CN101919062B - 钠/钼复合金属粉末、其产品以及光伏电池的生产方法 - Google Patents
钠/钼复合金属粉末、其产品以及光伏电池的生产方法 Download PDFInfo
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- CN101919062B CN101919062B CN200980102060.1A CN200980102060A CN101919062B CN 101919062 B CN101919062 B CN 101919062B CN 200980102060 A CN200980102060 A CN 200980102060A CN 101919062 B CN101919062 B CN 101919062B
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- sodium
- molybdenum
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000000843 powder Substances 0.000 title claims abstract description 153
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000002184 metal Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 239000011734 sodium Substances 0.000 title claims description 172
- 229910052708 sodium Inorganic materials 0.000 title claims description 162
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims description 160
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 121
- 239000011733 molybdenum Substances 0.000 title claims description 121
- 238000000034 method Methods 0.000 title claims description 89
- 239000002002 slurry Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 235000015393 sodium molybdate Nutrition 0.000 claims description 50
- 239000011684 sodium molybdate Substances 0.000 claims description 49
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 49
- 239000000758 substrate Substances 0.000 claims description 46
- 238000005245 sintering Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 14
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- 230000008021 deposition Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 125000003827 glycol group Chemical group 0.000 claims 1
- 238000009704 powder extrusion Methods 0.000 claims 1
- 238000001228 spectrum Methods 0.000 claims 1
- 150000003388 sodium compounds Chemical class 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 description 42
- 238000002485 combustion reaction Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 17
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- 239000006185 dispersion Substances 0.000 description 10
- 238000005477 sputtering target Methods 0.000 description 10
- 239000013077 target material Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 229940126142 compound 16 Drugs 0.000 description 6
