo and Ni can form preferably the ohmic contact with the CIGS absorbed layer, these metals all can produce in various degree diffusion with CIGS in the process of preparation CIGS film.At high temperature Mo has the better stability than Ni.Though Mo and CIGS chemistry and CIGS sedimentary facies show it is compatible to high temperature, in the subsequent technique process, come off easily, promptly with the adhesion of substrate a little less than.
In Thin Solid Films 260 (1995) 26-31, the preparation method of CIGS back electrode of solar cell Mo layer is disclosed by " Sputteredmolybdenum bilayer back contact for copper indium diselenide-based polycrystalline thin-filmsolar cells " that the people showed such as John H.Scofield.Prepare double-deck Mo by magnetron sputtering in the document and satisfy battery respectively the adhesive force of having relatively high expectations of back electrode and lower resistance.This method is present general back electrode preparation technology.Reach requirement by double-decker, must increase Mo layer thickness and sputtering time like this, promptly increased the consumption of material and energy, brought extra cost.
The heterogeneous back electrode that is used for the CIS solar cell has been described in US005477088A.Adopt the Cu-Mo alloy as back electrode in the patent, this electrode can improve adhesive force and electric conductivity simultaneously.But Cu can be diffused into absorbed layer, thereby changes the metering ratio of element in the absorbed layer, influences the quality of forming film of absorbed layer.The diffusing capacity of Cu and uniformity are difficult to control, are unfavorable for the large tracts of land industrial production.
To sum up, the apparatus for preparation cost height of existing barrier layer, back electrode, power consumption is big, and substrate, barrier layer, the cracking of each layer of back electrode, the problem of coming off have reduced the rate of finished products of battery; The barrier layer of insulation makes needs expensive accurate etching instrument when preparation battery serial module structure, and the increase of etching technics has increased the defect rate of battery simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of flexible metal substrate that links to each other with back electrode of solar cell.This substrate comprises metallic substrates, conductive layer, multilayer diffusion impervious layer successively, and stronger adhesion is arranged between its each layer, and phenomenon such as can not occur ftractureing, come off.What link to each other with the multilayer diffusion impervious layer is back electrode.The multilayer diffusion impervious layer can effectively stop the diffusion of substrate harmful element to absorbed layer, simultaneously this barrier layer can and back electrode (Mo layer) carry out good binding; The design of conductive layer can reduce the demand to back electrode (Mo layer) thickness, reduces the consumption of noble metal Mo, reduces energy consumption simultaneously.And this flexible metal substrate can low-cost high-efficiency production in continuous coil type electroplating technology.
Another object of the present invention provides the preparation technology of above-mentioned flexible metal substrate.
A kind of flexible metal substrate that links to each other with back electrode of solar cell is substrate with the stainless steel band, and a side is plating conductive layer, multilayer diffusion impervious layer successively; Described conductive layer is a copper coating; Described multilayer diffusion impervious layer is made of two-layer at least nickel coating and two-layer at least nickel-molybdenum alloy coating successively, and described nickel coating links to each other with copper coating; What link to each other with back electrode is nickel-molybdenum alloy coating.
Described copper coating thickness is 1-3 μ m.
Described multilayer diffusion impervious layer preferably is made of 2-5 layer nickel coating and 2-10 layer nickel-molybdenum alloy coating successively.
The gross thickness of described 2～5 layers of nickel coating is 3-6 μ m; The gross thickness of described 2-10 layer (preferred 2-5 layer) nickel-molybdenum alloy coating is 1-3 μ m.
Nickel-molybdenum alloy coating in the described multilayer diffusion impervious layer successively is incremented to 80% along coating direction of growth molybdenum mass content by 10%.
Flexible metal substrate of the present invention is exactly to have copper coating, 2～5 layers of nickel coating, 2-10 layer nickel-molybdenum alloy coating to constitute in metallic substrates one side plating successively.
Described stainless steel band, thickness 0.1～0.3mm, surface roughness Ra is less than 0.5 μ m.
The preparation method of described flexible metal substrate comprises the steps:
1), stainless steel band is plated the front surface preliminary treatment;
2), the steel band after will handling places coating bath, a side is electroplated the thick copper coating of 1～3 μ m;
3), on copper coating, be electroplated to less two-layer nickel coating;
4), on nickel coating, electroplate nickel-molybdenum alloy coating two-layer at least and that successively increase progressively with coating direction of growth molybdenum content.
