CN102216496B - 适用作析氢阴极的电极 - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
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- 239000011609 ammonium molybdate Substances 0.000 claims description 2
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- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 claims 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical group N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 14
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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- 229910000975 Carbon steel Inorganic materials 0.000 description 1
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- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
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- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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Abstract
本发明提供了一种在电解槽中用于析氢的阴极，例如氯碱电解槽或用于生产氯酸盐或次氯酸盐的电解槽，其从电镀涂覆镍与非晶氧化钼共沉积的镍基材或其它导电材料开始而获得。
Description
技术领域
本发明涉及一种在电解槽中用作析氢阴极的电极。
背景技术
本发明涉及一种用于电解过程的电极，特别涉及一种在工业电解过程中适用于析氢的阴极。用于同时生产氯和碱的碱盐水的电解以及生产次氯酸盐和氯酸盐的电化学过程是利用阴极析氢的工业电极应用的最有代表性的实施例，但是电极不仅限于一些特定的使用。在电解过程中，工业竞争力决定于几个因素，其中最重要的是能耗的降低，其直接与运行电压相关：这证实目的在于降低后者的多个组成的许多努力是正确的，在其中必须将阴极过电压计入。虽然长久以来认为，在多个工业应用中利用不具有催化活性的化学耐受性材料(例如碳钢或镍)的电极能自然获得的阴极过电压是可接受的，但是，现在能量成本的升高使得催化系统的使用成为必要从而促进阴极析氢。在现有技术中，通过具有基于贵金属例如铂或钌的催化涂层的镍基材的使用给出了所实践的在电解过程中降低阴极析氢过电压的解决方法。但是，这意味着，由于贵金属的高价格而显著提高费用。因此，实施了一些基于作为贵金属的替代的材料的催化系统，其中在通过电共沉积或热过程，例如火焰或等离子热喷涂得到带有其它金属例如钼、锰、钛、钨、钒、铟、铬和锌的各种镍合金。在所有的这些系统中，镍-钼电镀合金给出最好的结果，但是其催化活性仍然与通过贵金属基涂层可获得的催化活性相差很远；正如通过其表现出的塔菲尔(Tafel)斜率与相关于纯镍(-120mV每以十为底的电流对数(current decade))的塔菲尔斜率相等的事实所证实的，实际上所引用的合金未表现出任何实质的促进效果，并且其朝向析氢反应提高的活性归因于纯几何效果。在碱性环境中，镍和钼的金属合金也表现出不足的开路稳定性的缺点，这导致用于氯碱过程或通过次氯酸盐产生而氯化水的相应电极的不适当的持久性。不管是偶然(例如由于相关电解器的故障)或计划的(例如在氯化电解槽情况下，其中将电势转换用于电极水垢沉积的周期性清洗)，问题在例如将电极用于阳极极化的情况中进一步增强。
因此，确定用于电极的不含贵金属的催化剂配制剂是必要的，所述电极适用于在工业电解槽中用作析氢阴极，表现出改善的析氢阴极电势和在碱性环境中较高稳定性的特征，任选地也可用在开路中或阳极极化下。
发明内容
在所附权利要求中说明了本发明的电极一些方面。
