JP2018511141A - Hydrogen storage alloy - Google Patents

Abstract

A hydrogen storage alloy comprising a metal oxide having ≧ 60 atomic% oxygen; and / or having a metal region separated by a boundary region, the boundary region having at least one flow path; and And / or having a metal region separated by a boundary region, wherein the boundary region has a length and an average width, wherein the average width is from about 12 nm to about 1100 nm; and / or the metal oxide A metal oxide zone containing, the oxide zone running side by side with at least one flow path; and / or a hydrogen storage alloy containing a Ni / Cr metal oxide has improved electrochemical Having properties such as improved low temperature electrochemical properties.

Description

The present invention relates to a hydrogen storage alloy having improved electrochemical properties. This alloy is, for example, a modified AB _x type alloy, where x is from about 0.5 to about 5.

  Alloys capable of absorbing and discharging hydrogen can be used as hydrogen storage media and / or as electrode materials for solid hydrogen storage media, metal hydride cells, fuel cells, metal hydride air cell systems, and the like. Such materials are known as metal hydride (MH) materials.

Efforts continue to improve the electrochemical properties of AB _x MH alloys, for example used as negative electrode active materials in batteries. Nickel metal hydride (NiMH) batteries are green technology and have been replaced by toxic nickel cadmium (NiCd) batteries in all applications except those requiring discharge performance at low temperatures (eg <25 ° C.). . Further improvements in the low temperature electrochemical properties of AB _x metal hydride alloys will make it possible to completely eliminate NiCd batteries from the consumer market.

  Surprisingly, certain metal hydride alloys have been found to exhibit improved electrochemical properties, such as improved low temperature electrochemical properties.

a) at least one electrochemically active main phase; and b) at least one electrochemically active secondary phase;
A hydrogen storage alloy containing is disclosed.

Also,
a) at least one main phase;
b) a hydrogen storage alloy having one or more rare earth elements, and c) a catalyst storage phase.
Here, the abundance of the occlusive secondary phase is> 0.5 mass%, and the abundance of the catalyst secondary phase is about 0.3 to about 15 mass% based on the alloy.

Also,
The discharge capacity measured at 50MAg ^-1, and defined as the ratio to the discharge capacity measured in 4MAg ^-1, the third-time cycles ≧ 93% of the high proportion of discharge performance, apply alkaline pre-treated before the half-cell measurements Without, measured with a liquid cell design on a partially precharged Ni (OH) ₂ cathode, where each sample electrode was charged at a constant current density of 50 mAg ⁻¹ for 10 hours and then 50 mAg and discharged at a current density of ^-1, 12 and 4MAg ^-1 twice pull (pull) followed, and / or ≦ 60 [Omega] · of g, the charge transfer resistance at -40 ℃ for one or more of the main phase (R) and / or ≦ 60 Ω · g, charge transfer resistance (−R) at −40 ° C., and / or surface catalyst at −40 ° C. for ≦ 30 seconds for one main phase or multiple main phases Hydrogen storage alloy showing performance is disclosed That.

  Also disclosed is a hydrogen storage alloy containing a metal oxide having oxygen ≧ 60 atomic%.

  Also disclosed is a hydrogen storage alloy having a metal region adjacent to the boundary region, the boundary region having at least one flow path.

  Also disclosed is a hydrogen storage alloy having a metal region adjacent to the boundary region, wherein the boundary region has a length and an average width, wherein the average width is from about 12 nm to about 1100 nm.

  Also disclosed is a hydrogen storage alloy having a metal oxide zone containing a metal oxide, the oxide zone running in parallel with at least one flow path.

  Also disclosed is a hydrogen storage alloy containing a Ni / Cr metal oxide.

  The hydrogen storage alloy according to the present invention has improved electrochemical properties, for example improved low temperature electrochemical properties.

Detailed Disclosure An alloy according to the present invention is, for example, a modified ABx type metal hydride (MH), where A is generally a hydride forming element and B is a weakly forming element of hydride, Or a forming element that does not form a hydride. A is generally a relatively large metal atom having 4 or less valence electrons, and B is generally a relatively small metal atom having 5 or more valence electrons. Suitable AB _x alloys include those where x is from about 0.5 to about 5. The alloy according to the present invention can reversibly absorb (charge) and discharge (discharge) hydrogen. For example, an alloy according to the present invention can reversibly absorb and desorb hydrogen at ambient conditions (25 ° C. and 1 atmosphere).

AB _x type alloys are for example of the following classification (just examples): AB (HfNi, TiFe, TiNi), AB ₂ (ZrMn ₂ , TiFe ₂ ), A ₂ B (Hf ₂ Fe, Mg ₂ Ni) , AB ₃ (NdCo ₃ , GdFe ₃ ), A ₂ B ₇ (Pr ₂ Ni ₇ , Ce ₂ Co ₇ ), and AB ₅ (LaNi ₅ , CeNi ₅ ).

The alloy according to the present invention is obtained, for example, by modifying an AB _x type base alloy (at least one element A and one element B) with one or more modifying elements. Modifications also include judicious selection of metals and their atomic ratios, and control of processing parameters during solidification, post-solidification process, annealing, and processing or processing of hydrogen storage alloys. Annealing can be performed in a vacuum, partial vacuum, or in an inert gas environment, followed by natural or forced circulation air or rapid cooling. Modifications also include activation techniques such as etching, pre-oxidation, electroless and electroplating and coating. The etching step includes a basic and / or acidic etching process for selectively or preferentially etching one or more elements or oxides or hydroxides or phases in the interfacial region of the hydrogen storage alloy. be able to.

  Prior to use, the metal or metal alloy electrode is typically activated and the process removes or reduces the original surface oxide in the interfacial region. The activation process can be accomplished by etching, electrical homing, pretreatment, or other suitable method for changing the surface oxide. Activation can be applied to the electrode alloy powder, to the finished electrode, or any time in between.

  The alloy according to the invention is obtained by using a combination of the above techniques. The alloy to be modified according to the invention is a “base alloy”.

  Suitable modifying elements include rare earth metals, Si, Al and V. The rare earth elements are Sc, Y, La and lanthanides. Misch metal (Mm) is included in the term “one or more rare earth elements”. The rare earth element is, for example, La.

  Metal hydride base alloys include alloys containing Ti, V and Mn (Ti-V-Mn alloys) and alloys containing Ti, V and Fe. For example, hydrides of alloys containing about 31 to about 46 atomic percent Ti, about 5 to about 33 atomic percent V, and about 36 to about 53 atomic percent Mn and / or Fe. Suitable alloys are taught, for example, in U.S. Pat. No. 4,116,689 (U.S. Pat. No. 4,111,689).

Metal hydride base alloy comprises an alloy of formula AB _x, wherein A contains less than about 50 to 100 atomic percent Ti, residue is Zr and / or Hf, B is about 30 Ni ˜100 atomic percent, the balance being one or more elements selected from Cr, V, Nb, Ta, Mo, Fe, Co, Mn, Cu and rare earths, and x is from about 1 to about 3 It is. These alloys are taught, for example, in US Pat. No. 4,16,0014 (US Pat. No. 4,160,014).

Metal hydride base alloy includes the following alloy: formula (TiV _2-x Ni x) alloy _1-y M _y, where x is from about 0.2 to about 1.0, M is Al and an / or Zr, alloys of formula _{Ti 2-x Zr x V 4} -y Ni y, where x is 0 is about 1.5, y is from about 0.6 to about 3.5 There, and alloys of the formula _{Ti 1-x Cr x V 2} -y Ni y, where x is 0 to about 0.75, y is from about 0.2 to about 1.0. These base alloys are disclosed, for example, in US Pat. No. 4,551,400 (US Pat. No. 4,551,400).

