EP3993925A1 - Process for purifying metal nanowires - Google Patents
Process for purifying metal nanowiresInfo
- Publication number
- EP3993925A1 EP3993925A1 EP20734078.7A EP20734078A EP3993925A1 EP 3993925 A1 EP3993925 A1 EP 3993925A1 EP 20734078 A EP20734078 A EP 20734078A EP 3993925 A1 EP3993925 A1 EP 3993925A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nanowires
- metallic
- nanoparticles
- equal
- fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002070 nanowire Substances 0.000 title claims abstract description 159
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 92
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 81
- 239000000725 suspension Substances 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 53
- 229910052752 metalloid Inorganic materials 0.000 claims abstract description 45
- 150000002738 metalloids Chemical class 0.000 claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 40
- 229910001111 Fine metal Inorganic materials 0.000 claims abstract description 35
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 24
- 239000002042 Silver nanowire Substances 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000010908 decantation Methods 0.000 claims description 18
- 238000000746 purification Methods 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 239000007769 metal material Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002082 metal nanoparticle Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010946 fine silver Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 230000001502 supplementing effect Effects 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a new process for the purification of fine metal nanowires, such as silver nanowires, with a high form factor, more particularly having a form factor greater than or equal to 50, and with an average diameter less than or equal to 60. nm.
- Metal nanowires in particular silver nanowires, find a particularly interesting application in the manufacture of electrically conductive and transparent materials, in particular transparent electrodes which are of interest for applications of the optoelectronic type (touch screen, heating film , OLED, photovoltaic cells).
- metallic nanowires for example silver nanowires, constitute a particularly advantageous alternative to films based on transparent conductive oxides (known by the abbreviation "TCOs” for "Transparent Conductive. Oxides ”in English), for example based on tin and indium oxide, traditionally used for the production of transparent electrodes.
- a conductive and transparent system based on metallic nanowires can then be obtained by forming, from a suspension of nanowires in a solvent (for example, in water, methanol, isopropanol, etc.), a network percolating metal nanowires on a surface, for example glass.
- a solvent for example, in water, methanol, isopropanol, etc.
- Many advantages are associated with this manufacturing process: low cost, flexibility of the electrodes obtained, processability by wet process and at low temperature, etc., as described in the publication Langley et al. [1].
- the performance criteria of the conductive system based on metallic nanowires are determined according to the targeted applications, the performance in terms of surface resistance (also known as “square resistance”) and optical properties, in particular of transmittance and Haze factor, being of primary importance.
- Metal nanowires are generally produced, easily and in large quantities, by chemical synthesis in solution, via the reduction of metal salts, for example silver nitrate to obtain silver nanowires, by a polyol, typically ethylene glycol.
- metal salts for example silver nitrate to obtain silver nanowires
- a polyol typically ethylene glycol.
- this synthesis in solution is not a selective reaction, and impurities are produced during the synthesis, in particular low form factor metal nanoparticles, for example of the rod type.
- nanowires to the exclusion of other particles, in particular nanowires with an average diameter of less than 60 nm, typically between 30 and 40 nm, to access transparent conductive systems, meeting the criteria. of the aforementioned performance, having a low Haze factor and good electrical conduction. Such systems are particularly useful for many optoelectronic applications.
- the proposed purification methods are not entirely satisfactory in the context of fine metal nanowires, of small diameter, typically of average diameter less than or equal to 60 nm, and of high form factor (length / diameter ratio), typically greater. to 50.
- the methods proposed until now require a very long purification time, in particular for the decantation step.
- the purity of the products obtained is not always sufficient, with the undesirable presence of residual nanoparticles or of nanowires with low form factors.
- the present invention aims precisely to meet this need.