在一个实施方案中，本发明涉及一种电极，该电极包含导电性基材(任选镍或铜)，其具有基于镍与至少一种无定形氧化钼共沉积的表层涂层。
实际上，发明人已经发现，当钼不以金属相而是例如可通过镍与预制备的MoO3颗粒的电共沉积获得的无定形氧化相存在时，镍钼催化系统表现出与一种贵金属相当的对于碱性环境的催化活性和稳定性。在一个实施方案中，在包含镍离子的电镀槽中进行电共沉积过程，例如在20和100mA/cm2之间的控制电流密度下包含预制备的MoO3颗粒的瓦特(Watt)浴；这具有促进MoO3以部分还原的无定形形式(形成具有表示为式HxMoO3的非化学计量氧化物，x为0到1)和/或以镍与钼混合氧化物(NiMoO4)的形式沉积的优点。
在一个实施方案中，利用分散在含镍离子的电镀槽中的NiMoO4的预制备颗粒或部分还原的氧化钼的预制备颗粒进行电共沉积，所述部分还原的氧化钼表示为式HxMoO3，x在0和1之间。
发明人发现，在约30-40mV每以十为底的电流对数的低电流密度下，所述的物质表现出与析氢反应相关的塔菲尔斜率，这清楚地表明的事实是，通过协同效应，对于在整个机理的确定中假设是同等重要的海尔霍夫斯基(Heyrovsky)和塔菲尔的部分反应，相对于一个镍电极的特征，反应机理发生了改变。在一个实施方案中，与金属镍共沉积到阴极基材上的无定形钼氧化物具有不超过50nm的颗粒尺寸，例如在10到50nm之间。
该特征可具有提高每单位表面的活性催化位置的数量的优点。不但可通过作用于沉积电流密度也可作用于悬浮在电镀槽中的氧化物颗粒的尺寸来控制无定形氧化物的颗粒尺寸。在一个实施方案中，通过前体盐例如钼酸铵的热分解获得亚微粒尺寸的MoO3颗粒，所述MoO3颗粒适用于所述颗粒尺寸的无定形钼氧化物到镍金属相中的共沉积。在一个实施方案中，在电极表层涂层中，所涉及元素的Ni∶Mo摩尔比在4和10之间。这可具有的优点是，生产与利用较低的钼含量获得的涂层相比活性更加显著的涂层，同时生产从机械结合角度看，比利用较高的钼含量获得的涂层更加稳定的涂层。
实施例1
通过从具有以下组成的瓦特浴开始同时沉积Ni和Mo无定形氧化物制备了一些电极：NiSO4·6H2O，330g/l；NiCl.6H2O，45g/l；H3BO3，38g/l；pH＝2，其包含悬浮的MoO3亚微粒颗粒。所使用的MoO3粉末通过在空气气氛中于500℃下热分解(NH4)6Mo7O24·4H2O 2小时和通过以2500rpm的磁搅拌下分散到浴中来制备。将浴中MoO3的含量改变到20g/l的最高浓度，以获得Ni∶Mo摩尔比为4到10的共沉积物。所使用的电极基材由10mm×10mm×0.2mm尺寸、在HCl蚀刻的镍片体构成。在恒流控制下，在搅拌下将浴保持在40℃，使用72C/cm2的恒定电荷转移下进行涂层沉积。对于不同的试样，沉积电流密度为10到100mA/cm2不等。使用显微照相和X-射线衍射表征由此获得的电极：此测试证明了氧化钼着色的镍沉积物的形成，致密度越高和破裂越少，沉积电流密度越高。在各种情况下，XRD谱显示了归于MoO3的特征峰(2Θ＝48°)的消失，这在通过热分解制备的粉末上是良好可见的。这表明，嵌入在镍沉积物中的氧化钼发生了相变，完全失去了其结晶性。接下来的EDS分析进一步显示了表示为式HxMoO3(x在0和1之间)的非化学计量氧化物的形成，例如H0.93MoO3和H0.34MoO3，这源自于根据下面反应的氧化钼的部分还原：
最终，也观察到在沉积期间形成的NiMoO4混合氧化物的存在。对于多个试样，沉积的氧化钼的颗粒尺寸结果为一般在10和50nm之间。
将上述描述的试样编号为1到18。
作为对比，制备了根据现有技术的基于在镍基材上的镍钼合金的电极。使用的电极基材由与用于上述试样的生产相同的镍片体构成。从具有下面组成的浴开始电镀沉积合金：Na2MoO4·2H2O，0.02M；NiCl2·6H2O，0.04M；Na2P2O7·10H2O，0.130M；NaHCO3，0.893M；ZnCl2，3×10-4M；硫酸肼，0.0254M；CdNO3·4H2O，3×10-4M；KSCN，5.8×10-4M；pH＝7.8。在15mA/cm2下进行沉积5分钟，随后增加到70mA/cm2再进行30分钟，通过与水和冰浴的热交换保持浴温低于20℃。
将上述描述的参比试样标记为0。