  The metal hydride base alloy is, for example, one or more elements selected from the group consisting of Mg, Ti, V, Zr, Nb, La, Si, Ca, Sc and Y, and Cu, Mn, Fe, Ni, Al And one or more elements selected from the group consisting of Mo, W, Ti, Re and Co. For example, the MH base alloy can contain one or more elements selected from Ti, Mg, and V, and can contain Ni. The MH base alloy advantageously contains Ti and Ni, for example in the atomic range of about 1: 4 to about 4: 1. The MH base alloy advantageously contains Mg and Ni, for example in the atomic range of about 1: 2 to about 2: 1. Suitable base alloys are disclosed, for example, in US Pat. No. 4,623,597 (U.S. Pat. No. 4,623,597).

Base alloys, include those of the formula _{(Ti 2-x Zr x V} 4-y Ni y) 1-z Cr z, where x is 0 to about 1.5, y is from about 0.6 ~ About 3.5 and z is ≤0.2. These base alloys are taught, for example, in US Pat. No. 4,728,586 (US Pat. No. 4,728,586).

The metal hydride base alloy contains, for example, V, Ti, Zr and Ni (Ti-V-Zr-Ni alloy) or contains V, Ti, Zr, Ni and Cr. The MH base alloy contains, for example, one or more elements selected from Ti, V and Ni, and Cr, Zr and Al. Examples of the MH base alloy include V ₂₂ Ti ₁₆ Zr ₁₆ Ni ₃₉ Cr ₇ , (V ₂₂ Ti ₁₆ Zr ₁₆ N ₃₉ Cr ₇ ) ₉₅ Al ₅ , (V ₂₂ Ti ₁₆ Zr ₁₆ N ₃₉ Cr ₇ ) ₉₅ Mn ₅ , ( _{V 22 Ti 16 Zr 16 N 39} Cr 7) 95 Mo 5, (V 22 Ti 16 Zr 16 N 39 Cr 7) 95 Cu 5, (V 22 Ti 16 Zr 16 N 39 Cr 7) 95 W 5, (V 22 _{Ti 16 Zr 16 N 39 Cr 7} ) 95 Fe 5, (V 22 Ti 16 Zr 16 N 39 Cr 7) 95 Co 5, V 22 Ti 16 Zr 16 N 32 Cr 7 Co 7, V 20.6 Ti 15 Zr 15 N 30 Including Cr _6.6 Co _6.6 Mn _3.6 Al _2.7 and V ₂₂ Ti ₁₆ Zr ₁₆ N _27.8 Cr ₇ Co _5.9 Mn _3.1 Al _2.2 alloy. MH base alloy, for example, comprise an alloy of formula _{(V y'-y Ni y Ti} x'-x Zr x Cr z) a M b, where y 'is from about 3.6 to about 4.4, y is from about 0.6 to about 3.5, x ′ is from about 1.8 to about 2.2, x is from 0 to about 1.5, and z is from 0 to about 1.44. , A is about 70 to about 100, b is 0 to about 30, and M is one or more elements selected from the group consisting of Al, Mn, Mo, Cu, W, Fe and Co. . These values are atomic percent (at%). Suitable MH base alloys are taught, for example, in US Pat. No. 5,096,667 (US Pat. No. 5,096,667).

Base alloys, include those of formula (metal _{alloy) a Co b Mn c Fe d} Sn e, where (a metal alloy) is about 0.1 to about 60 atomic percent Ti, about 0.1 Zr, About 40 atomic percent, V containing 0 to about 60 atomic percent, Ni containing about 0.1 to about 57 atomic percent, and Cr containing 0 to about 56 atomic percent, b being 0 to about 7.5 atomic percent, c is from about 13 to about 17 atomic percent, d is from 0 to about 3.5 atomic percent, and e is from 0 to about 1.5 atomic percent, where a + b + c + d + e = 100 atomic percent. Suitable MH base alloys are disclosed, for example, in US Pat. No. 5,536,591 (US Pat. No. 5,536,591).

Metal hydride base alloys include LaNi ₅ type alloys, alloys containing Ti and Ni, and alloys containing Mg and Ni. The Ti- and Ni-containing alloy can further contain one or more of Zr, V, Cr, Co, Mn, Al, Fe, Mo, La, or Mm (Misch metal). Mg and Ni-containing alloys further include Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Mm, One or more elements selected from Pd, Pt and Ca can be contained. Suitable base alloys are taught, for example, in US Pat. No. 5,554,456 (US Pat. No. 5,554,456).

The metal hydride base alloy is, for example, an alloy based on LaNi ₅ or TiNi. The MH base alloy includes, for example, one or more hydride forming elements selected from the group consisting of Ti, V, and Zr, Ni, Cr, Co, Mn, Mo, Nb, Fe, Al, Mg, Cu, Sn, and Ag. And one or more elements selected from the group consisting of Zn and Pd. The MH-based alloy includes, for example, one or more hydride forming elements selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, and Mm, and Ni, Cr, Co, Mn, Fe, Cu, Sn. And one or more elements selected from the group consisting of Al, Si, B, Mo, V, Nb, Ta, Zn, Zr, Ti, Hf and W. The MH base alloy can contain one or more elements selected from the group consisting of Al, B, C, Si, P, S, Bi, In and Sb.

Base _{alloys, (Mg x Ni 1-x} ) includes _a M _b alloy, where M is, Ni, Co, Mn, Al , Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn Th, Si, Zn, Li, Cd, Na, Pb, La, Mm, Pd, Pt and one or more elements selected from the group consisting of Ca, b is 0 to about 30 atomic% , A + b is 100 atomic percent and x is about 0.25 to about 0.75.

The base alloy also includes an hydride of an alloy of formula ZrMo _d Ni _e , where d is from about 0.1 to about 1.2, and e is from about 1.1 to about 2.5.

Base alloy comprises an alloy of the formula _{ZrMn w V x M y Ni z} , where M is Fe or Co, w is from about 0.4 to about 0.8 atomic%, x is from about 0. 1 to about 0.3 atomic%, y is 0 to about 0.2 atomic%, z is about 1 to about 1.5 atomic%, and w + x + y + z is about 2 to about 2.4 atomic%. is there.

MH base alloy comprises from about 0.1 to about 25 atomic percent of the alloy of the formula LaNi _5, wherein La or Ni is, Ia of the Periodic Table, II group, III-group, IV group and Va group (lanthanides except 1) or more metals selected from.

MH base alloys include those of the formula TiV _2-x Ni _x , where x is about 0.2 to about 0.6.

MH base alloy also includes an alloy of the formula _{Ti a Zr b Ni c Cr d} M x, where M is, Al, Si, V, Mn , Fe, Co, Cu, Nb, from the group consisting of Ag and Pd One or more selected elements, a is from about 0.1 to about 1.4, b is from about 0.1 to about 1.3, and c is from about 0.25 to about 1.95. D is from about 0.1 to about 1.4, x is from 0 to about 0.2, and a + b + c + d = about 3.

MH base alloy comprises an alloy of the formula _{Ti 1-x Zr x Mn 2} -yz Cr y V z, where x is about 0.05 to about 0.4, y is from 0 to about 1.0 And z is from 0 to about 0.4.

MH base alloys also include alloys of the formula LnM ₅ where Ln is one or more lanthanides and M is Ni and / or Co.

  The base alloy is, for example, one or more elements selected from group II, group IV and group V of the periodic table, and one or more elements selected from the group consisting of Ni, Cu, Ag, Fe and Cr—Ni steels. Contains from about 40 to about 75 weight percent metal.

  The MH base alloy can also contain a main texture Mm-Ni system. A base alloy suitable for modification is taught in US Pat. No. 5,840,440 (U.S. Pat. No. 5,840,440).