Described step 2) preparation of copper coating described in is to adopt acid bright copper plating; Solution composition: copper sulphate 150～220g/L, the concentrated sulfuric acid 50～70g/L, chloride ion 20～80mg/L, ethylenediamine tetra-acetic acid 50～70g/L; Technological parameter: 25～35 ℃ of temperature, current density 2～4A/dm
2
The preparation of nickel coating described in the described step 3) is in watts nickel solution, or the direct current ultrasonic wave is electroplated in the sulfamate nickel plating solution; Number of plies decision according to nickel coating is electroplated several times.
Described watt solution composition: nickelous sulfate 250～300g/L, nickel chloride 30～50g/L, boric acid 30～50g/L; Technological parameter: current density 3～6A/dm
2, pH value 3.4～4.5,50～60 ℃ of temperature, ultrasonic frequency 20～100kHz;
Described sulfamate solution composition: nickel sulfamic acid 300～450g/L, nickel chloride 0～15g/L, boric acid 30～45g/L; Technological parameter: current density 2～5A/dm
2, pH value 3.5～4.5,40～60 ℃ of temperature, ultrasonic frequency 20～100kHz.
The solution composition that nickel-molybdenum alloy coating described in the described step 4) is electroplated: sodium pyrophosphate 160g/L, sodium molybdate 20g/L, nickelous sulfate 40g/L, ammonium chloride 20g/L; Technological parameter: current density 2～20A/dm
2, pH value 7.8～9.3,20～40 ℃ of temperature; Current density is by 20A/dm during preparation
2Be reduced to 2A/dm gradually
2
The metallic substrates of flexible metal substrate of the present invention is selected stainless steel band for use, and thickness is 0.10～0.30mm, and preferred 0.10～0.20mm is to guarantee good flexibility and supporting role.Stainless steel band has stronger decay resistance, the high temperature corrosion environment in the time of can standing battery obsorbing layer and prepare.Therefore, when cell preparation, do not need to increase extra measure or coating and protect the stainless steel back side (being loaded with the another side of battery main body) not to be subjected to H
2Se, H
2The corrosion of S or S steam.
Back electrode not only will form good Ohmic contact with absorbed layer, is also bearing the effect of conduction current simultaneously, and prevents the task that battery comes off with the substrate strong bonded.For this reason, the preparation of back electrode Mo layer now realizes above requirement by double-decker usually, certainly will cause the thickness of Mo layer to increase like this, has increased the consumption and the energy consumption of material.Cu is that the copper of 0.2 micron thickness can provide the conductivity as the molybdenum of 0.5 micron thickness than Mo relatively economical and the better metal of conductivity.The present invention uses the copper layer to replace the conduction of current effect of molybdenum layer, and diversion function is separated with ohmic contact, and the effect that makes back electrode Mo layer just bear ohmic contact exists, and this will greatly reduce the demand to molybdenum layer thickness.But consider under the hot environment when CIGS prepares that the diffusion meeting of copper and base metals brings harm to absorbed layer.Therefore need between conductive copper layer and back electrode Mo layer, insert diffusion impervious layer.
Material for diffusion impervious layer is selected, and at first is conductor, and secondly this material can stop the diffusion of copper and base metals, can not introduce new harm element simultaneously.The present invention selects for use Ni and Ni-Mo alloy as diffusion impervious layer.Be substitution solid solution between Ni and Cu, the Fe, the solid solution of formation interface fuzzy mutually and between matrix reaches interatomic combination, helps combining between diffusion layer and matrix.Because Ni and Cu, Fe atomic size differ less, when diffusion, the diffusion coefficient between it is less.In electronics industry, Ni coating stops the diffusion of Cu to Si or Sn effectively always as the diffusion impervious layer between Cu/Si or the Cu/Sn.Defective in the metal, hole, crystal boundary are the express passways of diffusion.And single Ni coating, thickness reaches more than 25 microns just can reach atresia.The relative individual layer coating of the coating of sandwich construction more can effectively be avoided the existence of coating pin hole.In Ni coating, add diffusion barrier elements Mo atom, can improve the structure of Ni coating, increase diffusion barrier effect, reduce demand the Ni thickness of coating to the Cu atom.With the increase of Mo content in the coating, the Ni-Mo alloy layer changes fine and close amorphous structure, few, the free of pinholes of plating defect, and coating better heat stability into by crystalline state.But Ni-Mo alloy layer stress is bigger, and thickness of coating is prone to crackle when increasing.The present invention adopts Ni/Ni-Mo sandwich construction coating as diffusion impervious layer, and wherein Ni-Mo coating is increased to 80% gradient sandwich construction for the content along the direction Mo of coating growth by 10%.Sandwich construction can effectively be avoided the existence of pin hole in the coating, and sandwich construction can reduce the appearance that coating stress is avoided crackle simultaneously.