- 239000004567 concrete Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 238000007596 consolidation process Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000005361 soda-lime glass Substances 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 238000002083 X-ray spectrum Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000010349 pulsation Effects 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920005570 flexible polymer Polymers 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
- 230000005484 gravity Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 210000002445 nipple Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 238000010334 sieve classification Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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Abstract
在根据本发明的一个实施方式中,用于生产复合金属粉末的方法可以包括:提供一定量钼金属粉末;提供一定量钠化合物;使所述钼金属粉末和所述钠化合物与液体组合,从而形成浆液;将上述浆液加料到热气流中;和回收所述复合金属粉末。
Description
技术领域
本发明一般性地涉及一种含钼材料和涂层,更具体地,涉及一种适于用在光伏电池的制造中的钼涂层。
背景技术
钼涂层是本领域已知的,其可应用在各种应用领域的各个工艺中。钼涂层的一种应用是生产光伏电池。更具体地,一类高效多晶薄膜光伏电池包含含有CuInGaSe2的吸收层。上述光伏电池以吸收层包含的元素命名通常被称为CIGS光伏电池。在常见的结构中,CuInGaSe2吸收层形成或“生长”在其上沉积有钼膜的钠钙玻璃衬底上。令人感兴趣的是,业已发现少量来自钠钙玻璃衬底的钠扩散通过钼膜起到提高电池效率的作用。例如参见K.Ramanathan等人的Photovolt.Res.Appl.11(2003),225;John H.Scofield等人的Proc.of the 24th IEEE Photovoltaic Specialists Conference,IEEE,New York,1995,164-167。尽管上述效率的增加是以CIGS电池沉积在钠钙玻璃衬底上的结构自动实现的,但是已经证明了采用其它类型的衬底实现效率的增加相当困难。
例如,非常关注在柔性基材上形成CIGS电池,这样电池可以更轻并且容易适应各种形状。尽管已经制造并使用这种电池,但是所涉及的柔性衬底不含钠。结果,在这种衬底上制造的CIGS电池的性能可以通过用钠掺杂钼层来改善。例如,参见Jae Ho Yun等人的Thin Solid Films,515,2007,5876-5879。
发明内容
在根据本发明的一个实施方式中,用于生产复合金属粉末的方法可以包括:提供一定量钼金属粉末;提供一定量钠化合物;使所述钼金属粉末和所述钠化合物与液体组合,从而形成浆液;将上述浆液加料到热气流中;和回收所述复合金属粉末。还公开了根据这种方法生产的复合金属粉末。
用于生产复合金属粉末的另一实施方式可以包括:提供一定量钼金属粉末;提供一定量钼酸钠粉末;将所述钼金属粉末和所述钼酸钠粉末与水组合,从而形成浆液;将上述浆液加料到热气流中;和回收所述复合金属粉末。还公开了根据这种方法生产的复合金属粉末。
还公开了一种用于制备金属制品的方法,所述方法包括:(a)通过如下生产一定量复合金属:提供一定量钼金属粉末;提供一定量钠化合物;使所述钼金属粉末和所述钠化合物与液体组合,从而形成浆液;将上述浆液加料到热气流中;和回收所述复合金属粉末;和(b)固结所述复合金属粉末,从而形成所述金属制品,所述金属制品包含钠/钼金属基质。还公开了根据上述方法制成的金属制品。
根据本文的教导,光伏电池的生产方法可以包括:提供衬底;在所述衬底上沉积钠/钼金属层;在所述钠/钼金属层上沉积吸收层;和在所述吸收层上沉积结配对层(junction partner layer)。
在衬底上沉积钠/钼膜的方法可以包括:提供一定量含有钼和钠的复合金属粉末;通过热喷雾在所述衬底上沉积所述复合金属粉末。在衬底上沉积膜的另一方法可以包括:溅射含有钠/钼金属基质的靶材,来自所述靶材的所述经溅射材料形成所述钠/钼膜。涂布衬底的另一方法可以包括:提供一定量含有钼和钠的复合金属粉末;蒸发所述复合金属粉末,从而形成钠/钼膜。涂布衬底的方法可以包括:提供一定量含有钼和钠的复合金属粉末;将所述一定量复合金属粉末与载体混合;和通过印刷将所述复合金属粉末和载体的混合物沉积在所述衬底上。
附图说明
本发明的说明性和优选的实施方式示于如下附图中,其中:
图1示意性地表示基本工艺过程的一种实施方式,该实施方式可被用于生产钠/钼复合金属粉末;
图2是表示复合金属粉末混合物的加工方法的工艺流程图。
图3是具有钠/钼金属层的光伏电池的正视放大截面图。
图4是钠/钼复合金属粉末混合物的扫描电镜照片。
图5a是能量弥散X射线谱的光谱图,其表示图4照片中钠的分散。
图5b是能量弥散X射线谱的光谱图,其表示图4照片中钼的分散。
图6示意性地表示脉动燃烧喷射干燥装置的一种实施方式。
图7是表示根据本文教导生产的示意性复合金属粉末的筛分级分布(screen fraction distribution)的图表。