在25℃的温度下带有1M NaOH基阴极电解液的标准电化学电解槽中，将所获得的电极表征为析氢阴极；使用饱和甘汞电极(SCE)作为参考测量电极电势，由所述电极电势来计算相关过电压η。表1显示了获得的结果，其中J表示镍-无定形氧化钼涂层的沉积电流密度，Ni∶Mo表示在沉积物中所涉及元素的镍与钼氧化物比例，b1(V/以十为底的电流对数)表示在低电流密度(表示为lgj＜2，j以A/cm2表示)下的第一塔菲尔斜率，b2(V/以十为底的电流对数)表示在较高电流密度下的第二塔菲尔斜率，η(V)表示在0.1A/cm2的电流密度下的氢过电压。
表1
| 试样ID | J(mA/cm2) | Ni∶Mo | b1(V/dec) | b2(V/dec) | η(V) |
| 0 | --- | --- | -0.124 | --- | 0.264 |
| 1 | 10 | 4 | -0.042 | -0.172 | 0.250 |
| 2 | 30 | 4 | -0.043 | -0.123 | 0.160 |
| 3 | 40 | 4 | -0.042 | -0.110 | 0.166 |
| 4 | 50 | 4 | -0.048 | -0.128 | 0.154 |
| 5 | 70 | 4 | -0.046 | -0.124 | 0.184 |
| 6 | 100 | 4 | -0.048 | -0.128 | 0.195 |
| 7 | 10 | 6 | -0.042 | -0.147 | 0.235 |
| 8 | 20 | 6 | -0.042 | -0.138 | 0.183 |
| 9 | 30 | 6 | -0.044 | -0.120 | 0.173 |
| 10 | 40 | 6 | -0.043 | -0.116 | 0.208 |
| 11 | 50 | 6 | -0.044 | -0.119 | 0.158 |
| 12 | 100 | 6 | -0.049 | -0.122 | 0.202 |
| 13 | 20 | 10 | -0.043 | -0.124 | 0.189 |
| 14 | 30 | 10 | -0.044 | -0.117 | 0.180 |
| 15 | 40 | 10 | -0.042 | -0.111 | 0.172 |
| 16 | 50 | 10 | -0.043 | -0.124 | 0.155 |
| 17 | 70 | 10 | -0.046 | -0.118 | 0.192 |
| 18 | 100 | 10 | -0.046 | -0.123 | 0.212 |
如从表中可注意到的，具有基于镍与无定形钼氧化物共沉积的表层涂层的电极试样在低和高电流密度下表现出两个不同的塔菲尔斜率，与利用现有技术的电极可获得的那些相比，证明不同反应机理的开始。此外，在0.1A/cm2下，催化活性显著提高，特别是对于在证明为最佳值的约50mA/cm2的电流密度下沉积的涂层。相反地，在考虑范围中，Ni∶Mo摩尔比的影响表现为相当有限。利用在20到100mA/cm2的电流密度范围中沉积的试样可获得的阴极过电压与对于带有着色涂层的镍阴极所预期的阴极过电压相似，所述着色涂层基于在8-10g/m2左右的Ru负载与二氧化钌共沉积的镍，并且比对于带有超过15g/m2的Ru负载的镍和二氧化钌的着色涂层的相同阴极的所预期的阴极过电压高大约30-50mV。
实施例2
在85℃的温度下，在33％的NaOH中将与上述实施例的试样4相同的一些电极表征为析氢电极，并且在不同的电势下(V/SCE)进行持续1000秒的阳极极化以模仿氯碱设备中的故障条件。表2报道了在阳极极化之前和之后在塔菲尔斜率和在0.2A/cm2下的阴极电压(V/SCE)方面的结果。
表2
由表可推得，阴极活性不受所说明数量级的阴极电势的长期使用的影响。
实施例3
从与实施例1类似的包含预还原氧化钼的悬浮亚微粒颗粒的瓦特浴开始，通过Ni和无定形氧化Mo的同时沉积来制备一些电极。所使用的氧化钼粉末通过将由热分解如实施例1的(NH4)6Mo7O24·4H2O所得的MoO3粉末在623K下在氢气氛中进行还原1小时而得到。由此处理的粉末的XRD谱显示了部分还原的Mo(VI)氧化物的一些相的特征峰，其中可区分H0.93MoO3和H0.34MoO3，和可归于MoO3的显著更低强度的峰。在20-100mA/cm2的不同电流密度下进行沉积。如实施例1中，在25℃的温度下带有1M NaOH基阴极电解液的标准电化学电解槽中，将所获得的电极表征为析氢阴极；关于塔菲尔斜率和氢过电压的结果几乎与利用未还原的MoO3粉末获得的相似试样的那些结果一致。
