METHOD FOR PASSIVE METAL ACTIVATION AND USES THEREOF

• US 20170179464A1
• Filed: 03/31/2015
• Published: 06/22/2017
• Est. Priority Date: 03/31/2014
• Status: Active Grant

• Current Assignee: TECHNION RESEARCH AND DEVELOPMENT FOUNDATION, LTD.
• Original Assignee: TECHNION RESEARCH AND DEVELOPMENT FOUNDATION, LTD.
• Inventors: EIN-ELI, Yair, GELMAN, Danny, SHVARTSEV, Boris, KRAYTSBERG, Alexander
• Granted Patent: US 10,644,304 B2
• Time in Patent Office: Days
• CPC Class Codes: B23K 2103/04 Steel or steel alloys
• CPC Class Codes: B23K 2103/10 Aluminium or alloys thereof
• CPC Class Codes: B23K 35/3605 Fluorides
• CPC Class Codes: B23K 35/383 mainly containing noble gases or nitrogen
• CPC Class Codes: B23K 9/23 taking account of the properties of the materials to be welded
• CPC Class Codes: C25D 3/665 from ionic liquids
• CPC Class Codes: C25D 5/34 Pretreatment of metallic surfaces to be electroplated
• CPC Class Codes: C25D 5/38 of refractory metals or nickel
• CPC Class Codes: C25D 5/54 Electroplating of non-metallic surfaces C25D7/12 takes precedence
• CPC Class Codes: C25D 5/56 of plastics
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2300/0045 Room temperature molten salts comprising at least one organic ion
• CPC Class Codes: H01M 4/044 Activating, forming or electrochemical attack of the supporting material
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/463 Aluminium based
• CPC Class Codes: H01M 4/502 : for non-aqueous cells H01M4/505 takes precedence
• CPC Class Codes: H01M 4/628 : Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• CPC Class Codes: H01M 4/661 : Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

Disclosed is a method for activating a surface of metals, such as self-passivated metals, and of metal-oxide dissolution, effected using a fluoroanion-containing composition. Also disclosed is an electrochemical cell utilizing an aluminum-containing anode material and a fluoroanion-containing electrolyte, characterized by high efficiency, low corrosion, and optionally mechanical or electrochemical rechargeability. Also disclosed is a process for fusing (welding, soldering etc.) a self-passivated metal at relatively low temperature and ambient atmosphere, and a method for electrodepositing a metal on a self-passivated metal using metal-oxide source.

Claims

1-73. -73. (canceled)

74. A method of activating a surface of a metal or a metal alloy, the method comprising contacting the surface with a fluoroanion-containing composition, to thereby obtain an activated metal surface.

75. The method of claim 74, wherein said activated metal surface is essentially devoid of a passivation layer.

76. The method of claim 74, wherein said activated metal surface comprises fluorohydrogenate-metal species (HF-species).

77. The method of claim 76, wherein said activated metal surface exhibits at least two peaks in an attenuated total reflection infrared spectrum having a wavenumber range selected from the group consisting of from 3150 cm⁻

1 to 2840 cm<sup>−

1</sup>, from 1110 cm<sup>−

1</sup> to 800 cm<sup>−

1</sup>, from 2505 cm<sup>−

1</sup> to 2200 cm<sup>−

1</sup>, from 1920 cm<sup>−

1</sup> to 1600 cm<sup>−

1</sup> and/or from 1170 cm<sup>−

1</sup> to 870 cm<sup>−

1</sup>.

78. The method of claim 74, wherein said metal or metal alloy comprises a self-passivated metal or a self-passivated metal alloy.

79. The method of claim 78, wherein said self-passivated metal alloy is aluminum.

80. The method of claim 78, wherein said self-passivated metal alloy is alloy steel.

81. The method of claim 74, wherein said fluoroanion-containing composition comprises a at least one [(HF)_nF]⁻

species.

82. The method of claim 74, wherein said fluoroanion-containing composition comprises a room temperature ionic liquid (a fluoroanion-RTIL).

83. The method of claim 82, wherein said RTIL is EMIm(HF)_2.3F and/or Pyr₁₄(HF)_2.3F.

84. An electrochemical cell device comprising an anode, a cathode, and an electrolyte, wherein said anode comprises aluminum and said electrolyte being a fluoroanion-containing composition.

85. The device of claim 84, wherein said anode exhibits at least two of the peaks of an attenuated total reflection infrared spectrum as presented in Plot 8 of FIG. 9.