- the present invention relates to a method for purifying metallic nanowires, comprising at least the steps consisting of: (i) have a suspension of metallic nanoobjects in a hydroalcoholic solvent medium having a viscosity at 25 ° C strictly less than 10 mPa.s, said metallic nanoobjects including:
- Nanowires called “fine nanowires”, having a form factor greater than or equal to 50 and an average diameter less than or equal to 60 nm;
- - ancillary nanoparticles distinct from said fine nanowires, having a form factor less than or equal to 30, in particular less than or equal to 10, and an average equivalent diameter by volume less than or equal to 200 nm;
- fine nanowires is understood to denote metallic nanowires, in particular silver nanowires, having a form factor (length / diameter ratio) greater than or equal to 50 and an average diameter less than or equal. at 60 nm.
- the method of the invention is more particularly useful for isolating the fine metal nanowires from other secondary metal nanoparticles of low form factor, present in the reaction mixture after the synthesis in solution of the metal nanowires.
- the suspension of metallic nanoobjects in step (i) of the process of the invention is obtained, from the reaction mixture obtained at the end of a conventional synthesis of nanowires in solution, by carrying out a first decantation step, as described in document EP 3 021 230, aimed at removing some of the small undesirable particles.
- the nanoparticles of metal oxide (s) or metalloid (s) used according to the invention can be constituted by a material chosen from metal oxides, metalloid oxides, and mixtures thereof, in particular from metal oxides.
- they are silica nanoparticles.
- the nanoparticles of metal oxide (s) or metalloid (s) are more particularly introduced into the suspension of metal nanoobjects comprising said fine nanowires of interest, in a weight ratio of fine metal nanowires / oxide nanoparticles (s) metallic or metalloid (s) between 1: 1 and 1: 100, preferably between 1: 2 and 1: 20 and more preferably from 1: 8 to 1: 12, in particular about 1: 10.
- silica nanoparticles together with silver nanowires, has already been proposed in the context of the preparation of nanocomposites based on an epoxy resin, in order to improve and facilitate the dispersion of the nanowires.
- silver in the polymer matrix without impacting the quality of the inter-object contacts ([2], [3]).
- metal oxide s
- metalloid s
- metallic nanowires
- the inventors have observed that the addition of nanoparticles of metal oxide (s) or metalloid (s), such as silica nanoparticles, to the suspension of nanoobjects including fine metal nanowires to be purified, advantageously allows optimization of the purification process by settling.
- metal oxide s
- metalloid s
- the nanoparticles of metal oxide (s) or metalloid (s) are deposited on the fine metal nanowires.
- the purification by decantation according to the invention can be carried out in a significantly reduced time, compared to a decantation carried out from a suspension of metallic nanoobjects, without adding oxide nanoparticles ( metal (s) or metalloid (s).
- effective settling can thus be carried out in a period of less than 6 hours, in particular between 2 and 4 hours.
- the process thus makes it possible to save significant time, and therefore to save on the use of synthesis and purification tools.
- the purification process according to the invention makes it possible to achieve, with rapid settling, better selectivity in the separation between the fine metal nanowires and the other ancillary metal nanoparticles.
- the decantate based on fine metal nanowires obtained at the end of the decantation assisted by the nanoparticles of metal oxide (s) or metalloid (s) according to the invention, has less than 5% of nanoparticles. distinct metallic nanowires of interest.
- the yield of fine metal nanowires is also improved, even for rapid settling, typically lasting less than 6 hours.
- the process of the invention makes it possible to recover, at the end of the settling, more than 70%, in particular more than 80%, of the fine metal nanowires, present in the suspension of the starting metal nanoobjects.
- the process of the invention makes it possible to combine an acceleration of purification by settling, a gain in performance and a better selectivity of the separation between the fine nanowires of interest and the ancillary metal nanoparticles.
- the process of the invention based on a settling process, is particularly easy and inexpensive to implement. In particular, it does not require long and expensive centrifugation steps.
- FIG 1 represents the image, obtained by scanning electron microscopy (SEM), of fine silver nanowires.
- FIG 2 represents the photograph, obtained by scanning electron microscopy (SEM), of fine silver nanowires after addition of silica nanoparticles, as described in Example 3 which follows.
- the method of the invention is useful for isolating fine metal nanowires from a suspension containing other unwanted ancillary metal nanoparticles.
- fine nanowires is understood to denote metal nanowires having a form factor greater than or equal to 50 and a diameter less than or equal to 60 nm.