可通过以下方式得到类似的结果：在电镀槽中，从混合镍和钼氧化物的预制备颗粒的悬浮物例如NiMoO4开始进行共沉积，其例如可通过来自硝酸镍和七钼酸氨溶液的水合形式的共沉积并随后在550℃下热分解而获得，或从各种还原的、未还原的或部分还原的MoO3和根据不同组合的其它钼的混合氧化物开始，其任选地通过不同的钼前体盐的热分解得到。
前面的说明不应该被认为是限制本发明，其可根据不同的实施方案使用而不背离开其范围，并且其范围仅由所附权利要求限定。
在本申请的说明书和权利要求书中，术语“包含”和其变体如“包括”和“含有”不意在排除其它元素或添加物的存在。
仅为了对本发明提供背景的目的，将对文献、条例、材料、装置、制品等的讨论包含在此说明书中。这不暗示或表示，在本申请的每个权利要求的优先权日之前，这些内容中的任何或所有形成与本发明相关的现有技术基础的一部分或形成本领域的公知技术。
Claims (11)
1.一种电极，其在电解过程中适于用作析氢的阴极，包含具有基于镍与至少一种无定形氧化钼共沉积的表层涂层的导电基材。
2.根据权利要求1所述的电极，其中所述无定形氧化钼包含至少一种选自MoO3，NiMoO4和部分还原的表示为式HxMoO3的Mo(VI)氧化物的物质，x为0到1。
3.根据权利要求1或2所述的电极，其中所述无定形氧化钼具有10到50nm的颗粒尺寸。
4.根据权利要求1或2所述的电极，其中所述表层涂层所涉及元素的Ni∶Mo摩尔比在4到10之间。
5.一种制造根据上述权利要求中任一项所述的电极的方法，其包括以下同时进行或顺序进行的步骤：
-将选自MoO3的物质的颗粒添加到包含镍离子的电镀槽中；
-在20到100mA/cm2的电流密度下，将镍与至少一种无定形氧化钼电共沉积到浸入所述电镀槽中的阴极基材上。
6.根据权利要求5所述的方法，其中所述MoO3颗粒通过前体盐的热分解获得。
7.根据权利要求6所述的方法，其中所述前体盐是钼酸铵。
8.根据权利要求5到7中任一项所述的方法，其中所述电镀槽为在pH3到4下包含硫酸镍、氯化镍和硼酸的瓦特浴。
9.根据权利要求5所述的方法，其中所述阴极基材由镍或铜制成。
10.根据权利要求6所述的方法，其中所述前体盐是(NH4)6Mo7O24.4H2O。
11.用于采用阴极析氢的电解方法的电解槽，其包含至少一个根据权利要求1到4中任一项的电极作为阴极。
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| CN103515620B (zh) * | 2012-06-20 | 2015-09-30 | 江苏氢阳能源有限公司 | 一种电极材料、其应用、直接燃料电池、及电化学加氢电解槽 |
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| CN103952719B (zh) * | 2014-03-28 | 2017-05-03 | 中国科学院物理研究所 | 一种用于电分解水制氢的催化剂及其制备方法 |
| CN104894595B (zh) * | 2015-05-19 | 2017-09-12 | 派新（上海）能源技术有限公司 | 一种高催化活性的非晶金属氧化物析氢电极及其制备方法 |
| US20200040471A1 (en) * | 2017-04-24 | 2020-02-06 | Sumitomo Electric Industries, Ltd. | Oxide-dispersed metal porous body, electrolysis electrode, and hydrogen generation apparatus |
| CN107519879A (zh) * | 2017-09-01 | 2017-12-29 | 武汉氢阳能源有限公司 | 一类二元、三元过渡金属氢化物及其制备方法和应用 |
| CN108048895B (zh) * | 2017-12-20 | 2019-12-17 | 福州大学 | 一种嵌入钌锆复合氧化物的镍基活性电极材料及其制备方法 |
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| CN108048869B (zh) * | 2017-12-20 | 2019-08-09 | 福州大学 | 一种嵌入钌铪复合氧化物的镍基活性电极材料及其制备方法 |
| CN108588754A (zh) * | 2018-05-11 | 2018-09-28 | 上海应用技术大学 | 一种用于电催化析氢的钼酸镍/石墨烯复合材料及制备方法 |