86. The device of claim 84, wherein said anode is essentially devoid of a passivation layer.

87. The device of claim 84, wherein said anode comprises fluorohydrogenate-metal species (HF-species).

88. The device of claim 84, wherein said anode exhibits at least two peaks of an attenuated total reflection infrared spectrum having a wavenumber range selected from the group consisting of from 3150 cm⁻

1 to 2840 cm<sup>−

1</sup>, from 1110 cm<sup>−

1</sup> to 800 cm<sup>−

1</sup>, from 2505 cm<sup>−

1</sup> to 2200 cm<sup>−

1</sup>, from 1920 cm<sup>−

1</sup> to 1600 cm<sup>−

1</sup> and/or from 1170 cm<sup>−

1</sup> to 870 cm<sup>−

1</sup>.

89. The device of claim 84, wherein said anode comprises at least 99% aluminum.

90. The device of claim 84, wherein said fluoroanion-containing composition comprises a at least one [(HF)_nF]⁻

species.

91. The device of claim 84, wherein said fluoroanion-containing composition comprises a room temperature ionic liquid (a fluoroanion-RTIL).

92. The device of claim 91, wherein said RTIL is EMIm(HF)_2.3F and/or Pyr₁₄(HF)_2.3F.

93. A process for fusing a first metal or a first metal alloy to a second metal or a second metal alloy, wherein at least one of said first metal or said second metal is a self-passivated metal, the process comprising contacting a surface of said first metal and/or said second metal being said self-passivating metal with a fluoroanion-containing composition, to thereby obtain an activated metal surface, melting at least one of the first metal and the second metal, and/or optionally melting a filler metal so as to fill an interface between the first metal and the second metal, and cooling the first metal and the second metal or cooling said filler, to thereby fuse the first metal to the second metal.

94. The process of claim 93, further comprising contacting a surface of said first metal or said second metal which is not said self-passivated metal with a fluoroanion-containing composition, to thereby obtain an activated metal surface.

95. The process of claim 93, comprising melting said filler metal, the process further comprising contacting a surface of said filler metal with a fluoroanion-containing composition, to thereby obtain an activated metal surface.

96. The process of claim 93, wherein said filler metal is a self-passivated metal.

97. The process of claim 93, wherein said activated metal surface is essentially devoid of a passivation layer.

98. The process of claim 97, effected at a temperature lower than a melting temperature of said passivation layer.

99. The process of claim 93, wherein said activated metal surface comprises fluorohydrogenate-metal species (HF-species).

100. The process of claim 93, wherein said activated metal surface exhibits at least two peaks in an attenuated total reflection infrared spectrum having a wavenumber range selected from the group consisting of from 3150 cm⁻

1 to 2840 cm<sup>−

1</sup>, from 1110 cm<sup>−

1</sup> to 800 cm<sup>−

1</sup>, from 2505 cm<sup>−

1</sup> to 2200 cm<sup>−

1</sup>, from 1920 cm<sup>−

1</sup> to 1600 cm<sup>−

1</sup> and/or from 1170 cm<sup>−

1</sup> to 870 cm<sup>−

1</sup>.

101. The process of claim 93, wherein said self-passivated metal is aluminum.

102. The process of claim 93, wherein said first metal alloy or said second metal alloy is an alloy steel.

103. The process of claim 93, wherein said fluoroanion-containing composition comprises a at least one [(HF)_nF]⁻

species.

104. The process of claim 93, wherein said fluoroanion-containing composition comprises a room temperature ionic liquid (a fluoroanion-RTIL).

105. The process of claim 104, wherein said RTIL is EMIm(HF)_2.3F and/or Pyr₁₄(HF)_2.3F.

106. A method for electrodepositing a first metal on a surface of a second metal, the method comprising contacting the second metal with a fluoroanion-containing composition to thereby afford an activated metal surface, and depositing the first metal on said activated surface.

107. The method of claim 106, further comprising:

separating the second metal from said fluoroanion-containing composition,

placing the second metal in an electrolyte that comprises a source of said first metal,

applying a cathodic potential or a cathodic current between the second metal while in said electrolyte and an electrode which is in an electrical communication with said electrolyte,

to thereby effect electrodepositing.

108. The method of claim 106, further comprising adding a source of said first metal into said fluoroanion-containing composition.

109. The method of claim 108, further comprising applying a cathodic potential or a cathodic current between the second metal while in contact with said fluoroanion-containing composition, and an electrode which is in an electrical communication with said fluoroanion-containing composition to thereby effect electrodepositing.

110. The method of claim 106, the second metal is a self-passivated metal.

111. The method of claim 106, the first metal is copper and the second metal comprises tantalum.

112. The method of claim 106, effected without seeding the second metal with the first metal.

113. The method of claim 106, wherein said fluoroanion-containing composition comprises a at least one [(HF)_nF]⁻

species.

114. The method of claim 106, wherein said fluoroanion-containing composition comprises a room temperature ionic liquid (a fluoroanion-RTIL).

115. The method of claim 114, wherein said RTIL is EMIm(HF)_2.3F and/or Pyr₁₄(HF)_2.3F.