Relative single layer structure, nickel coating adopt sandwich construction to have for the pin hole that occurs in the coating, defective and better prevent effect.The coating of MULTI-LAYER NICKEL can be realized by the number that increases coating bath on tinuous production.With the watt nickel plating bath and the sulfamate nickel plating solution that do not add brightener, the nickel coating crystalline state that obtains is a column structure, and the nickel coating crystalline state that obtains in adding the watt plating bath of brightener is a block structure.Bulk nickel contains a lot of fine crystal, and crystal boundary is more.Be lower than under 700 ℃ of temperature, the diffusion of Cu in Ni is mainly the crystal boundary diffusion, and therefore, the column nickel that watts nickel solution that does not add brightener that the present invention adopts or sulfamate nickel plating solution obtain is higher to the diffusion efficiency ratio of copper.Adopt ultrasonic wave to electroplate simultaneously, can accelerate separating out of hydrogen, reduce the porosity of coating, reduce the internal stress of coating, avoid coating cracking to occur, make coating more smooth, fine and close.
The flexible metal substrate that is used for the production of CIGS thin-film solar cells coiling that the present invention is designed, each layer adhesion height cracking can not occur, come off, and improves the battery production rate of finished products.The preparation equipment needed thereby is simple, does not need large-scale expensive instrument, the stock utilization height, and preparation time is short.The present invention can reduce material cost and the manufacturing cost in the battery production link effectively.The metal barrier of conduction can be realized the series connection of battery by the mode with the imbrication sheet between the battery sheet, has avoided the use to the high accuracy visual device of costliness, has simplified preparation process, and has improved the rate of finished products of battery.
Between each layer of flexible metal substrate of the present invention: can form firm adhesion between Ni and Fe, Ni and Cu, Ni and the Ni-Mo, the problem that coating comes off can not occur.And the Ni-Mo coating with high Mo content has improved the adhesion between Mo and the back electrode.The Cu layer is taken on main conduction of current layer simultaneously, makes Mo layer (back electrode) just as forming the back contact that good ohmic contacts with absorbed layer.Therefore, adopt flexible metal substrate of the present invention can reduce demand greatly to the Mo layer thickness, and flexible metal substrate of the present invention can be on continuously plating product line low-cost production.The preparation equipment needed thereby is simple, does not need large-scale expensive instrument, the stock utilization height, and preparation time is short.The present invention can reduce material cost and the manufacturing cost in the battery production link effectively.
Description of drawings
Fig. 1 is a flexible metal substrate cross-sectional structure schematic diagram of the present invention;
1-substrate among the figure, 2-copper coating, 3-nickel coating, 4-nickel-molybdenum alloy coating;
(600 ℃, 30min) after the annealing, the cross section element is swept range distribution figure with the EDS line to Fig. 2 for the embodiment of the invention 1 prepares environment at the simulated battery absorbed layer.
As we can see from the figure, Ni coating does not stop the diffusion of diffuse elements such as Fe, Cr and Cu fully, but the diffusion barrier effect of process Ni, the relative amount of diffuse elements in coating reduces rapidly.At last, the Ni-Mo alloy layer that is increased gradually by Mo content is blocked the diffusion of diffuse elements to the absorbed layer direction fully.From figure, see between coating and substrate and each coating certain diffusion layer mutually being arranged simultaneously, guaranteed the binding ability between coating and substrate and each layer.
Fig. 3 be embodiment 1 sample coating surface sputter back electrode Mo layer film annealing (600 ℃, the 30min) surface topography after.