The metal hydride base alloy contains, for example, V, Ti, Zr, Ni, Cr and Mn. MH-based alloys are, for example, V, Ti, Zr, Ni, Cr, Mn and Al; V, Ti, Zr, Ni, Cr, Mn and Sn; V, Ti, Zr, Ni, Cr, Mn and Co; Contains Ti, Zr, Ni, Cr, Mn, Al, Sn, and Co, or contains V, Ti, Zr, Ni, Cr, Mn, Al, Sn, Co, and Fe. MH base alloy comprises an alloy of formula (metal _{alloy) a Co b Fe c Al d} Sn e, where (a metal alloy) is about 0.1 to about 60 atomic percent Ti, and Zr about 0.1 About 40 atomic percent, V from 0 to about 60 atomic percent, Ni from about 0.1 to about 57 atomic percent, Mn from about 5 to about 22 atomic percent, and Cr from 0 to 56 atomic percent, b is About 0.1 to about 10 atomic percent, c is about 0 to about 3.5 atomic percent, d is about 0.1 to about 10 atomic percent, and e is about 0.1 to about 3 atomic percent A + b + c + d + e = 100 atomic%. Suitable MH base alloys are taught, for example, in US Pat. No. 6,270,719 (US Pat. No. 6,270,719).

The metal hydride base alloy includes one or more alloys selected from the group consisting of AB, AB ₂ , AB ₅ and A ₂ B type alloys, where A and B are transition metals, rare earths or combinations thereof Where component A is generally more prone to form hydrides than component B. In the AB hydrogen storage base alloy, A includes one or more elements selected from the group consisting of Ti, Zr and V, for example, and B is Ni, V, Cr, Co, Mn, Mo, Nb, Al, Mg And one or more elements selected from the group consisting of Ag, Zn and Pd. AB base alloys include ZrNi, ZrCo, TiNi, TiCo and their modified forms. A ₂ B type base alloys include Mg ₂ Ni and its modified form according to the Ovshinsky rule, where either or both of Mg and Ni are completely or partially replaced by a multi-orbital reformer. ing. The AB ₂ type base alloy is a Laves phase compound, wherein A contains one or more elements selected from the group consisting of Zr and Ti, and B is Ni, V, Cr, Mn, Co, Mo, Ta and An alloy containing one or more elements selected from the group consisting of Nb. AB ₂ type base alloys include alloys modified according to the Ovshinsky law. AB ₅ metal hydride base alloys include those in which A contains one or more elements selected from the group consisting of lanthanides and B contains one or more transition metals. This includes LaNi ₅ and Ni partially replaced by one or more elements selected from the group consisting of Mn, Co, Al, Cr, Ag, Pd, Rh, Sb, V and Pt. cage, and / or La is, Ce, a LaNi ₅ are replaced partially Pr, Nd, by one or more elements selected from the group consisting of other rare earth and Mm. Also included are AB ₅ type base alloys modified according to the Ovshinsky law. Such base alloys are taught, for example, in US Pat. No. 6,830,725 (US Pat. No. 6,830,725).

The base alloy includes a TiMn ₂ type alloy. Metal hydride based alloys include, for example, Zr, Ti, V, Cr and Mn, where Zr is about 2 to about 5 atomic%, Ti is about 26 to about 33 atomic%, and V is about 7 to about 13 atomic percent, Cr is about 8 to about 20 atomic percent, and Mn is about 36 to about 42 atomic percent. These alloys can further include one or more elements selected from the group consisting of Ni, Fe and Al, such as from about 1 to about 6 atomic percent Ni, from about 2 to about 6 atomic percent Fe, And about 0.1 to about 2 atomic percent of Al. These base alloys can also contain up to about 1 atomic percent of Mm. Alloys suitable for modification include: Zr _3.63 Ti _29.8 V _8.82 Cr _9.85 Mn _39.5 Ni _2.0 Fe _5.0 Al _1.0 Mm _0.4 ; Zr _3.6 Ti _29.0 V _8.9 Cr _10.1 Mn _40.1 Ni _2.0 Fe _5.1 Al _1.2 ; Zr _3.6 Ti _28.3 V _8.8 Cr _10.0 Mn _40.7 Ni _1.9 Fe _5.1 Al _1.6 and Zr ₁ Ti ₃₃ V _12.54 Cr ₁₅ Mn ₃₆ Fe _2.25 Al _0.21 . Suitable base alloys are taught, for example, in US Pat. No. 6,536,487 (US Pat. No. 6,536,487).

The metal hydride base alloy can contain 40 atomic% or more of the structure of the type La _a R _1-ab Mg _b Ni _cde of A ₅ B ₁₉ type, where 0 ≦ a ≦ 0.5 atomic%, 0.1 ≦ b ≦ 0.2 atomic%, 3.7 ≦ c ≦ 3.9 atomic%, 0.1 ≦ d ≦ 0.3, and 0 ≦ d ≦ 0.2. Suitable base alloys are taught, for example, in US Pat. No. 7,829,220 (US Pat. No. 7,829,220).

The alloy of the present invention may be in the form of hydrogen storage alloy particles containing at least Ni and a rare earth. The particles can have a surface layer and an interior, wherein the surface layer has a nickel content greater than the interior, and nickel particles having a size of about 10 nm to about 50 nm are present in the surface layer. . The metal hydride base alloy may be an alloy of the formula Ln _1-x Mg _x Ni _abc Al _b Z _c , where Ln is one or more rare earth elements, Z is Zr, V, Bn, One or more of Ta, Cr, Mo, Mn, Fe, Co, Ga, Zn, Sn, In, Cu, Si, P and B, 0.05 ≦ x ≦ 0.3 atomic%, 2.8 ≦ a ≦ 3.9 atomic%, 0.05 ≦ b ≦ 0.25 atomic%, and 0.01 ≦ c ≦ 0.25. Suitable base alloys are taught, for example, in US Pat. No. 8,053,114 (US Pat. No. 8,053,114).

The alloys of the present invention can have a crystal structure having a multiphase having at least an A ₂ B ₇ type structure and an A ₅ B ₁₉ type structure and a surface layer having a nickel content greater than the bulk. Metal hydride base alloy may have an alloy of the formula _{Ln 1-x Mg x Ni yab} Al a M b, where Ln is one or more rare earth containing Y, M is, Co, Mn And one or more of Zn, wherein 0.1 ≦ x ≦ 0.2 atomic%, 3.5 ≦ y ≦ 3.9 atomic%, 0.1 ≦ a ≦ 0.3 atomic%, and 0 ≦ b ≦ 0.2. Suitable base alloys are disclosed, for example, in US Pat. No. 8,124,281 (US Pat. No. 8,124,281).

The metal hydride base alloy may be of the formula Ln _1-x Mg _x (Ni _1-y Ty) _z , where Ln is the lanthanide element, Ca, Sr, Sc, Y, Ti, Zr and Hf Is one or more elements that are washed from T, and T is selected from V, Nb, Ta, Cr, Mo, Mn, Fe, Co, Al, Ga, Zn, Sn, In, Cu, Si, P, and B One or more elements, where 0 <x ≦ 1 atomic%, 0 ≦ y ≦ 0.5 atomic%, and 2.5 ≦ z ≦ 4.5 atomic%. Suitable base alloys are taught, for example, in US Pat. No. 8,257,862 (US Pat. No. 8,257,862).

  The alloys of the present invention are La, Nd, Mg, Ni and Al, as taught in US Pat. No. 8,409,753 (US Pat. No. 8,409,753); La, Nd, Mg, Ni, Al and Co; La, Pr, Nd, Mg, Ni and Al, or La, Ce, Pr, Nd, Ni, Al, Co and Mn can be contained.

Metal hydride alloy may be of the formula _{Ti A Zr BX Y X V C} Ni D M E, wherein, A, B, respectively C and D, greater than 0, be 50 atomic% or less , X is greater than 0 and 4 atomic percent or less, M is one or more metals selected from Co, Cr, Sn, Al and Mn, and E is 0 to 30 atomic percent. Suitable base alloys are taught, for example, in US 2013/0277607 (US Pub. No. 2013/0277607).