具体实施方式
用于生产钠/钼复合金属粉末12的工艺或方法10示于图1中,其简单描绘为可以包括提供一定量钼金属粉末12和一定量钠化合物16,例如钼酸钠(Na2MoO4)粉末。钼金属粉末14和钼酸钠粉末16与液体(诸如水)组合,从而形成浆液20。然后,为了生产钠/钼复合金属粉末12,可以例如通过脉动燃烧喷射干燥器22喷射干燥浆液20。
现在主要参照图2,钠/钼复合金属粉末12可以以其回收形式或“生料”形式用作各种工艺和应用的原料24,这些工艺和应用中的一些在本文中示出并描述,另一些对于熟悉本文提供的教导之后的本领域普通技术人员来说是明显可得的。或者,可以例如通过烧结26、通过分类28、或通过二者组合对“生料”复合金属粉末12进行进一步加工,然后再用作原料24。为了如图3所示在衬底34上沉积钠/钼膜32,可以将钠/钼复合金属粉末原料24(例如“生料”形式或经加工形式)用在热喷射沉积工艺30中。上述钠/钼膜32可以用在各种应用中具有优势。例如并将进一步详细描述的,钠/钼膜32可以构成光伏电池36的一部分,其可用于改善光伏电池36的效率。在可供选择的沉积工艺中,复合金属粉末12也可以作为印刷工艺38中的原料,其也可以在衬底34上形成钠/钼膜或涂层32’。
在另一实施方式中,为了生产金属制品42(例如溅射靶材44),可以在步骤40中对复合金属粉末原料24(“生料”形式或经加工形式)进行固结。可以“原样”使用直接得自固结40的金属制品42。或者,可以例如通过烧结46对经固结的制品进行进一步加工,在该情况下,金属制品42将包含经烧结的金属制品。在金属制品42包含溅射靶材44(即,经烧结形式或未经烧结形式)的情况下,为了在衬底34上沉积钠/钼膜32”,可以在溅射沉积装置(未示出)中使用溅射靶材44。见图3。
现在主要参照图4,图5a和图5b,钠/钼复合金属粉末12包含多个一般为球形的粒子,这些粒子自身是更小粒子的聚集体(agglomeration)。因此,复合金属粉末12在本文中也可以表征为由“BB’s”形成的“足球”。此外,正如图5a和5b所证明的,钠高度分散在钼中。也就是说,本发明的钠/钼复合粉末不仅仅是钠金属粉末和钼金属粉末的组合体,而是包含熔融或团聚在一起的钠亚粒子和钼亚粒子的基本上均匀的分散体或者复合混合物。钠/钼金属粉末复合物还具有高密度并且具有有利的流动特性。正如本文更详细地讨论的那样,根据本文的教导生产的示例性钠/钼复合金属粉末12具有在约2g/cc至约3g/cc范围内的Scott密度。对于本文所示以及描述的各种实例组成而言,霍尔流动性(Hall flowability)在小于约35s/50g至低至30s/50g的范围内。
本发明的显著优势在于,它提供了一种通过传统方法难以或不可能实现的钼和钠的金属组合。然而,即使钠/钼复合金属粉末包含粉末状材料,但它不是钠和钼粒子的简单混合物。更确切的说,钠亚粒子和钼亚离子实际上熔合在一起,结果粉末状金属制品的单个粒子中包含钠和钼二者。因此,包含本发明的钠/钼复合粉末的粉末状原料24将不会分离成钠粒子和钼粒子(例如由于比重差异)。此外,由钠/钼复合金属粉末制成的涂层或膜具有与钠/钼金属粉末的组成类似的组成,这是因为,上述沉积工艺并不依赖于各自具有不同沉积速率的单独钼粒子和单独钠粒子的共沉积(codeposition)。
除了与能够提供其中钠高度均匀地分布在整个钼中的复合金属粉末相关的优势以外,本文公开的复合金属粉末还具有高密度和流动性特征,从而允许该种复合金属粉末有利地用在各种本领域现在已知的或未来可能开发的粉末冶金工艺中。例如,钠钼复合金属粉末易于用在各种热喷射沉积装置中以及相关工艺中,从而在各种衬底上沉积钠/钼膜或涂层。这种粉末还易于用在各种固结工艺中,例如冷等压压制工艺和热等压压制工艺以及挤压和烧结工艺。高流动性允许本文公开的粉末容易填充模腔,而高密度使在随后烧结期间发生的收缩最小。烧结可以通过如下完成:在惰性环境中进行加热或者在氢气中进行加热以进一步减少压缩体中的氧含量。
在另一实施方式中,钠/钼复合金属粉末可用于形成溅射靶材,该靶材然后可用在随后的溅射沉积工艺中以形成钠/钼膜或涂层。在一个实施方式中,这种钠/钼膜可用于提高光伏电池的能量转换效率。
已经简单描述了本发明的钠/钼复合金属粉末12,其制备方法以及如何将其用于制造在衬底上的钠/钼涂层或膜,现在详细描述复合粉末的各种实施方式以及制备和使用复合粉末的方法。
现在主要参照图1,用于制备钠/钼复合粉末12的方法10可以包括提供一定量钼金属粉末14和一定量钠化合物16。钼金属粉末14可以包括粒子尺寸在约0.1μm至约15μm范围内的钼金属粉末,但是具有其它尺寸的钼金属粉末14也可用。适于用在本发明中的钼金属粉末可商购自ClimaxMolybdenum(Freeport-McMoRan Company)和Climax MolybdenumCompany(Freeport-McMoRan Company),Ft.Madison Operations,Ft.Madison,Iowa(US)。或者,也可以使用来自其它来源的钼金属粉末。
钠化合物16可以包括钼酸钠(无水形式(即Na2MoO4)或二水合形式(即Na2MoO4·2H2O)),但是也可以使用其它含钠材料,包括但不限于单质钠、Na2O和Na(OH)。钼酸钠通常以粉末形式得到,可以包括宽尺寸中的任意一种。钼酸钠粉末16的粒子尺寸在其中水被用作液体18的实施方式中不是特别关键,因为钼酸钠可溶于水中。适于用在本发明中的钼酸钠粉末可商购自Climax Molybdenum(Freeport-McMoRan Company),Ft.Madison Operations,Ft.Madison,Iowa(US)。或者,钼酸钠可得自其它来源。