- the fine metal nanowires have an average diameter ranging from 10 to 60 nm, in particular from 20 to 50 nm and more particularly from 30 to 40 nm.
- the average length of the nanowires can be more particularly between 0.5 ⁇ m and 200 ⁇ m, in particular between 1 ⁇ m and 50 ⁇ m.
- the dimensions of metal nanowires can be evaluated by transmission electron microscopy (TEM) or by scanning electron microscopy (SEM).
- the mean diameter (mean length) refers to the mean value of the diameters (lengths) of a population of nanowires.
- the form factor is the length / diameter ratio.
- the fine metal nanowires more particularly have a form factor strictly greater than 50, preferably greater than or equal to 100 and more preferably greater than or equal to 150, in particular greater than or equal to 200 and more particularly between 200 and 1000 .
- the fine metal nanowires to be isolated according to the invention can more particularly be metal nanowires having an average diameter of between 20 and 50 nm and a form factor greater than or equal to 200.
- the metallic nanowires are formed from a metallic material, which can be chosen from elementary metals.
- the metallic material can also be a material bimetallic or a metal alloy which includes at least two types of metals, for example cupronickel (alloy of copper and nickel).
- the nanowires are formed from one or more metals.
- metals such as silver, gold, copper, nickel, core-shell systems having a core of copper, silver, nickel, platinum or palladium.
- the metallic nanowires of the invention are nanowires based on silver, gold, copper and / or nickel, that is to say that their composition by mass comprises at least 50 % by mass of one or more of these metals.
- metallic nanowires are nanowires of silver, gold, copper and / or nickel.
- the metal nanowires according to the invention are silver or copper nanowires.
- the metallic nanowires according to the invention are silver nanowires.
- ancillary metallic nanoparticles denotes the metallic nanoobjects present in said starting suspension, distinct from the fine nanowires according to the invention.
- nanoparticles are of the same chemical nature as the metal nanowires to be isolated. They are more particularly metallic nanoparticles co-produced during the synthesis of metallic nanowires.
- nanoparticles can be of spherical or anisotropic morphology.
- the ancillary metal nanoparticles more particularly have a form factor of less than or equal to 30, in particular less than or equal to 10, in particular between 1 and 8 and more particularly between 2 and 5.
- They may more particularly have a mean equivalent diameter by volume of less than or equal to 200 nm, in particular less than or equal to 100 nm and more particularly between 1 and 50 nm.
- equivalent diameter of a particle is understood to mean the diameter of the sphere of the same volume as the particle.
- the mean equivalent diameter is the mean value by volume of the equivalent diameters of a population of particles. This mean equivalent diameter can be determined by laser particle size distribution, by dynamic light scattering (DLS for "Dynamic light scattering" in English terminology) or by scanning electron microscopy.
- the ancillary metallic nanoparticles can be of a larger dimension strictly less than 200 nm, in particular between 1 and 100 nm. They may, for example, be globally spherical particles with an average diameter of between 5 and 80 nm.
- the term "dimensions" of a particle is understood to mean the size of the particle measured along the different axes (x), (y) and (z) of an orthogonal coordinate system.
- the dimensions of the particle may be its diameter and length.
- the dimensions measured along each of the (x), (y) and (z) axes are identical and correspond to the diameter of the particle.
- the ancillary metallic nanoparticles distinct from said fine nanowires, can thus be globally spherical nanoparticles, or strongly anisotropic nanoparticles, such as rods.
- the rods can, for example, have an average diameter greater than or equal to 200 nm, and a form factor typically between 2 and 30.
- the suspension in step (i) can be a suspension comprising fine silver nanowires, together with ancillary silver nanoparticles, distinct from said fine nanowires.
- the fine metallic nanowires and the ancillary metallic nanoparticles are present in the suspension in step (i) of the process of the invention in a nanowires / ancillary nanoparticles mass ratio of between 70/30 and 99.5 / 0 , 5.
- the metallic nanoobjects are formed only from said fine metallic nanowires and said ancillary metallic nanoparticles, as described above.