The alloy of the present invention contains a modified A ₂ B ₇ type hydrogen storage alloy. For example MH base alloys may be A _x B _y alloys, wherein A comprises at least one rare earth element, and also include Mg, B includes at least Ni, the atomic ratio of X to Y is about 1: 2 to about 1: 5, such as about 1: 3 to about 1: 4. The MH base alloy may further contain one or more elements selected from the group consisting of B, Co, Cu, Fe, Cr and Mn. The atomic ratio of Ni to additional elements can be from about 50: 1 to about 200: 1. The rare earth includes La, Ce, Nd, Pr and Mm. The atomic ratio of rare earth to Mg can range from about 5: 1 to about 6: 1. Element B can further include Al, wherein the atomic ratio of Ni to Al can be from about 30: 1 to about 40: 1.

The metal hydride base alloy includes a high capacity hydrogen storage alloy of AB _x , where x is about 0.5 to about 5, which is ≧ 400 mAh / g, ≧ 425 mAh / g, ≧ 450 mAh / g, or It has a discharge capacity of ≧ 475 mAh / g.

Metal hydride based alloys include high capacity MH alloys containing magnesium (Mg), including, for example, AB, AB ₂ or A ₂ B type alloys containing Mg and Ni. For example, the MH base alloy includes MgNi, MgNi ₂ and Mg ₂ Ni. Such Mg and Ni-containing alloys can further contain one or more elements selected from the group consisting of rare earth elements and transition metals. For example, an alloy containing Mg and Ni further includes Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, One or more elements selected from the group consisting of La, Ce, Pr, Nd, Mm, Pd, Pt, Nb, Sc and Ca can be contained.

  MH-based alloys include, for example, Mg and Ni, and optionally Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb , La, Ce, Pr, Nd, Mm, Pd, Pt, Nb, Sc, and one or more elements selected from the group consisting of Ca.

  Mm is “Mish Metal”. Misch metal is a mixture of rare earth elements. Mm is, for example, a mixture containing La, Nd and Pr, such as a mixture containing Ce, La, Nd and Pr.

For example, MH base alloys include: MgNi, Mg _0.8 Ti _0.2 Ni, Mg _0.7 Ti _0.3 Ni, Mg _0.9 Ti _0.1 Ni, Mg _0.8 Zr _0.2 Ni, Mg _0.7 Ti _0.225 La _0.075 Ni, Mg _0.8 Al _0.2 Ni, Mg _0.9 Ti _0.1 Ni, Mg _0.9 Ti _0.1 NiAl _0.05 , Mg _0.08 Pd _0.2 Ni, Mg _0.09 Ti _0.1 NiAl _0.05 , Mg _0.09 Ti _0.1 NiAl _0.05 Pd _0.1 , Mg ₅₀ Ni ₄₅ Pd ₅ , Mg _0.85 Ti _0.15 Ni _1.0 , Mg _0.95 Ti _0.15 Ni _0.9 , Mg ₂ Ni, Mg _2.0 Ni _0.6 Co _0.4 , Mg ₂ Ni _0.6 Mn _0.4 , Mg ₂ Ni _0.7 Cu _0.3 , Mg _0.8 La _0.2 Ni, Mg _2.0 Co _0.1 Ni, Mg _2.1 Cr _{0.1 Ni, Mg 2.0 Nb 0.1 Ni,} Mg 2.0 Ti 0.1 Ni, Mg 2.0 V 0.1 Ni, Mg 1.3 Al 0.7 Ni, Mg 1.5 Ti 0.5 Ni, Mg 1.5 Ti 0.3 Zr 0.1 A _{0.1 Ni, Mg 1.75 Al 0.25 Ni} , and _{(MgAl) 2 Ni, Mg 1.70} Al 0.3 Ni.

  For example, MH-based alloys include alloys of Mg and Ni in an atomic ratio of about 1: 2 to about 2: 1, which further includes Co, Mn, Al, Fe, Cu, Mo, W, Cr, An element selected from the group consisting of V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Ce, Pr, Nd, Mm, Pd, Pt, Nb, Sc and Ca. Contains one or more. The additional element or elements may be about 0.1 to about 30 atomic percent (at%), or about 0.25 to about 15 atomic percent, or about 0.5, about 1, about 2 based on the total alloy. , About 3, about 4, or about 5 atom% to about 15 atom%. The atomic ratio of Mg to Ni is, for example, about 1: 1. Thus, both Mg and Ni may be present from about 70 atomic percent to about 99.9 atomic percent based on the total alloy. The Mg-NiMH base alloy may be free of further elements, in which case Mg and Ni are present together at 100 atomic%.

  The metal hydride alloy can contain Mg and Ni in an atomic ratio of about 1: 2 to about 2: 1, where Mg and Ni are combined at a level of ≧ 70 atomic% based on the total alloy. Exists.

  The metal hydride base alloy can contain ≧ 20 atomic% of Mg.

The metal hydride base alloy can contain Mg and Ni in an atomic ratio of about 1: 2 to about 2: 1, and can further contain Co and / or Mn. The alloys of the present invention include modified Mg ₅₂ Ni ₃₉ Co ₆ Mn ₃ or modified Mg ₅₂ Ni ₃₉ Co ₃ Mn ₆ .

  The metal hydride base alloy can contain ≧ 90% by weight of Mg and one or more additional elements. The one or more additional elements can be selected from the group consisting of Ni, Mm, Al, Y and Si. These alloys can contain, for example, about 0.5 to about 2.5% by weight of Ni and about 1.0 to about 4.0% by weight of Mm. These alloys also have an Al content of about 3 to about 7 weight percent, and / or a Y content of about 0.1 to about 1.5 weight percent, and / or a Si content of about 0.3 to about 1.5 weight percent, Can be contained.

  Suitable high performance MH base alloys are, for example, US Pat. No. 5,506,069 (US Pat. No. 5,506,069), US Pat. No. 5,616,432 (US Pat. No. 5,616,432) and US Pat. No. 6,193,929 ( US Pat. No. 6,193,929).

  The alloy of the present invention can, for example, store at least 6% by weight of hydrogen at 300 ° C. for 5 minutes and / or store at least 80% of the full hydrogen storage capacity, or store hydrogen at 300 ° C. for 2 minutes. It can contain at least 6.5% by weight and / or can store at least 80% of its full hydrogen storage capacity, or it can contain at least 6.9% by weight hydrogen at 300 ° C. for 1.5 minutes. And / or at least 80% of the full hydrogen storage capacity.

Metal hydride base alloy comprises an alloy of the formula _{Ti a Zr bx Y x V c} Ni d M e, where a, b, respectively c and d, greater than 0 and less than 50 atomic%, x Is greater than 0 and less than or equal to 4 atomic percent, M is one or more metals selected from the group consisting of Co, Cr, Sn, Al and Mn, and e is from 0 to about 30 atomic percent. These alloys are disclosed, for example, in US Patent Publication No. 2013/0277607 (US Pub. No. 2013/0277607).

  Alloys according to the present invention can be produced, for example, by arc melting or induction melting under an inert atmosphere, by melt casting, rapid solidification, mechanical alloying, sputtering or gas spraying, or other methods taught in the above references. Can be manufactured.

  Unless otherwise stated, the amount of element in an alloy or phase is atomic percent (at%) based on the entire alloy or phase.

  Unless otherwise stated, the amount of each phase is reported in mass% (wt%) based on the total alloy.

  Low temperature electrochemical properties can be defined by charge transfer resistance (R) at −40 ° C.

  Electrochemical performance can also be defined by high rate discharge characteristics (HRD).

  Low temperature electrochemical properties can also be defined as surface catalyst performance at low temperatures, eg, -40 ° C. Surface catalyst performance is defined as the product (R · C) of charge transfer resistance (R) and double layer capacity (C). The values of R and C are calculated from curve fitting of a Cole-Cole plot of AC impedance measurement.