钼金属粉末14和钼酸钠16可以与液体18混合形成浆液20。一般来说,液体18可以包括去离子水,但是也可以使用其它液体,诸如醇、挥发性液体、有机液体及其各种混合物,这对于熟悉本文教导后的本领域普通技术人员来说是容易理解的。因此,本发明不应被认为局限于本文所述的具体液体18。除了液体18之外,还可以使用粘合剂48,但是粘合剂的添加不是必需的。适于用在本发明中的粘合剂包括但不限于聚乙烯醇(PVA)、聚乙二醇(如Carbowax)及其混合物。可以在添加钼金属粉末14和钼酸钠之前将粘合剂48与液体18混合。或者,粘合剂可以加入浆液20中,即在钼金属14和钼酸钠已与液体18组合之后。
浆液20可以包含约15重量%至约25重量%的液体(例如液体18本身或者液体18与粘合剂48组合),剩余部分包含钼金属粉末14和钠化合物16。钠化合物16(例如钼酸钠)的添加量适于提供具有所希望的“保留”钠(retained sodium)的含量的复合金属粉末12和/或最终制品。因为保留钠的含量依据各种因素变化,所以本发明不应被认为局限于提供任意特定量的钠化合物16。各种因素可以影响被提供到浆液20中的钠化合物的量,其包括但不限于待生产的具体制品、待使用的特定“下游”工艺,例如取决于是否钠/钼复合金属粉末12被烧结,以及是在粉末原料(例如24)中还是在沉积膜或涂层(例如32、32’、32”)中保留希望量的钠。然而,作为实例,钼金属14和钼酸钠16的混合物可以包含约1重量%至约15重量%的钼酸钠18。然而,总的来说,浆液20可以包含约0重量%(即没有粘合剂)至约2重量%的粘合剂48。浆液20的其余部分可以包含钼金属粉末14(例如,用量在约58重量%至约84重量%的范围内)和钼酸钠16(例如,用量在约1重量%至约15重量%的范围内)。
然后,为了生产复合金属粉末产品12,可以通过本领域现在已知的或者未来开发出的各种工艺中的任意一种对浆液22进行喷射干燥,这对于熟悉本文教导后的普通技术人员来说是容易理解的。因此,本发明不应被认为局限于任何特定干燥工艺。然而,作为实例,在一个实施方式中,浆液20在脉动燃烧喷射干燥器22中进行喷射干燥。更具体地,脉动燃烧喷射干燥器22可以是Larink,Jr.的美国专利申请公开号2006/0219056,标题为“Metal Powders and Methods for Producing the Same”中所示以及所描述的类型,上述专利文献公开的全部内容通过引用具体***本文。
现在参照图1和图6,浆液20可以加料到脉动燃烧喷射干燥器22中,于是,浆液20撞击以声速或接近声速脉动的热气流50。声速脉动的热气体50与浆液20接触并馏出基本上全部水,从而形成复合金属粉末产品12。热气50的脉动流的温度可以在约300℃至约800℃的范围内,诸如约465℃至约537℃,更优选为约500℃。一般而言,热气50的脉动流的温度低于浆液组分的熔点,但不低于单质钠的熔点。然而,浆液20通常不与热气50接触足够长,以避免将大量热量转移到浆液中,因为钠金属的熔点很低所以这很重要。例如,在典型的实施方式中,估计浆液20在与热气50的脉动流接触期间通常被加热至在约93℃至约121℃的范围内的温度。
如上所述,热气50的脉动流可以通过本领域已知且容易商购类型的脉动燃烧***22生成。作为实例,在一个实施方式中,脉动燃烧***22可以包括在美国专利申请公开号2006/0219056中所示且描述类型的脉动燃烧***。现在,参照图6,燃烧空气51可以通过入口52被加料(例如泵送)到低压下的脉动燃烧***22的外壳54中,于是,燃烧空气流过单向空气阀56。然后,空气进入已被调节的燃烧室58中,其中通过燃料阀或端口60添加燃料。然后,通过引火嘴62点燃燃料-空气混合物,从而形成热燃烧气体64的脉动流,该脉动流可被加压至各种压力,例如在比燃烧扇压力高约15000Pa(约2.2psi)至约20000Pa(约3psi)的范围内。热燃烧气体64的脉动流朝向雾化器68向下冲出排气管66。就在雾化器68上方,淬火空气70可以通过入口72加料并且可以与热燃烧气体64共混,从而得到具有所需温度的热气脉动流50。通过雾化器68将浆液20进入热气50的脉动流中。然后,将经雾化的浆液分散在圆锥出口74中,然后进入传统的落地型(tall-form)干燥室(未示出)。在更下游,复合金属粉末制品12可以使用标准收集装置来回收,所述收集装置诸如为漩风集尘器和/或集尘袋(也未示出)。
在脉动操作中,空气阀56循环打开、关闭,使空气进入燃烧室58及其燃烧停止交替进行。在上述循环中,空气阀56可以就在先前燃烧事件之后被重新打开用于随后的脉动。于是,重新打开允许随后的气料(例如燃烧空气51)进入。然后,燃料阀60重新允许燃料进入,如上所述,混合物在燃烧室58中自动点燃。在室58中以脉动方式打开和关闭空气阀56和燃烧燃料的循环可以以各种频率控制,例如约80Hz至约110Hz,但是也可以使用其它频率。
通过本文所述的脉动燃烧喷射干燥工艺生产的“生料”钠/钼复合金属粉末产品12表示在图4、图5a和图5b中,其包含多个通常为球形的粒子,这些粒子自身是更小粒子的聚集体。正如已经描述的,钠高度分散在钼内,包括被熔合到一起的钠亚粒子和钼亚粒子的复合混合物或者基本上均匀的分散体。更具体,图5a是通过能量弥散X射线谱(EDS)得到的光谱图,其表示图4所示复合金属材料12的样品中钠的存在情况。图5b是通过能量弥散X射线谱(EDS)得到的光谱图,其表示样品中钼的存在情况。通过比较图4、图5a和图5b可以看出,钠通常均匀地、广泛地分散在整个复合金属粉末产品12内。