- the suspension in step (i) of the process of the invention is formed from a mixture of fine metal nanowires and ancillary metal nanoparticles, as described above, in a hydroalcoholic solvent medium.
- the suspension in step (i) of the method of the invention is a suspension of silver nanoobjects.
- the metallic nanoobjects of the suspension in step (i) comprise, or even are formed, of a mixture of fine silver nanowires and additional silver nanoparticles distinct from said fine nanowires.
- solvent medium is meant a single solvent or a mixture of at least two solvents.
- hydroalcoholic solvent medium is intended to denote a medium comprising one or more solvents chosen from water and / or alcohols, in particular C 1 to C 10 alcohols.
- the water can be present in an amount of 0 to 100% by mass in the aqueous-alcoholic solvent medium.
- the hydroalcoholic solvent medium comprises, or even is formed, of one or more solvents chosen from water and / or alcohols, preferably monoalcohols, C 1 to C 10, in particular C 1 to C 6, in particular chosen from methanol, ethanol and propanol, preferably methanol.
- solvents chosen from water and / or alcohols, preferably monoalcohols, C 1 to C 10, in particular C 1 to C 6, in particular chosen from methanol, ethanol and propanol, preferably methanol.
- the aqueous-alcoholic solvent medium in step (i) can be methanol.
- the hydroalcoholic solvent medium has a viscosity at 25 ° C. strictly less than 10 mPa.s.
- the aqueous-alcoholic solvent medium may have a viscosity at 25 ° C. less than or equal to 5 mPa.s, preferably less than or equal to 3 mPa.s, more particularly less than or equal to 2 mPa.s and in particular ranging from 0 , 1 to 1 mPa.s.
- the viscosity can be measured by any conventional method known to those skilled in the art, for example using a rotating viscometer, vibrating body or capillary tube.
- the suspension of metallic nanoobjects comprising the fine metallic nanowires in step (i) of the method of the invention has a mass concentration of metallic material (constituting said metallic nanowires and ancillary nanoparticles) of between 0.01 % and 5% by mass, in particular between 0.1 and 2.0% by mass.
- the silver concentration of the suspension of metallic nanoobjects in step (i) can thus be between 0.01% and 5% by mass, in particular between 0.1 and 2, 0% by mass.
- the suspension of metallic nanoobjects comprising the fine metallic nanowires in step (i) of the process of the invention may have a mass concentration of metallic material constituting said metallic nanowires, for example silver in the case of silver nanowires, between 0.1 and 10 g / L, in particular between 1 and 5 g / L.
- This concentration can for example be measured by plasma torch spectrometry (ICP-MS or ICP-OES) or atomic absorption.
- the suspension of metallic nanoobjects from step (i) of the process of the invention can be obtained from the reaction mixture obtained at the end of a conventional synthesis of nanowires in solution, and more particularly after a first decantation step as described in document EP 3 021 230.
- the suspension of metallic nanoobjects in step (i) can be more particularly obtained via the steps consisting of:
- (a) have a mixture of metallic nanoobjects including fine nanowires as described above and ancillary nanoparticles, in particular as defined above, in the state of dispersion in a solvent medium with a viscosity at 25 ° C. greater than or equal to 10 mPa.s, in particular between 10 and 50 mPa.s;
- step (b) allowing the dispersion of step (a) to settle under conditions conducive to the formation of a supernatant phase comprising said small particles and a precipitate comprising said metallic nanoobjects;
- the method for purifying metal nanowires according to the invention can be implemented to isolate fine metal nanowires from their synthetic reaction mixture, and include the following steps:
- the starting mixture comprising the metallic nanoobjects including fine metallic nanowires as described above, together with small undesirable metallic particles, in the state of dispersion in a solvent medium, can be the reaction mixture, obtained at the end of 'a conventional synthesis of nanowires in solution, where appropriate diluted with one or more solvents.
- metal nanowires are well known to those skilled in the art. In general, they implement the reduction of metal salts, for example silver nitrate for the synthesis of silver nanowires, by a polyol, typically ethylene glycol, in the presence of a nucleating agent. (usually NaCl) and polyvinylpyrrolidone (PVP). PVP acts as a blocking agent, able to control the growth rates of different surfaces of silver nanocrystals.