  The low temperature is defined by, for example, <25 ° C., ≦ 10 ° C., ≦ 0 ° C., ≦ −10 ° C., ≦ −20 ° C. or ≦ −30 ° C.

  The charge transfer resistance (R) is measured in Ω · g. Double layer capacity (C) is measured in farads / g.

  Here, AC impedance is measured using a SOLARTRON 1250 frequency characteristic analyzer in a sine wave with an amplitude of 10 mV and a frequency range of 0.1 mHz to 10 kHz. Prior to measurement, the electrode was subjected to one complete charge / discharge cycle using a battery test galvanostat called SOLARTRON 1470 at a rate of 0.1 C, charged to 100% state of charge (SOC), and discharged to 80% SOC. And then cooled to -40 ° C.

The half-cell HRD is defined as the ratio of the discharge capacity measured at 50 mAg ⁻¹ to the discharge capacity measured at 4 mg ⁻¹ . The discharge capacity of the alloy is measured with a liquid cell design against a partially precharged Ni (OH) ₂ positive electrode. No pretreatment with alkali is applied before half-cell measurement. Each sample electrode, 10 hours at a constant current density of 50MAg ^-1, charged, then discharged at a current density of 50MAg ^-1, this two pull continues at 12 and 4mAg ^-1. The capacity is measured in the third cycle.

  The alloy according to the invention advantageously contains multiple phases. For example, the alloy according to the invention can have at least one main phase and a secondary phase. For example, the alloy according to the invention has at least one main phase, an occlusion secondary phase, and a catalyst secondary phase.

  One main phase or a plurality of main phases are electrochemically active. “Electrochemically active” means that hydrogen can be reversibly absorbed and discharged electrochemically at ambient conditions (25 ° C. and 1 atmosphere).

  Advantageously, the occlusive secondary phase is also an electrochemically active phase. This is “observable” by deviation from the conventional curve of the Cole-Cole plot for AC impedance measurements; for example, the presence of additional curves in the Cole-Cole plot. For example, the Cole-Cole plot of an alloy according to the present invention has two curves, where one curve relates to the active main phase and the other relates to the active secondary phase.

  For example, deviations from the conventional curve of the Cole-Cole plot for AC impedance measurements taken at low temperatures (eg −40 ° C.) are observed for the alloys according to the invention. This indicates that the secondary phase is electrochemically active at −40 ° C. in addition to one or more main phases. The alloys according to the invention can have one or more main phases which are electrochemically active and a secondary phase which is electrochemically active at −40 ° C.

  The Cole-Cole plot for AC impedance measurements is achieved by curve fitting.

  In conventional metal hydride alloys, only one curve exists in the Cole-Cole plot for one main phase or multiple main phases. Deviations from conventional curves are observed by the presence of at least one inflection point. For a normal curve, the tangent slope at every point will decrease along the x-axis (concave curve). At the inflection point, the tangent slope will begin to increase. The inflection point indicates the appearance of the second curve.

  The expression “each active phase can be clearly represented in the Cole-Cole plot of the AC impedance measurement” means that a conventional curve is observed and at least one inflection point is observed.

  Without being bound by theory, the secondary storage phase, like the main (storage) phase, can reversibly store and release hydrogen, while the secondary catalyst phase, the “catalytic phase” It is believed that this reversible reaction serves to assist the main phase and / or the occlusion phase.

  Different phases seem to work synergistically together. This may be that one having a relatively weak metal hydrogen bond acts as a catalyst while the other acts as a hydrogen storage phase. With simplification from the catalyst phase, hydrogen in one or more storage phases can be removed more easily.

  Simply mixing two different phases mechanically does not lead to a synergistic effect according to the invention. The alloy according to the invention provides intimate contact of the different phases, thereby providing an approximation in proton conduction. The Cole-Cole plot of AC impedance measurement is one way to observe this synergy. Simple mechanical mixing shows one semicircular curve combining R and C measurements as a component in parallel connection, while the alloy according to the present invention has two components from positive and negative electrodes. Similar to measuring the AC impedance of the entire cell, showing the semicircle separately, two semicircular curves can be shown.

  Instead of different phases acting in parallel connection, an alloy according to the invention having an electrochemically active secondary phase has an active phase (main phase and active two) acting in series as observed in the Cole-Cole plot. Next phase). When acting in series, a conventional curve is observed and at least one inflection point is observed.

  The charge transfer resistance (R) at −40 ° C. is, for example, ≦ 150, ≦ 140, ≦ 130, ≦ 120, ≦ 110, ≦ 100, ≦ 90, ≦ 80, ≦ 70, ≦ 60, ≦ 40, ≦ 30, ≦ 25, ≦ 20, ≦ 19, ≦ 18, ≦ 17, ≦ 16, ≦ 15, ≦ 14, ≦ 13, ≦ 12 or ≦ 11 Ω · g.

  The charge transfer resistance (R) at −40 ° C. is, for example, about 3 to about 50, about 5 to about 20, about 7 to about 18, about 9 to about 16, about 10 to about 15, or about 11 to about 15 Ω · g.

  Low temperature performance can also be specified at 10 ° C., 0 ° C., −10 ° C., −20 ° C. or −30 ° C .; that is, a clear indication of the two active phases can also be observed at these temperatures .

  For alloys having an electrochemically active secondary phase, the charge transfer resistance is the sum of the resistance for one or more main phases and the resistance for one or more active secondary phases.

  For one main phase or a plurality of main phases of the alloy according to the present invention, the charge transfer resistance (R) at −40 ° C. is, for example, ≦ 150, ≦ 140, ≦ 130, ≦ 120, ≦ 110, ≦ 100, ≦ 90. ≦ 80, ≦ 70, ≦ 60, ≦ 40, ≦ 30, ≦ 25, ≦ 20, ≦ 19, ≦ 17, ≦ 16, ≦ 15, ≦ 14, ≦ 13, ≦ 12 or ≦ 11, ≦ 10, ≦ 9, ≦ 8, ≦ 7, ≦ 6, ≦ 5 or ≦ 4 Ω · g. (R) at −40 ° C. for one main phase or multiple main phases is, for example, about 1 to about 30, about 2 to about 20, about 2 to about 15, about 2 to about 10, about 3 to about 9 About 3 to about 8, about 3 to about 7, about 3 to about 6, about 3 to about 5, or about 3 to about 4 Ω · g.

  The expression “for one main phase or a plurality of main phases” means the sum for the main phase.

  The surface catalyst performance at −40 ° C. of the main phase or phases of the alloy according to the present invention is about 1 to about 20, about 1 to about 15, about 1 to about 10, about 1 to about 5, about 1 to about 4, about 1 to about 3, or about 1.5 to about 2.5 seconds. The surface catalyst performance at −40 ° C. of one main phase or a plurality of main phases is, for example, ≦ 30, ≦ 25, ≦ 20, ≦ 15, ≦ 12, ≦ 10, ≦ 8, ≦ 7, ≦ 6. ≦ 5, ≦ 4, ≦ 3 or ≦ 2 seconds.

  The alloys according to the invention exhibit, for example, about 93%, about 94%, about 95%, about 96% or about 97% HRD in the third cycle. The HRD in the third cycle is, for example, ≧ 93%, ≧ 94%, ≧ 95%, ≧ 96% or ≧ 97%.

  The alloy has at least one main phase and at least one secondary phase. Each of the at least one main phase, the occlusion secondary phase and the catalyst secondary phase has a different chemical composition and / or physical structure. The physical structure is a crystalline structure and an amorphous structure. The abundance of the phase can be determined by X-ray diffraction (XRD). The composition of the phase can be determined by a scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS).