一般说来,根据本文的教导生产的复合金属粉末产品12具有宽范围的尺寸,尺寸在约1μm至约100μm范围内的粒子,诸如尺寸在约5μm至约45μm、约45μm至约90μm范围内的粒子,易于通过如下本文提供的教导生产出来。如果需要,复合金属粉末产品12可以例如在步骤28(图2)中进行分类,以得到具有更窄尺寸范围的产品12。图7中提供了各种示例性的复合金属粉末制品12的筛分分析,其为通过浆液组合物生产的“生料”复合金属粉末产品12的粒子尺寸分布(通过U.S.Tyler目)图,所述浆液组合物包含3、7、9和15重量%的钼酸钠18。
如上所述,钠/钼复合金属粉末12还具有高密度,通常相当易流动。示例性的复合金属粉末产品12具有在约2g/cc至约3g/cc范围内的Scott密度(即表观密度),在本文阐述的各种实施例中确认了。霍尔流动性在约35s/50g至低至30s/50g的范围内,也在本文阐述的各种实施例中确认了。然而,一个实例组合物(即实施例12)不具有流动性。
如已所述的,脉动燃烧***22提供热气50的脉动流,其中浆液20被加入该脉动流中。接触区域和接触时间非常短,接触时间通常为几分之毫秒的数量级。因此,热气50、声波和浆液20的物理相互作用产生复合金属粉末产品12。更具体地,浆液20的液体组分18基本上被热气50的声速(或接近声速)脉动波除去或驱赶走。短接触时间还确保了浆液组分以最低程度被加热,例如在接触时间结束时被加热至约93℃至约121℃的水平,该温度足以蒸发液体组分18。
在某些情况下,残余量的液体(例如液体18和/或,如果使用的话,粘合剂48)可以残留在所得“生料”复合金属粉末产品12中。可以通过随后的烧结或加热步骤26驱除(例如部分驱除或完全驱除)任何残留的液体18。见图2。一般说来,为了驱除液体组分和氧气但不驱除大量钠,加热或烧结工艺26在中等温度下进行。加热26期间可能损失一些钠,这将减少烧结原料24中的保留钠量。通常还优选在氢环境下进行加热26,以使复合金属粉末12的氧化最小,但这不是必需的。保留的氧很低,小于约6%,通常小于约2%,这在如下提供的实施例中示明了。加热26可以在约500℃至约825℃范围内的温度下进行。或者,可以短时间使用高达1050℃的温度。然而,这种较高温度通常会降低最终产品中的保留钠量。
还可以注意到:金属粉末产品的聚集体优选保持其形状(在一些情况下基本上为球形,但不是必需的),甚至在加热步骤26后也保持其形状。经加热形式和/或生料形式的流动数据(霍尔数据)通常也非常好(例如在约30-35s/50g的范围内),这相对于本文提供的实施例进行说明。
正如以上所表明的,在一些情况下,可以在干燥工艺期间生产各种尺寸的聚集产品,可能希望的是进一步将复合金属粉末产品12分离或分类成尺寸范围在所需产品尺寸范围内的金属粉末产品。例如,所生产的大多数复合金属粉末材料具有宽范围的粒子尺寸(例如约1μm至约150μm),其中,相当大量的产品在约5μm至约45μm(即,-325 U.S.Tyler目)的范围内,还有在约45μm至90μm(即,-170+325 U.S.Tyler目)的范围内。参见表7。上述方法可以生产相当高百分率的在这个产品尺寸范围内的产品;然而,可以存在在所需产品尺寸范围以外的剩余产品,特别是较小产品,它们可被循环通过体系,但是还必须补充液体(例如水)以形成适当的浆液组合物。上式回收是可选的(或附加的)一个步骤或多个步骤。
复合金属粉末12可以以其回收形式或“生料”形式用作各种工艺和应用的原料24,这些工艺和应用中的一些在本文中示出并描述,另一些对于熟悉本文提供的教导之后的本领域普通技术人员来说是明显可得的。或者,可以例如通过烧结、通过分类、或通过二者组合对“生料”复合金属粉末产品12进行进一步加工,然后其被用作原料24。
如上所述,钠/钼复合金属粉末12可用在各种装置和工艺中,以在衬底上沉积钠/钼膜。在一项应用中,这种钠/钼膜可以有利地用于构建光伏电池。例如,已知如果使钠扩散进入通常用于形成光伏电池的欧姆接触的钼层,那么可能提高CIGS光伏电池的能量转换效率。上述效率的增加是在其中钼欧姆接触沉积在钠钙玻璃衬底上的CIGS结构中自动实现的。然而,在钠钙玻璃未作为衬底的结构上不能实现上述效率的增加。
现在,参照图3,光伏电池36可以包含衬底34,该衬底上可以沉积钠/钼膜32、32’、32”。衬底34可以包括各种衬底中的任意一种,例如不锈钢、柔性聚合膜(poly films)、或者其它本领域现在已知的或者未来可能开发的适用于该装置的衬底材料。然后,钠/钼膜32、32’、32”可以通过本领域现在已知的或者未来可能开发出的各种工艺沉积在衬底34上,但是一定形式使用钠/钼复合金属粉末材料12。例如,如以下详细描述的,钠/钼膜可以通过热喷射沉积、通过印刷、通过蒸发或者通过溅射进行沉积。
一旦钠/钼膜(例如,32、32′、32″)沉积在衬底34上了,就可以将吸收层76沉积在钠/钼膜上。作为实例,吸收层76可以包含选自如下组成的组中的一种或多种:铜、铟和硒。吸收层可以通过本领域已知的或者未来可能开发适用于预期应用的各种方法中的任意一种沉积。结果,本发明不应认为局限于任何特定沉积过程。
然后,结配对层78可以沉积在吸收层76上。结配对层78可以包含选自如下组成的组中的一种或多种:硫化镉和硫化锌。最后,可以将透明的导电氧化物层80沉积在结配对层78上,从而形成光伏电池。结配对层78和透明的导电氧化物层80可以通过本领域已知的或者未来可能开发适用于沉积这些材料的各种工艺和方法中的任意一种沉积。结果,本发明不应被认为局限于任何特定的沉积工艺。此外,因为制造CIGS光伏电池的工艺是本领域已知的(在衬底上提供钠/钼膜除外)并且容易由熟悉本文的教导后的本领域普通技术人员执行,所以可以用来制造CIGS光伏电池的具体制造技术未在本文中进一步详细地进行描述。