As we can see from the figure, the Mo layer film that on sample of the present invention, prepares, after annealing, homogeneous grain size is arranged closely, the phenomenon that cracking comes off do not occur.This explanation, adhesion height between flexible metal substrate of the present invention and the Mo layer film, and thermal coefficient of expansion is close with the Mo layer film, so through Overheating Treatment, the phenomenon that the Mo layer film on flexible metal substrate surface does not have cracking to come off.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Selecting 0.2 millimeters thick, roughness for use is that 0.2 micron stainless steel band is substrate.
Steel band is plated the front surface preliminary treatment, i.e. oil removing, nickel preplating are handled.Oil removing is the high temeperature chemistry oil removing, NaOH 70g/L, sodium carbonate 40g/L, sodium phosphate 25g/L, sodium metasilicate 10g/L, 80 ℃ of temperature, oil removing 3 minutes.After the oil removing fully, specimen surface is rinsed well, put into the nickel preplating coating bath again and carry out preplating one deck nickel to improve adhesion, nickel chloride 240g/L, concentrated hydrochloric acid 120ml/L, current density 3A/dm with distilled water
2, preplating 1 minute.
Steel band after handling is inserted in the copper facing coating bath, electroplate the copper coating of 2 micron thickness in a side.The copper facing condition, copper sulphate 180g/L, concentrated sulfuric acid 55g/L, chloride ion 70mg/L, ethylenediamine tetra-acetic acid 55g/L, 35 ℃ of temperature, current density 2A/dm
2
Do not adding in the mode that adopts ultrasonic wave to electroplate on the copper coating in the watts nickel solution of brightener and electroplating 4 layers of nickel coating, gross thickness is 3 microns.4 watt nickel coating baths are set in this example, and plating bath is identical in each coating bath, electroplate liquid formulation: nickelous sulfate 270g/L, nickel chloride 45g/L, boric acid 40g/L, technological parameter: current density 4A/dm
2, pH value 4.5,55 ℃ of temperature, anode is the pure nickel plate, ultrasonic frequency is respectively 28kHz, 50kHz, 80kHz, 45kHz.
On nickel coating, electroplate 5 layers, and the nickel-molybdenum alloy coating that increases in gradient with coating direction of growth molybdenum content, 2.5 microns of gross thickness.Preparation technology, sodium pyrophosphate 160g/L, sodium molybdate 20g/L, nickelous sulfate 40g/L, ammonium chloride 20g/L, current density 2～20A/dm
2, pH value 8.0,35 ℃ of temperature, inert anode.Current density is by 20A/dm in the preparation
2Be reduced to 2A/dm gradually
2, Mo content increases to 80% by 10% in the coating.On continuously plating product line, through 5 nickel molybdenum coating baths, current density is followed successively by 20A/dm to band in each coating bath successively
2, 15A/dm
2, 10A/dm
2, 5A/dm
2, 2A/dm
2
Selecting thickness for use is that 0.10 millimeter, roughness are that 0.3 stainless steel band is substrate.
Steel band is plated the front surface preliminary treatment.Processing method is identical with embodiment 1.
Steel band after handling is inserted in the copper facing coating bath, electroplate the copper coating of 1 micron thickness in a side.Solution composition copper sulphate 200g/L, concentrated sulfuric acid 60g/L, chloride ion 45mg/L, ethylenediamine tetra-acetic acid 65g/L, 30 ℃ of temperature, current density 4A/dm
2
Do not adding the MULTI-LAYER NICKEL coating of electroplating 6 microns of gross thickness in the watts nickel solution of brightener in the mode that adopts ultrasonic wave to electroplate on the copper coating.On continuously plating product line, obtain the nickel coating of sandwich construction by the number that increases the nickel coating bath.5 watt nickel coating baths are set in this example, and plating bath is identical in each coating bath, just changes frequency of ultrasonic.Electroplate liquid formulation: nickelous sulfate 250g/L, nickel chloride 40g/L, boric acid 45g/L, current density 3A/dm
2, pH value 4.5,50 ℃ of temperature, anode is the pure nickel plate, ultrasonic frequency is followed successively by 28kHz, 45kHz, 100kHz, 50kHz, 80kHz along the tape transport direction.