One main phase or a plurality of main phases are present in a higher mass abundance than each secondary phase. The main phase or phases are generally AB _x phases, such as AB, AB ₂ , AB ₃ , A ₂ B ₇ or AB ₅ phases.

  The structure of each phase is advantageously different. That is, each phase has a structure selected from the group consisting of a crystalline structure and an amorphous (amorphous) structure, where each is different.

The hydrogen storage alloy according to the present invention is, for example, a modified AB _x type alloy, where x is about 0.5 to about 5.

The alloy according to the invention is
i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) V, Cr, Mn, Ni, Sn, Al, Co, Cu, Mo, W, Fe, Si, and One or more elements selected from the group consisting of rare earth elements can be contained.

Alternatively, the alloy according to the invention is
i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) selected from the group consisting of Ni, Cr and B, Al, Si, Sn, other transition metals and rare earth elements I) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni, Cr, and V, Mn, One or more elements selected from the group consisting of Sn, Al, Co, Cu, Mo, W, Fe, Si, and rare earth elements can be contained.

Alloys according to the invention are, for example, a AB ₂ type alloy that has been modified, this is for example of ii), i) atomic ratio is from about 2.02～ about 2.45, a AB ₂ type alloys. The atomic ratio of ii) to i) is, for example, from about 2.04 to about 2.40, from about 2.10 to about 2.38, from about 2.20 to about 2.36, or from about 2.20 to about 2. .36.

  The atomic ratio of ii) to i) according to the present invention is, for example, about 2.03, about 2.05, about 2.07, about 2.09, about 2.11, about 2.13, about 2.15, About 2.17, about 2.19, about 2.21, about 2.23, about 2.25, about 2.27, about 2.29, about 2.31, about 2.33, about 2.35, About 2.37 or about 2.39.

The modified AB ₂ type alloy according to the invention has, for example, a C14 or C15 Laves main phase, or a C14 and C15 Laves main phase. The abundance of the C14 phase is, for example, from about 70 to about 95% by weight, such as from about 80 to about 90% by weight, or from about 83 to 89% by weight, based on the alloy. The abundance of the C15 phase is, for example, from about 2 to about 20% by weight, for example from about 3 to about 17% by weight, or from about 3 to 16% by weight, based on the alloy.

  The alloys according to the invention contain, for example, a C14 or C15 Laves phase, or contain a C14 and C15 Laves phase, where the occlusive secondary phase and the catalytic secondary phase are non-Laves phases.

  The abundance of the catalyst secondary phase is, for example, from about 0.3 to about 15% by weight, from about 0.5 to about 10% by weight, for example from about 0.7 to about 5% by weight, based on the alloy. The abundance of the secondary catalyst phase is about 0.1%, about 0.4%, about 0.9%, about 1.1%, about 1.3%, about 1% based on the alloy. 0.5%, about 1.7%, about 2.0%, about 2.5%, about 3.0%, about 3.5%, or about 4.0% by weight. .

  The abundance of the occlusive secondary phase is, for example, about 0.51 to about 15% by mass, about 0.52 to about 12% by mass, about 0.55 to about 11% by mass, about 0.6, based on the alloy. To about 9%, about 0.7 to about 7%, about 0.9 to about 5%, or about 1.0 to about 3% by weight.

  The abundance of the occlusive secondary phase is, for example, about 0.6% by mass, about 0.9, about 1.2, about 1.5, about 1.7, about 1.9, about 2. 1, about 2.3, about 2.5, about 2.7, or about 2.9% by weight.

  The alloy advantageously has a catalyst secondary phase containing Ti and Ni, based on the total alloy, of about 0.1 to about 4.0, about 0.2 to about 3.5, or about 0.3 to about 3 About 0.1 to about 4.0, about 0.2 to about 3.5, or about 0.3 to about 3.3% by weight, and a occlusive secondary phase containing La and Ni, contains.

  In general, in a series of similar composition alloys, the low temperature electrochemical properties increase as the mass ratio of the catalyst secondary phase abundance to the storage secondary phase abundance decreases. The mass ratio of the abundance of the catalyst secondary phase to the abundance of the occlusive secondary phase is advantageously about 5 to about 0.1, about 4 to about 0.1, about 3 to about 0.1, about 2 to about 0.1, or about 1 to about 0.1. The mass ratio of the abundance of the catalyst secondary phase to the abundance of the occlusion secondary phase is, for example, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0. 0.7, about 0.8, about 0.9, about 1.1, about 1.3, about 1.5, about 1.7, or about 1.9, and levels in between.

  For example, the mass ratio of the abundance of the catalyst secondary phase to the abundance of the occlusion secondary phase is <3.0, ≦ 2.5, ≦ 2.0, ≦ 1.5, ≦ 1.0 or ≦ 0.5.

  The catalytic secondary phase advantageously has a TiNi (B2) crystal structure. That is, the crystal structure of the catalyst secondary phase is advantageously a known TiNi (B2) crystal structure as specified by X-ray diffraction (XRD). In order to have a known TiNi (B2) crystal structure, the catalyst secondary phase need not contain Ti and / or Ni.

  The catalyst secondary phase can contain Ti and / or Ni.

  The catalyst secondary phase contains, for example, one or more elements selected from the group consisting of Ti, Zr, Nb, and Hf, and also contains Ni. The catalyst secondary phase contains, for example, Ti and Ni, or contains Ti, Zr and Ni.

  The catalyst secondary phase contains, for example, about 13 to about 45 atomic percent Ti, about 15 to about 30 atomic percent Ti, or about 20 atomic percent to about 30 atomic percent Ti.

  The catalyst secondary phase contains, for example, about 5 to about 30 atomic percent Zr, about 7 to about 25 atomic percent Zr, or about 10 to about 22 atomic percent Zr.

  The catalyst secondary phase contains, for example, about 38 to about 60 atomic percent Ni, about 40 to about 55 atomic percent Ni, or about 42 atomic percent to about 47 atomic percent Ni.

  The crystal structure of the secondary phase of the catalyst according to the present invention containing Ti and Ni at the above levels is the known Ti (B2) crystal structure, but these contain significant amounts of other metals soluble in the TiNi phase, such as Zr. , Can be contained.

  For example, the catalyst secondary phase contains about 42 to about 47 atomic percent Ni, about 20 to about 29 atomic percent Ti, and about 12 to about 22 atomic percent Zr, where (Ti + Zr) is about 39 To about 43 atomic percent. When present together in the catalyst secondary phase, the atomic% of Zr is advantageously not more than the atomic% of Ti. For example, when present together in the catalyst secondary phase, the atomic% of Zr is less than the atomic% of Ti.

  The occlusion secondary phase has, for example, a structure different from the structure of the catalyst secondary phase.

  The occlusive secondary phase contains one or more rare earth elements. The occlusive secondary phase contains, for example, Ni and contains one or more rare earth elements and Ni or contains La and Ni.

  The occlusive secondary phase contains, for example, about 30 to about 60 atomic percent, about 40 to about 55 atomic percent, about 41 to about 52 atomic percent, or about 44 to about 50 atomic percent of one or more rare earth elements To do. The rare earth element is, for example, La.

  The occlusive secondary phase contains, for example, about 30 to about 60 atomic percent, about 40 to about 55 atomic percent, about 42 to about 52 atomic percent, or about 45 to about 50 atomic percent of Ni.

  The occluded secondary phase contains, for example, about 41 to about 51 atomic percent La and about 44 to about 50 atomic percent Ni, or about 48 to about 50 atomic percent La, and about 49 to about Ni. Contains 50 atomic%.

  The atomic% (at%) discussed herein for each phase is based on the phase.

  The atomic% (at%) discussed herein for the alloy is based on the entire alloy.

  The rare earth elements are Sc, Y, La and lanthanides. Misch metal is included in the term “one or more rare earth elements”. The rare earth element is, for example, La.