| CN110129825B (zh) * | 2019-05-23 | 2022-02-01 | 天津市大陆制氢设备有限公司 | 一种高效Ni/Ni(OH)2析氢电极及其制备方法 |
| CN111118539B (zh) * | 2019-06-06 | 2022-03-22 | 天津大学 | 电沉积法制备氧化镍纳米片上负载镍-氧化钼量子点 |
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- 2011-04-10 IL IL212229A patent/IL212229A0/en unknown
- 2011-04-20 ZA ZA2011/02994A patent/ZA201102994B/en unknown
- 2011-06-01 EG EG2011060890A patent/EG26148A/en active
- 2011-06-02 US US13/151,520 patent/US8696877B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4323595A (en) * | 1979-01-24 | 1982-04-06 | Ppg Industries, Inc. | Nickel-molybdenum cathode |
| CN85108839A (zh) * | 1984-12-14 | 1986-08-20 | 奥罗茨奥·诺拉电化学工厂联合股票公司 | 电极的制备及其在电化学加工上的应用 |
| CN1602557A (zh) * | 2001-12-12 | 2005-03-30 | 三洋电机株式会社 | 镍氢蓄电池 |
Non-Patent Citations (1)
| Title |
|---|
| JP昭56-22636A 1981.03.03 * |
Also Published As
| Publication number | Publication date |
|---|---|
| PL2361324T3 (pl) | 2013-09-30 |
| ZA201102994B (en) | 2012-06-27 |
| EP2361324B1 (en) | 2013-04-10 |
| TW201022477A (en) | 2010-06-16 |
| US20110226627A1 (en) | 2011-09-22 |
| BRPI0923229A2 (pt) | 2016-01-26 |
| DK2361324T3 (da) | 2013-07-08 |
| ES2421232T3 (es) | 2013-08-29 |
| JP2012510567A (ja) | 2012-05-10 |
| CL2009002144A1 (es) | 2010-01-22 |
| AR074457A1 (es) | 2011-01-19 |
| EA201170743A1 (ru) | 2011-12-30 |
| WO2010063695A2 (en) | 2010-06-10 |
| JP5442757B2 (ja) | 2014-03-12 |
| CN102216496A (zh) | 2011-10-12 |
| IT1392168B1 (it) | 2012-02-22 |
| MX2011005634A (es) | 2011-06-24 |
| EG26148A (en) | 2013-03-27 |
| KR20110106303A (ko) | 2011-09-28 |
| CA2744299A1 (en) | 2010-06-10 |
| WO2010063695A3 (en) | 2010-08-05 |
| EA018528B1 (ru) | 2013-08-30 |
| IL212229A0 (en) | 2011-06-30 |
| US8696877B2 (en) | 2014-04-15 |
| EP2361324A2 (en) | 2011-08-31 |
| PT2361324E (pt) | 2013-06-25 |
| AU2009324182B2 (en) | 2014-07-24 |
| AU2009324182A1 (en) | 2010-06-10 |
| ITMI20082130A1 (it) | 2010-06-03 |
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