On nickel coating, electroplate 3 layers, and the nickel-molybdenum alloy coating that increases in gradient with coating direction of growth molybdenum content; 1 micron of gross thickness.Preparation technology, sodium pyrophosphate 160g/L, sodium molybdate 20g/L, nickelous sulfate 40g/L, ammonium chloride 20g/L, current density 2～20A/dm
2, pH value 8.0,35 ℃ of temperature, inert anode.Current density is by 18A/dm in the preparation
2Be reduced to 3A/dm gradually
2, Mo content increases to 70% by 15% in the coating.On continuously plating product line, through 3 nickel molybdenum coating baths, current density is followed successively by 18A/dm to band in each coating bath successively
2, 10A/dm
2, 3A/dm
2
Embodiment 3
Selecting thickness for use is that 0.10 millimeter, roughness are that 0.2 stainless steel band is substrate.
Steel band is plated the front surface preliminary treatment.Method is identical with embodiment 1.
Steel band after handling is inserted in the copper facing coating bath, electroplate the copper coating of 3 micron thickness in a side.The copper facing condition, copper sulphate 200g/L, concentrated sulfuric acid 65g/L, chloride ion 50mg/L, ethylenediamine tetra-acetic acid 60g/L, 30 ℃ of temperature, current density 3A/dm
2
On copper coating, electroplate 2 layers of nickel coating, 3 microns of gross thickness.Nickel coating is to prepare in nickel aminosulfonic bath.3 coating baths are set in this example, and plating bath is identical in each coating bath, electroplate liquid formulation: nickel sulfamic acid 380g/L, nickel chloride 10g/L, boric acid 40g/L, technological parameter: current density 4A/dm
2, pH value 4.0,55 ℃ of temperature, anode is the pure nickel plate, ultrasonic frequency 28kHz, 100kHz, 45kHz.
On nickel coating, electroplate 8 layers, and the nickel-molybdenum alloy coating that increases in gradient with coating direction of growth molybdenum content; 3 microns of gross thickness.Preparation technology, sodium pyrophosphate 160g/L, sodium molybdate 20g/L, nickelous sulfate 40g/L, ammonium chloride 20g/L, current density 2～20A/dm
2, pH value 8.0,35 ℃ of temperature, inert anode.Current density is by 20A/dm in the preparation
2Be reduced to 2A/dm gradually
2, Mo content increases to 80% by 10% in the coating.On continuously plating product line, through 8 nickel molybdenum coating baths, current density is followed successively by 20A/dm to band in each coating bath successively
2, 15A/dm
2, 12A/dm
2, 10A/dm
2, 8A/dm
2, 5A/dm
2, 3A/dm
2, 2A/dm
2
Claims (10)
1. flexible metal substrate that links to each other with back electrode of solar cell, it is characterized in that: described flexible metal substrate is substrate with the stainless steel band, and a side is plating conductive layer, multilayer diffusion impervious layer successively; Described conductive layer is a copper coating; Described multilayer diffusion impervious layer is made of two-layer at least nickel coating and two-layer at least nickel-molybdenum alloy coating successively, and described nickel coating links to each other with copper coating; What link to each other with back electrode is nickel-molybdenum alloy coating.
2. flexible metal substrate according to claim 1 is characterized in that, described copper coating thickness is 1-3 μ m.
3. flexible metal substrate according to claim 1 is characterized in that, described multilayer diffusion impervious layer is made of 2-5 layer nickel coating and 2-10 layer nickel-molybdenum alloy coating successively.
4. flexible metal substrate according to claim 1 is characterized in that, the gross thickness of described 2～5 layers of nickel coating is 3-6 μ m; The gross thickness of described 2-10 layer nickel-molybdenum alloy coating is 1-3 μ m.
5. according to claim 1 or 3 or 4 described flexible metal substrate, it is characterized in that: the nickel-molybdenum alloy coating in the described multilayer diffusion impervious layer successively is incremented to 80% along coating direction of growth molybdenum mass content by 10%.
6. flexible metal substrate according to claim 1 is characterized in that: described stainless steel band, and thickness 0.1～0.3mm, surface roughness Ra is less than 0.5 μ m.
7. the preparation method of the described flexible metal substrate of claim 1 is characterized in that, comprises the steps:
1), stainless steel band is plated the front surface preliminary treatment;
2), the steel band after will handling places coating bath, a side is electroplated the thick copper coating of 1～3 μ m;
3), on copper coating, be electroplated to less two-layer nickel coating;
4), on nickel coating, electroplate nickel-molybdenum alloy coating two-layer at least and that successively increase progressively with coating direction of growth molybdenum content.