  Alloys according to the present invention may contain, for example, one or more rare earth elements from about 0.1 atomic percent to about 10.0 atomic percent, from about 0.7 to about 8.0 atomic percent, from about 1.0 to about 7.0. Atom%, about 1.5 to about 6.0 atom%, or about 2.0 to about 5.5 atom%. Alloys according to the present invention may include, for example, one or more rare earth elements at about 1.5, about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, About 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5 or about 8.0 atomic percent, and levels in between.

  The alloy according to the present invention contains, for example, Ti, Zr, V, Ni, one or more rare earth elements, and one or more elements selected from the group consisting of Cr, Mn and Al. The alloy contains, for example, Ti, Zr, V, Ni, Cr, Mn, Al, Co, and one or more rare earth elements. The alloy contains, for example, Ti, Zr, V, Ni, Cr, Mn, Al, Co and La.

  Alloys according to the present invention include, for example, Ti from about 0.1 to about 60%, Zr from about 0.1 to about 40%, 0 <V <60%, Cr from 0 to about 56%, and Mn from about 5 to about 22%, Ni from about 0.1 to about 57%, Sn from 0 to about 3%, Al from about 0.1 to about 10%, Co from about 0.1 to about 11%, and one or more rare earths Contains from about 0.1 to about 10% of the elements, where the percentages are atomic% and equal to 100% in total.

  About 5 to about 15% Ti, about 18 to about 29% Zr, about 3.0 to about 13% V, about 1 to about 10% Cr, about 6 to about 18% Mn, about Ni about Ni Also disclosed are alloys containing 29 to about 41%, Al about 0.1 to 0.7%, Co about 2 to about 11%, and one or more rare earth elements about 0.7 to about 8%. , Where the percentages are atomic% and are equal to 100% in total.

  The alloy is advantageously about 11% to about 13% Ti, about 21% to about 23% Zr, about 9% to about 11% V, about 6% to about 9% Cr, about 6% to about 9% Mn. %, Ni from about 31 to about 34%, Al from about 0.3 to about 0.6%, Co from about 2 to about 8%, and one or more rare earth elements from about 1 to about 7%, The percentages here are atomic%, which is equal to 100% in total.

  Alloys according to the present invention generally have a bulk region and a surface region. A surface region is at or near the surface, also known as a surface layer, interfacial phase, interface region, and the like. The surface or interface region constitutes an interface between the electrolyte and the bulk portion of the hydrogen storage alloy.

  Surface oxides are often present in the interfacial region of the hydrogen storage alloy after fabrication. Surface oxides are usually insulative, which generally impedes the performance of electrodes utilizing alloys.

  The alloy according to the invention can contain metal oxides with a high degree of oxidation. The metal oxide is, for example, based on the total elements of the metal oxide, oxygen ≧ 60 atomic%, oxygen ≧ 62 atomic%, oxygen ≧ 64 atomic%, oxygen ≧ 66 atomic%, or oxygen ≧ 68 atoms %,contains.

  The metal oxide present generally refers to an oxidized metal, including, for example, metal oxides and hydroxides.

The alloy according to the invention can contain metal oxides with ≧ 60 atomic% oxygen and / or the alloy according to the invention can have a metal region adjacent to a boundary region having at least one flow path. And / or the alloy according to the invention can have a metal region adjacent to a boundary region having an average width of about 12 nm to about 1100 nm, and / or the alloy according to the invention comprises at least one flow path and It can have parallel metal oxide zones.

  The highly oxidized metal oxide according to the present invention is present in the “metal oxide zone”. The metal oxide zone may contain the metal oxide according to the invention, or the metal oxide zone may consist essentially of the metal oxide according to the invention or consist of the metal oxide according to the invention.

  The metal oxide according to the invention contains, for example, oxygen ≧ 60 atomic%, oxygen ≧ 62 atomic%, oxygen ≧ 64 atomic%, oxygen ≧ 66 atomic%, or oxygen ≧ 68 atomic%, or oxygen About 60 atom% to about 82 atom%, oxygen about 63 atom% to about 77 atom%, oxygen about 64 atom% to about 75 atom%, oxygen about 65 atom% to about 72 atom%, or oxygen About 66 atom% to about 70 atom% is contained.

  The metal oxide is, for example, about 60 atomic%, about 61 atomic%, about 62 atomic%, about 63 atomic%, about 64 atomic%, about 65 atomic%, about 66 atomic%, based on the metal oxide, About 67 atom%, about 68 atom%, about 69 atom%, about 70 atom%, about 71 atom%, about 72 atom%, about 73 atom%, about 74 atom%, about 75 atom%, about 76 atom%, About 77 atomic percent, about 78 atomic percent, about 79 atomic percent, about 80 atomic percent, about 81 atomic percent, or about 82 atomic percent.

  The amounts of elements discussed for oxides are based on metal oxides.

The metal oxide can contain Ni and / or Cr. The metal oxide can be a Ni / Cr oxide. Since Ni / Cr alloys are difficult to oxidize, the formation of Ni / Cr oxides is unusual. The metal oxide is, for example, a Ni / Cr oxide containing about 64 atomic percent to about 71 atomic percent oxygen, about 3 atomic percent to about 8 atomic percent Cr, and about 16 atomic percent to about 21 atomic percent Ni. is there. The Ni / Cr oxide can contain Ni (Cr) OOH and / or Ni (Cr) (OH) ₂ .

  The Ni / Cr oxide can contain Ni and Cr, where each is present in an atomic percentage that is higher than the percentage of each other metal (or metalloid), eg, as in the examples according to the invention. . Metalloids such as B and Si are included in the metal for this definition.

  For example, the metal oxide contains Cr ≧ 2 atomic%, Cr ≧ 3 atomic%, Cr ≧ 4 atomic%, or Cr ≧ 5 atomic%, or Cr from about 2 atomic% to about 8 atomic%. About 3 atomic percent to about 8 atomic percent of Cr, or about 4 atomic percent to about 7 atomic percent of Cr. The metal oxide contains, for example, about 2 atomic%, about 3, about 4, about 5, about 6, about 7 or about 8 atomic% of Cr.

  The metal oxide may contain, for example, Ni ≧ 16 atomic%, Ni ≧ 17 atomic%, Ni ≧ 18 atomic%, or Ni ≧ 19 atomic%, or Ni from about 16 atomic% to about 23 atomic% Ni from about 17 atomic percent to about 22 atomic percent, or Ni from about 18 atomic percent to about 21 atomic percent. For example, the metal oxide contains about 16 atomic percent, about 17, about 18, about 19, about 20, about 21, about 22 or about 23 atomic percent of Ni.

  The metal oxide is one or more elements selected from the group consisting of B, Al, Si, Sn and transition metals, for example one selected from the group consisting of Al, Ti, V, Mn, Co, and Zr The above elements can be contained. One or more of these elements may be present in the oxide in a total of about 1 atom% to about 17 atom%, about 2 atom% to about 14 atom%, about 3 atom% to about 12 atom%, about 3 atom% to About 10 atomic percent, or about 4 atomic percent to about 9 atomic percent may be present.

  The metal oxide may be present in a boundary region adjacent to the metal region, and the boundary region may have at least one flow path. The boundary region separates the metal region, for example. The boundary region has, for example, at least one channel having a length and an average width and running in the length direction of the boundary region (along the length). The flow path can have an average width of about 4 nm to about 40 nm, about 5 nm to about 35 nm, about 7 nm to about 30 nm, or about 8 nm to about 25 nm. For this reason, the boundary region is also named “metal oxide boundary region”.

  The flow path can have direct access of the electrolyte to the bulk alloy. The flow path is not occupied, is open and is not dense. A “metal region” is a bulk alloy or “bulk metal region”. The flow path is capable of allowing electrolyte transport to the bulk metal region, which is believed to provide excellent electrochemical performance.