- a nucleating agent usually NaCl
- PVP polyvinylpyrrolidone
- reaction mixture obtained at the end of the synthesis described in the publication Toybou et al., Environ. Sci. : Nano, 2019, 6, 684 [4].
- the solvent medium for the dispersion of step (a) is formed from a single solvent. It may for example be formed from the reaction solvent which has been used for the synthesis of metallic nanowires, conventionally chosen from polyols having from 2 to 6 carbon atoms, typically ethylene glycol.
- the solvent medium for the dispersion of step (a) can be formed from one or more solvents different from the reaction solvent used for the synthesis of metallic nanowires.
- the mixture in step (a) can for example be obtained from the synthesis reaction mixture, after separation of the reaction solvent, and addition of one or more solvents of a different nature.
- the solvent medium for the dispersion of step (a) can be formed from the reaction solvent, typically ethylene glycol, to which one or more solvents have been added, preferably chosen from among monoalcohols, in particular C 1 to C 10, more particularly C 1 to C 6, such as isopropanol.
- the mixture in step (a) can be the reaction mixture, directly obtained at the end of the synthesis of the nanowires, to which has optionally been added, for the purposes of dilution, an additional volume of solvent (s), in particular chosen from monoalcohols, for example isopropanol.
- solvent (s) in particular chosen from monoalcohols, for example isopropanol.
- the additional solvent (s), preferably the monoalcohol (s), for example isopropanol, is / are used in the reaction mixture for the synthesis of nanowires (also called the “reaction crude”), in a solvent (s): reaction mixture volume ratio ranging from 1: 10 to 10: 1, preferably from 2: 1 to 1: 2 and more particularly from 1: 1.
- the solvent medium for the dispersion in step (a) comprises, in particular is formed, one or more solvents chosen from polyols having from 2 to 6 carbon atoms, preferably diols having 2 to 4 carbon atoms, in particular chosen from ethylene glycol and propylene glycol; optionally as a mixture with one or more monoalcohols, in particular C 1 to C 10, preferably isopropanol.
- said polyol (s), preferably ethylene glycol, and said monoalcohol (s), in particular isopropanol, are present in a polyol (s) / monoalcohol (s) volume ratio ranging from 1: 10 to 10: 1 , preferably from 2: 1 to 1: 2 and more particularly from 1: 1.
- the mixture of step (a) has a concentration of metallic material constituting said metallic nanowires of between 0.1 and 10 g / L, in particular between 1 and 4 g / L.
- the silver concentration of the mixture in step (a) can thus be between 0.1 and 10 g / L, in particular between 1 and 4 g / L.
- This concentration can for example be measured by plasma torch spectrometry (ICP-MS or ICP-OES) or atomic absorption.
- the mixture from step (a) is then allowed to settle. This first settling makes it possible to separate some of the small undesirable particles as described above from the metallic nanoobjects (fine nanowires and ancillary nanoparticles) present in the mixture.
- this first settling leads to a supernatant comprising a part of the small particles dispersed in the solvent medium, while the precipitate (also called “deposit” or “settling”), resulting from the settling, comprises the metallic nanoobjects including the nanowires. purposes of interest.
- the decantation can be carried out at room temperature.
- the decantation in step (b) can be carried out for a period ranging from 2 hours to 18 hours, preferably from 4 hours to 12 hours, in particular about 10 hours.
- the precipitate, obtained at the end of this first decantation step, comprising the majority of the fine metal nanowires initially present in the mixture (a), is then isolated and then dispersed in a hydroalcoholic solvent medium as described above.
- the decanted product can for example be recovered by removing the supernatant phase by means of a suction system, for example a pipette.
- the removed supernatant phase can be treated separately to recover the raw materials, in particular the recycling of the metallic material, such as silver.
- the suspension of metallic nanoobjects including the fine nanowires of interest is supplemented with nanoparticles of metallic oxide (s) (s) or metalloid (s).