如上所述,钠/钼层或膜32、32′、32″可以通过各种工艺中的任意一种沉积。一般说来,我们相信约1重量%的钠浓度将足以提供所需要的效率增强。因此,可以根据需要调节或改变保留在原料24中的钠,从而在所得钠/钼膜32上提供所需水平的钠。一般说来,保留在原料24中的钠水平在约0.2重量%至约3.5重量%的范围内将足以在钠/钼膜32上提供所需程度的钠富集。如实例所示,在通过含有约3wt%至约15wt%钼酸钠的浆液29生产的“生料”和烧结的(即加热的)原料中可以实现上述保留的钠水平(例如约0.2wt%至约3.5wt%)。
在一个实施方式中,可以利用原料24通过热喷射工艺30沉积钠/钼膜32。热喷射工艺30可以通过使用各种热喷枪中的任意一种实现,其根据各种参数中的任意一种进行操作,从而在衬底34上沉积具有所需厚度和性质的钠/钼膜32。然而,因为热喷射工艺是本领域已知的,并且因为本领域普通技术人员在熟悉本文提供的教导后能够利用这个工艺,所以可以使用的特定热喷射工艺30未在本文中进一步详细地进行描述。
在另一实施方式中,可以利用原料24通过印刷工艺38在衬底34上沉积钠/钼膜32’。原料24可以与适当的载体(未示出)混合,从而形成然后可以通过各种印刷工艺中的任意一种沉积在衬底34上的“油墨”或“油漆”。这里也是一样,因为上述印刷工艺是本领域已知的,并且因为本领域普通技术人员在熟悉本文提供的教导后能够轻易的完成这个工艺,所以可以使用的具体印刷工艺38未在本文中进一步详细地进行描述。
在另一实施方式中,可以利用原料24通过蒸发工艺39在衬底34上沉积钠/钼膜32”。作为实例,在一个实施方式中,蒸发工艺39包括:将原料24置于适当蒸发装置(未示出)的坩锅(也未示出)中。原料24可以以松散的粉末形式、压制的小球形式、或其它固结形式、或其任意组合形式放置在坩锅中。原料24在坩锅中被加热至蒸发,于是,蒸发的材料将沉积在衬底34上,从而形成钠/钼膜32”。蒸发工艺39可以利用本领域现在已知的或者将来开发出用于蒸发原料24和将膜32”沉积在衬底34上的各种蒸发装置中的任意一种。结果,本发明不应不应被认为局限于使用任何根据任何特定参数操作的特定蒸发装置。此外,因为这种蒸发装置是本领域已知的,并且因为本领域普通技术人员在熟悉本文提供的教导后能够轻易地实现这种蒸发装置,所以可以使用的具体蒸发装置未在本文中进一步详细地进行描述。
在另一实施方式中,可以通过溅射沉积工艺将钠/钼膜32”’沉积在衬底34上。原料24可被加工成或形成溅射靶材44,然后对其进行溅射,从而形成膜32”’。本领域现在已知的或者未来可以开发出来出的各种溅射沉积装置中的任意一种可用于在衬底34上溅射沉积膜32”’。结果,本发明不应被认为局限于使用任何根据任何特定参数操作的特定蒸发装置。此外,因为这种溅射沉积装置是本领域已知的,并且因为本领域普通技术人员在熟悉本文提供的教导后能够轻易地实现这种溅射沉积装置,所以可以使用的具体溅射沉积装置未在本文中进一步详细地进行描述。
正如所提及的,溅射靶材44可以包括可通过在步骤40中固结或成型钠/钼复合金属粉末而制成的金属制品42。或者,溅射靶材可以通过热喷射30形成。如果溅射靶材44通过固结40制成的话,那么原料24(以“生料”形式或经加工形式)可以在步骤40中固结或成型,从而生产金属制品(例如溅射靶材44)。固结工艺40可以包括本领域现在已知的或者未来可能开发出的适用于特定应用的各种压缩工艺、挤压工艺、成形工艺中的任意一种。结果,本发明不应被认为局限于任何特定的固结工艺。
作为实例,固结工艺40可以包括本领域已知的各种冷等压压制工艺中的任意一种或各种热等压压制工艺中的任意一种。众所周知,冷等压压制工艺和热等压压制工艺二者通常包括施加相当程度的压力和热量(在热等压压制的情况下),从而使复合金属粉末原料24固结或成形成所需形状。热等压压制工艺可以在900℃或更高的温度下进行,这取决于钠/钼复合金属粉末压缩体的生料密度和最终产品可以容忍的保留钠的损耗。
固结40后,所得金属制品42(例如溅射靶材44)可以“原样”使用,或者,可以被进一步加工。例如,金属制品42可在步骤46中进行加热或烧结,从而进一步提高金属制品42的密度。希望在氢气氛中进行上述加热过程46,从而将金属制品42氧化的可能性降到最低。一般而言,优选地,上述加热在低于约825℃的温度下进行,因为较高的温度可能导致保留钠的量大量下降,但是也可以使用较高温度(例如1050℃或更高的温度)。如果需要或希望,所得金属制品42在被使用之前还可以进行机加工。不管对最终产品42是否进行烧结,都可以进行上述机加工。
实施例
若干实施例利用本文具体说明的钼金属和钼酸钠粉末14、16进行,这些原料得自Climax Molybdenum和/或Climax Molybdenum,Ft.MadisonOperations。将各种比例的粉末14和16与去离子水组合,从而形成浆液。更具体地,各个实施例利用的浆液20包含约20重量%的水(即液体18),其余为钼金属和钼酸钠粉末。钼金属粉末与钼酸钠的比值在各个实施例中在约3重量%至约15重量%钼酸钠的范围内变化。更具体地,实施例包含3、7、9和15重量%的钼酸钠量。
然后,将浆液20以本文所述方式加入脉动燃烧喷射干燥***22中。热气50的脉动流的温度被控制在约465℃至约537℃的范围内。通过脉动燃烧***22生产的热气50的脉动流将浆液20中的水基本上驱除,从而形成复合金属粉末12。接触区域和接触时间非常短,接触区域为约5.1cm,接触的时间为约0.2毫秒。
由更小颗粒的聚集体构成的所得金属粉末产品12基本上是实心的(即非空心的)并且通常具有球形形状。图4表示由含有9重量%的钼酸钠的浆液20生产的“生料”钠/钼复合金属粉末12的SEM照片。表I和II表示各个实施例的“生料”形式以及在氢气氛中在指定的温度下烧结或加热所指定时间后的数据。表I和表II还列出了经筛分生料(+325目钼)的数据。
表I
实施例 | 批次 | 钼金属(wt%) | 钼酸钠(SoMo)(wt%) | 表观密度(g/cc) | 霍尔流速(s/50g) |