8. method according to claim 7 is characterized in that,
Described step 2) preparation of copper coating described in is to adopt acid bright copper plating; Solution composition: copper sulphate 150～220g/L, the concentrated sulfuric acid 50～70g/L, chloride ion 20～80mg/L, ethylenediamine tetra-acetic acid 50～70g/L; Technological parameter: 25～35 ℃ of temperature, current density 2～4A/dm
2
9. method according to claim 7 is characterized in that,
The preparation of nickel coating described in the described step 3) is in watts nickel solution, or the direct current ultrasonic wave is electroplated in the sulfamate nickel plating solution;
Described watt solution composition: nickelous sulfate 250～300g/L, nickel chloride 30～50g/L, boric acid 30～50g/L; Technological parameter: current density 3～6A/dm
2, pH value 3.4～4.5,50～60 ℃ of temperature, ultrasonic frequency 20～100kHz;
Described sulfamate solution composition: nickel sulfamic acid 300～450g/L, nickel chloride 0～15g/L, boric acid 30～45g/L; Technological parameter: current density 2～5A/dm
2, pH value 3.5～4.5,40～60 ℃ of temperature, ultrasonic frequency 20～100kHz.
10. method according to claim 7 is characterized in that,
The solution composition that nickel-molybdenum alloy coating described in the described step 4) is electroplated: sodium pyrophosphate 160g/L, sodium molybdate 20g/L, nickelous sulfate 40g/L, ammonium chloride 20g/L; Technological parameter: current density 2～20A/dm
2, pH value 7.8～9.3,20～40 ℃ of temperature; Current density is by 20A/dm during preparation
2Be reduced to 2A/dm gradually
2
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| CN102443831A (en) * | 2011-12-26 | 2012-05-09 | 上海华友金镀微电子有限公司 | Electroplating process and production line of solar cell sheet solder strip |
| CN102828152A (en) * | 2012-09-20 | 2012-12-19 | 成都欣源光伏科技有限公司 | Preparation method of Mo film with low resistance rate |
| CN103258896A (en) * | 2012-02-17 | 2013-08-21 | 任丘市永基光电太阳能有限公司 | Manufacturing technology of soft CIGS thin film solar cell absorbing layer |
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| CN105206695A (en) * | 2014-06-05 | 2015-12-30 | 中物院成都科学技术发展中心 | Flexible solar cell with back protection layer and preparation method thereof |
| CN105206695B (en) * | 2014-06-05 | 2017-08-11 | 中物院成都科学技术发展中心 | Flexible solar battery with back of the body protective layer and preparation method thereof |
| CN105449010A (en) * | 2015-11-18 | 2016-03-30 | 北京四方创能光电科技有限公司 | Stainless-steel-substrate flexible CIGS film solar cell barrier layer manufacturing method |
| CN105449010B (en) * | 2015-11-18 | 2018-07-31 | 北京四方创能光电科技有限公司 | Stainless steel lining bottom flexible CIGS thin-film solar cell barrier layer preparation method |
| WO2019011932A1 (en) * | 2017-07-12 | 2019-01-17 | Hille & Müller GMBH | Low interfacial contact resistance material, use thereof and method of producing said material |
| CN110892553A (en) * | 2017-07-12 | 2020-03-17 | 希勒及穆勒有限公司 | Low interfacial contact resistance material, use thereof and method for manufacturing said material |
| CN110892553B (en) * | 2017-07-12 | 2022-12-30 | 希勒及穆勒有限公司 | Low interfacial contact resistance material, use thereof and method for manufacturing said material |
| US11732324B2 (en) | 2017-07-12 | 2023-08-22 | Hille & Müller GMBH | Low interfacial contact resistance material, use thereof and method of producing said material |
| CN113430557A (en) * | 2021-06-09 | 2021-09-24 | 有研工程技术研究院有限公司 | Multifunctional power layer electrode material and preparation method thereof |
| CN113430557B (en) * | 2021-06-09 | 2023-01-13 | 有研工程技术研究院有限公司 | Multifunctional power layer electrode material and preparation method thereof |
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