- nanoparticles of metal oxide (s) or metalloid (s) can advantageously be of spherical shape.
- spherical particle is intended to denote particles having the shape or substantially the shape of a sphere.
- the nanoparticles of metal oxide (s) or metalloid (s) used according to the invention have an average diameter less than or equal to 50% of the average diameter of the fine metal nanowires, in particular less than or equal to 20% the average diameter of the fine metal nanowires, preferably less than or equal to 10% of the average diameter of the fine metal nanowires.
- they may have an average diameter less than or equal to 25 nm, preferably less than or equal to 15 nm, in particular between 5 and 12 nm.
- the nanoparticles of metallic or metalloid oxide (s) can have a specific surface area, measured according to the BET method, of between 80 and 500 m 2 / g, in particular between 100 and 250 m 2 / g.
- the nanoparticles consist of a material chosen from metal oxides, metalloid oxides, and mixtures thereof, in particular from alumina (AI 2 O 3 ), silica (S1O 2 ), iron oxides, manganese oxides , titanium and zinc.
- the nanoparticles of metal oxide (s) or metalloid (s) used according to the invention are silica nanoparticles.
- the nanoparticles of metal oxide (s) or metalloid (s) can be added to the suspension of metallic nanoobjects, in the form of a suspension of said nanoparticles in a hydroalcoholic solvent medium, as defined above.
- they can be implemented in the form of a suspension of nanoparticles of metal or metalloid oxide (s) in one or more solvents chosen from water and C 1 to C 10 monoalcohols, for example methanol.
- solvents chosen from water and C 1 to C 10 monoalcohols, for example methanol.
- the suspension of nanoparticles of metal oxide (s) or metalloid (s) may be commercially available or else be prepared by dilution, for example in one or more monoalcohols, from a commercially available suspension .
- Examples include suspensions of silica nanoparticles, sold under the references Ludox ® by the company Sigma-Aldrich.
- the nanoparticles of metal oxide (s) or metalloid (s) are introduced into the suspension of metallic nanoobjects comprising said fine nanowires of interest, in a weight ratio of fine metallic nanowires / oxide nanoparticles (s). ) metallic (s) or metalloid (s) between 1: 1 and 1: 100.
- the mass ratio of fine metallic nanowires / nanoparticles of metallic or metalloid oxide (s) can be between 1: 2 and 1: 20 and more particularly from 1: 8 to 1: 12, in particular be about 1:10.
- the suspension of metallic nanoobjects supplemented with said nanoparticles of metallic oxide (s) or metalloid (s) advantageously has a mass concentration of metallic material constituting said metallic nanowires, for example of silver in the case of the purification of nanowires of silver, between 0.1 and 10 g / L, in particular between 1 and 5 g / L.
- step (iii) of the method of the invention the suspension of metallic nanoobjects, supplemented with said nanoparticles of metallic oxide (s) or metalloid (s), is left to settle.
- This second settling leads to a precipitate (settling) comprising the fine metal nanowires, while the separate ancillary nanoparticles of said nanowires remain in the supernatant.
- the decantation can be carried out at room temperature.
- good separation of the fine metal nanowires and the ancillary nanoparticles can be obtained for a short settling time, in particular for a period less than or equal to 6 hours, more particularly between 2 and 4 hours.
- the settling comprises more than 80% of the fine metallic nanowires present in the suspension of starting nanoobjects, in particular more than 90% of the fine metallic nanowires.
- the decantate comprises less than 10% by mass, in particular less than 5% by mass and advantageously less than 2% by mass of metallic nanoobjects other than the desired fine nanowires.
- the duration of the settling can be reduced to the detriment of the quality of the separation, depending on the quantity of by-products admissible with the fine metal nanowires.
- the decantate formed essentially of fine metallic nanowires having on their surface said nanoparticles of metallic oxide (s) or metalloid (s), is isolated from the supernatant phase.
- the supernatant phase comprising the ancillary metallic nanoparticles, for example silver nanoparticles, distinct from said fine nanowires, it can be treated separately for recovery of the raw materials, in particular recycling of the metallic material, for example silver.