1 | 3%SoMo生料 | 97% | 3% | ||
2 | 7%SoMo生料 | 93% | 7% | 2.89 | 33 |
3 | 9%SoMo生料 | 91% | 9% | ||
4 | 15%SoMo生料 | 85% | 15% | ||
5 | 3%SoMo+325目 | 97% | 3% | ||
6 | 9%SoMo+325目 | 91% | 9% | ||
7 | 15%SoMo+325目 | 85% | 15% | ||
8 | 9%SoMo烧结1h,1050℃ | 91% | 9% | ||
9 | 7%SoMo烧结10h,640℃ | 93% | 7% | 2.79 | 32 |
10 | 9%SoMo烧结10h,640℃ | 91% | 9% | ||
11 | 3%SoMo烧结6h,825℃ | 97% | 3% | ||
12 | 9%SoMo烧结6h,825℃ | 91% | 9% | 2.62 | 不流动 |
13 | 15%SoMo烧结6h,825℃ | 85% | 15% |
表II
实施例 | 浆液粘度秒.Zahn#1 | 钠浓度(wt%) | %O | %N | 烧结期间的重量损耗% | Na分布(EDS) |
1 | 33.8 | 0.74% | 1.23% | 0.0020% | ||
2 | 1.39% | 2.14% | 0.2500% | |||
3 | 35 | 1.74% | 2.64% | 0.0075% | Na在粒子中从3%至12%变化 | |
4 | 3.11% | 5.58% | 0.0295% | |||
5 | 1.22% | 0.0061% | ||||
6 | 1.84% | 2.93% | 0.0101% | EDS未见Na峰 | ||
7 | 3.09% | 5.16% | 0.196% | |||
8 | 0.73% | EDS未见Na峰 | ||||
9 | 1.36% | 1.36% | 0.0000% | 0.97% | ||
10 | 1.85% | 1.85% | 0.0018% | 1.85% | 4% | |
11 | 0.22% | 0.22% | 0.0011% | 1.79% | ||
12 | 1.32% | 1.32% | 0.0010% | 3.90% | 1.86% | |
13 | 2.39% | 2.39% | 0.0015% | 4.84% | 2.89% |
本文已经参数了本发明的优选实施方式,预料到可以对其进行适当的修正,但这仍包括在本发明的范围内。因此,本发明应当仅根据权利要求书进行解释。
Claims (30)
1.一种用于生产钠/钼复合金属粉末的方法,所述方法包括:
提供一定量钼金属粉末;
提供一定量钼酸钠粉末;
使所述钼金属粉末和所述钼酸钠粉末与液体组合,从而形成浆液,其中,在与所述液体组合前,以在3重量%至15重量%钼酸钠粉末范围内的量将所述钼酸钠粉末添加到所述钼金属粉末中;
将上述浆液加料到热气流中;和
回收所述钠/钼复合金属粉末,所述钠/钼复合金属粉末包含钠和钼,使所述钼金属粉末和所述钼酸钠粉末的所述组合进一步包括,所述钼酸钠粉末的添加量足以使所述钠/钼复合金属粉末包含0.2重量%至3.5重量%保留钠的量,其中所述保留钠以足以增强具有由所述钠/钼复合金属粉末制成的、用于形成光伏电池的欧姆接触的钠/钼膜的光伏电池的能量转换效率的量存在。
2.如权利要求1所述的方法,其中,将上述浆液加料到热气流中包括雾化所述浆液,并使所述经雾化的浆液与热气流接触。
3.如权利要求1所述的方法,其中,使所述钼金属粉末和所述钼酸钠粉末与液体组合包括使所述钼金属粉末和所述钼酸钠粉末与水组合,从而形成浆液。
4.如权利要求1所述的方法,其中,所述浆液包含介于15重量%至25重量%之间的液体。
5.如权利要求1所述的方法,进一步包括:
提供一定量粘合剂材料;和
使所述粘合剂材料与所述钼金属粉末、所述钼酸钠粉末和所述液体组合,从而形成浆液。
6.如权利要求5所述的方法,其中,所述粘合剂包括选自由聚乙烯醇和聚乙二醇组成的组中的一种或两种。
7.如权利要求5所述的方法,其中,所述浆液包含15重量%至25重量%的液体,0重量%至2重量%的粘合剂,3重量%至15重量%的钼酸钠和58重量%至82重量%的钼金属粉末。
8.如权利要求5所述的方法,进一步包括:在足以驱除基本上所有所述粘合剂的温度下加热所述经回收的复合金属粉末。
9.如权利要求8所述的方法,其中,所述加热进一步包括在氢气氛下加热。
10.如权利要求9所述的方法,其中,在氢气氛中的所述加热在500℃至825℃的温度下进行。
11.一种通过权利要求1所述的方法生产的钠/钼复合金属粉末。
12.如权利要求11所述的钠/钼复合金属粉末,其具有在30-35秒/50克范围内的霍尔流动性。
13.如权利要求11所述的钠/钼复合金属粉末,其具有在2g/cc至3g/cc范围内的Scott密度。
14.如权利要求11所述的钠/钼复合金属粉末,其包含少于6重量%的残留氧。
15.一种用于制备金属制品的方法,所述方法包括:
通过权利要求1的方法生产一定量钠/钼复合金属粉末;以及
固结所述复合金属粉末,从而形成所述金属制品,所述金属制品包含钠/钼金属基质。
16.如权利要求15所述的方法,所述固结所述复合金属粉末包括冷等压压制。
17.如权利要求15所述的方法,其中,所述固结包括将所述复合金属粉末挤压成形,并烧结所述成形体。
18.如权利要求17所述的方法,其中,所述烧结在氢气氛下进行。
19.如权利要求18所述的方法,其中,所述烧结在低于825℃的温度下进行。
20.如权利要求15所述的方法,其中,所述固结包括热等压压制。
21.一种用于生产光伏电池的方法,所述方法包括:
提供衬底;
在所述衬底上提供一定量的通过权利要求1所述的方法生产的钠/钼复合金属粉末以沉积钠/钼金属层;
在所述衬底上沉积钠/钼金属层;
在所述钠/钼金属层上沉积吸收层;和
在所述吸收层上沉积结配对层。
22.如权利要求21所述的方法,其中,沉积钠/钼金属层包括:溅射含有钠/钼金属基质的靶材,来自所述靶材的经溅射材料形成所述钠/钼膜。
23.如权利要求21所述的方法,其中,沉积钠/钼金属层包括:
通过热喷射在所述衬底上沉积所述复合金属粉末。
24.如权利要求21所述的方法,其中,沉积钠/钼金属层包括:
通过印刷在所述衬底上沉积所述复合金属粉末。
25.如权利要求21所述的方法,其中,沉积钠/钼金属层包括:
通过蒸发在所述衬底上沉积所述复合金属粉末。
26.如权利要求21所述的方法,进一步包括:在所述结配对层上沉积透明的导电氧化物层。
27.如权利要求26所述的方法,其中,所述吸收层包括选自由铜、铟和硒组成的组中的一种或多种。
28.如权利要求27所述的方法,其中,所述结配对层包括选自由硫化镉和硫化锌组成的组中的一种或两种。
29.一种在衬底上沉积膜的方法,所述方法包括:
提供一定量通过权利要求1所述的方法生产的钠/钼复合金属粉末;和
通过热喷射在所述衬底上沉积所述钠/钼复合金属粉末。
30.一种在衬底上沉积膜的方法,所述方法包括:通过权利要求15所述方法生产包含钠/钼金属基质的金属制品;并且溅射含有所述钠/钼金属基质的靶材,来自所述靶材的经溅射材料形成所述钠/钼金属层。
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US12/013,263 US20090181179A1 (en) | 2008-01-11 | 2008-01-11 | Sodium/Molybdenum Composite Metal Powders, Products Thereof, and Methods for Producing Photovoltaic Cells |
US12/013,263 | 2008-01-11 | ||
PCT/US2009/030561 WO2009089421A1 (en) | 2008-01-11 | 2009-01-09 | Sodium/molybdenum composite metal powders, products thereof, and methods for producing photovoltaic cells |
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CN (1) | CN101919062B (zh) |
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CN103045925B (zh) * | 2013-01-29 | 2015-01-28 | 洛阳高新四丰电子材料有限公司 | 一种钼钠合金旋转溅射管形靶材的制备工艺 |
CN103160791B (zh) * | 2013-03-26 | 2015-04-22 | 无锡舒玛天科新能源技术有限公司 | 一种钠掺杂钼平面溅射靶材的制备方法 |
CN103196933A (zh) * | 2013-03-27 | 2013-07-10 | 金堆城钼业股份有限公司 | 钼化合物/钼合金粉末掺杂元素分布微观均匀性检测方法 |
CN103898345B (zh) * | 2014-04-29 | 2016-04-06 | 金堆城钼业股份有限公司 | 一种钼钠合金材料的制备方法 |
CN104117685B (zh) * | 2014-07-30 | 2016-08-24 | 金堆城钼业股份有限公司 | 一种钼酸钠掺杂钼粉的制备方法 |
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CN107452818A (zh) * | 2017-08-16 | 2017-12-08 | 蚌埠兴科玻璃有限公司 | 一种铜铟镓硒薄膜太阳能电池背电极及其制备方法 |
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KR101533133B1 (ko) | 2015-07-01 |
US20090181179A1 (en) | 2009-07-16 |
EP2232565B1 (en) | 2014-03-12 |
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US8465692B2 (en) | 2013-06-18 |
TW200942492A (en) | 2009-10-16 |
CN101919062A (zh) | 2010-12-15 |
JP5574978B2 (ja) | 2014-08-20 |
MY157342A (en) | 2016-05-31 |
EP2232565A1 (en) | 2010-09-29 |
JP2011511886A (ja) | 2011-04-14 |
US20110147208A1 (en) | 2011-06-23 |
HK1151389A1 (zh) | 2012-01-27 |
EP2232565A4 (en) | 2012-07-25 |
TWI405723B (zh) | 2013-08-21 |
WO2009089421A1 (en) | 2009-07-16 |
US20140342497A1 (en) | 2014-11-20 |
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