- the decantate obtained at the end of step (iv), consisting essentially of fine metallic nanowires, for example fine silver nanowires, on the surface of which are present nanoparticles of metal oxide (s) or metalloid (s), can be redispersed in a hydroalcoholic solvent medium, for example in water or methanol, said dispersion then being able to be used to form a percolating network of metallic nanowires.
- a hydroalcoholic solvent medium for example in water or methanol
- P is for those skilled in the art to adjust the content of aqueous-alcoholic solvent medium to obtain the desired concentration of metallic nanowires, typically a concentration of metallic material of between 50 and 1000 mg / L.
- the metallic nanowires purified at the end of the process of the invention, dispersed in a hydroalcoholic solvent medium, can be used for the manufacture of electrically conductive and transparent materials, for example a transparent electrode.
- a percolating network of nanowires can be deposited on the surface of a substrate, for example glass, from the suspension of nanowires, for example by nebulization, vaporization, spin coating, coating, screen printing, etc., preferably by spraying (or “spray coating” in English).
- the presence of nanoparticles of metal oxide (s) or metalloid (s) in the dispersion of fine metal nanowires does not affect the performance of the percolating network based on said metal nanowires.
- the presence of such nanoparticles of metal oxide (s) or metalloid (s), such as silica nanoparticles is likely to improve the dispersion of metal nanowires, such as silver nanowires, in the matrices polymers, such as epoxy matrices, for the formation of nanocomposites.
- the silver nanowires are synthesized according to the synthesis in polyol medium described in the publication Environ. Sci. : Nano, 2019, 6, 684 [4], for obtaining nanowires with an average length of 10 ⁇ m and an average diameter of 30 nm.
- the reaction mixture is cooled after synthesis of the nanowires.
- the mixture with a mass concentration of silver of 4 g / kg, is then distributed in crystallizers 10 cm in diameter.
- the suspension is present on a height of 6 cm.
- the mixture is left to settle for 72 hours. At the end of 72 hours of decantation, the separation between the nanoparticles and the nanowires of interest is insufficient and few nanoobjects can be recovered.
- the nanowires present in the isolated decantate can be used for the manufacture of electrodes, but still contain a not insignificant quantity of ancillary nanoparticles.
- the silver nanowires are synthesized as described in Example 1.
- reaction mixture is cooled after synthesis of the nanowires.
- isopropanol (1: 1 by volume).
- the decantate obtained after 12 hours is isolated and redispersed in methanol.
- This suspension containing most of the silver nanoobjects (unwanted silver nanowires and nanoparticles), is left to settle for 4 hours in crystallizers with a liquid height of 6 cm.
- the silver nanowires are synthesized as described in Example 1.
- reaction mixture is cooled after synthesis of the nanowires.
- isopropanol (1: 1 by volume).
- the decantate obtained after 12 hours is isolated and redispersed in methanol.
- Each of the Ludox ® solutions is diluted in methanol in order to obtain a mass concentration close to that of the solution of silver nanowires (approximately 4 g per kg of solution).
- One volume of silver nanowire solution is mixed with one volume of hydroalcoholic solution of Ludox ® . These mixtures are made for different nanowire / silica nanoparticle mass ratios: 1/1; 1/10 and 1/100.
- Figures 1 and 2 represent the SEM images obtained respectively for silver nanowires, and for the mixture of silver nanowires with silica nanoparticles originating from the Ludox ® AM-30 solution, with a nanowires / nanoparticles mass ratio of 1/10. It can be observed that the nanowires are well covered by the silica nanoparticles.
- nanowires thus purified make it possible to achieve the same electro-optical performance for two-dimensional percolating networks as the nanowires obtained after settling for three weeks, without the addition of metal oxide nanoparticles.
Abstract
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FR1907312A FR3098134B1 (en) | 2019-07-02 | 2019-07-02 | Process for the purification of metallic nanowires |
PCT/EP2020/068098 WO2021001280A1 (en) | 2019-07-02 | 2020-06-26 | Process for purifying metal nanowires |
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