  The boundary region may have a transition oxide zone adjacent to the metal region, which transition zone may run along the length of the boundary region. The transition oxide zone has an average width of, for example, about 4 nm to about 30 nm, about 5 nm to about 25 nm, about 7 nm to about 20 nm, or about 8 nm to about 17 nm.

  Transition oxide is present in the transition oxide zone. The transition oxide is a metal oxide having a composition similar to the highly oxidized metal oxide according to the present invention, but has a slightly lower degree of oxidation. For example, the transition oxide contains <60 atomic% oxygen or <55 atomic% oxygen based on the transition oxide.

  The boundary region can have a metal oxide band that can run along the length of the boundary region, for example, about 5 nm to about 500 nm, about 6 to about 400 nm, about 7 nm to about 300 nm, about 8 nm. Having an average width of about 200 nm, or about 8 nm to about 100 nm.

  The boundary region has, for example, a length and an average width, and has a first transition oxide zone, a metal oxide zone, and a second transition oxide zone over the width, each of which is the length of the boundary region. Or a first transition oxide zone, a flow path, and a second transition oxide zone across its width, each running along the length of the boundary region; Or a first transition oxide zone, a metal oxide zone, a flow path, and a second transition oxide zone across its width, each running along the length of the boundary region; or its width Having a first transition oxide zone, a first metal oxide zone, a flow path, a second metal oxide zone, and a second transition oxide zone, each along the length of the boundary region Running.

  The term “running along the length” means running in parallel. The boundary region is, for example, a narrow linear and / or curvilinear “passage” structure, which has a structure selected from a transition oxide zone, a metal oxide zone, and a flow path. The transition oxide zone, the metal oxide zone, and the flow path, for example, each run parallel to the boundary region, in other words, parallel to each other along their passages.

  The border region is adjacent to and / or separates the metal region. The metal region is a bulk metal alloy.

  The boundary region can be nanoscale, and the boundary region can be, for example, about 12 nm to about 1100 nm, about 17 to about 1000 nm, about 20 nm to about 1000 nm, about 20 nm to about 900 nm, about 20 nm to about 800 nm, about 20 nm to about It can have an average width of 700 nm, about 17 nm to about 600 nm, about 20 nm to about 500 nm, about 25 nm to about 400 nm, about 30 nm to about 300 nm, about 35 nm to about 200 nm, or about 40 nm to about 100 nm. The boundary region has, for example, a length and an average width, where the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times, or ≧ 24 times the average width. The boundary region has, for example, a length and an average width, where the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times, or ≧ 24 times the average width; Here, the width is substantially uniform along the length.

  Without being bound by theory, it is believed that the modifying elements and / or methods according to the present invention affect the structure and composition of metal oxides and boundary regions.

  The alloys according to the invention, which generally have a bulk metal alloy region and a surface oxide region, advantageously also have an open channel in and / or across the bulk region. The flow paths may be interconnected to form a three-dimensional network. The flow path may run in parallel with the metal oxide zone and / or the transition oxide zone according to the invention. The flow path may extend over the surface oxide region. The electrolyte can “flow” through the open flow path, thereby increasing accessibility to the bulk alloy. Another way of describing the alloys according to the invention with flow paths is that they have a much larger surface area than conventional alloys, the open flow paths constituting the surface of the alloy.

  This “surface oxide” is a conventional metal oxide / hydroxide. The alloys according to the invention may or may not contain conventional surface oxides in addition to the highly oxidized metal oxides according to the invention.

Alloys according to the invention are, for ^{example, ≧ 3.0m 2 /g,≧3.2m 2 /g,≧3.4m 2} /g,≧3.6m 2 /g,≧3.8m 2 / g, ≧ 4. ^{0m 2 /g,≧4.2m 2 /g,≧4.4m 2 /g,≧4.6m 2} / g or ≧ 4.8 m BET of ² / g (Brunauer-Emmett-Teller) having a surface area, Can do. The BET surface area is measured by a liquid nitrogen immersion type BET method.

  The alloy according to the invention has a functionally high surface area. This high surface area cannot be completely detected by conventional BET measurements. This is because the narrow channel is too long for liquid nitrogen to penetrate. Functional surface area can be measured by capacitance. Thus, the alloy of Example 5 will have a much higher surface area than Alloy 0.

  The highly oxidized Ni / Cr oxide in the narrow boundary region is highly oriented, for example crystalline. The alloy according to the invention can also have a larger (wider) boundary region containing a randomly oriented, very dense metal oxide, which can be rich in Cr and Ni. Thus, an alloy according to the present invention can have a narrow boundary region containing crystalline Ni / Cr metal oxide and a wide boundary region containing random Ni / Cr metal oxide.

  The alloy according to the invention can absorb and discharge hydrogen reversibly.

  A further subject matter of the invention comprises at least one anode capable of reversibly storing and releasing hydrogen, at least one cathode capable of reversible oxidation, a casing in which the anode and the cathode are arranged, a cathode and an anode. A metal hydride battery having a separator to separate and an electrolyte in contact with both the anode and the cathode, wherein the anode contains a hydrogen storage alloy according to the present invention.

  The battery according to the present invention can store a large amount of hydrogen under a certain polarity, and can release a desired amount of hydrogen under the opposite polarity.

  The subject of the present invention is also an alkaline fuel cell having at least one hydrogen electrode, at least one oxygen electrode, and at least one gas diffusion material, wherein the hydrogen electrode contains a hydrogen storage alloy according to the present invention.

  The subject of the present invention is also a metal hydride air cell having at least one air permeable cathode, at least one anode, at least one air intake, and an electrolyte in contact with both the anode and the cathode, wherein the anode Contains a hydrogen storage alloy according to the invention.

  The US patent applications, US patent application publications, and US patents discussed herein are each incorporated herein by reference.

  The term “one (a)” referring to an element of an embodiment can mean “one” or can mean “one or more”.

  The term "about" can be caused by, for example, normal measurement and handling procedures, inadvertent mistakes in these procedures, differences in the purity of the manufacturer, manufacturer, or ingredients used, differences in the technique used, etc. Say mutation. The term “about” also includes different amounts for compositions obtained from a particular initial mixture due to various equilibrium conditions. Whether or not the term “about” is included, the embodiments and embodiments include equivalents of the stated amounts.

  All numerical values herein are modified by the term “about” whether or not explicitly stated. The term “about” generally refers to a range of numbers that one of ordinary skill in the art believes to be equal to (ie, have the same function and / or result of) the referenced value. In many cases, the term “about” can include numbers rounded to the nearest significant number.

  The value modified by the term “about” includes, of course, certain values. For example, “about 5.0” must include 5.0.

  Hereinafter, some embodiments of the present invention will be described.

  E1: a hydrogen storage alloy containing a metal oxide having an oxygen content of ≧ 60 atomic% based on the metal oxide, for example, a hydrogen storage alloy having improved low-temperature electrochemical properties, wherein the alloy is Shows charge transfer resistance (R) at −40 ° C. of ≦ 50% of charge transfer resistance (R) at −40 ° C. of an alloy containing no oxide, for example, where the alloy contains the oxide A hydrogen storage alloy exhibiting a charge transfer resistance at -40 ° C. of ≦ 60%, ≦ 40%, ≦ 30%, ≦ 20% or ≦ 10% of the charge transfer resistance at −40 ° C.

  E2: The metal oxide contains ≧ 62 atomic% oxygen, ≧ 64 atomic% oxygen, ≧ 66 atomic% oxygen, or ≧ 68 atomic% oxygen based on the metal oxide, or oxygen About 60 atom% to about 82 atom%, oxygen about 63 to about 77 atom%, oxygen about 64 atom% to about 75 atom%, oxygen about 65 atom% to about 72 atom%, or oxygen about 66 atom % To about 70 atomic%, or about 60 atomic%, about 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69, about 70, about 71 , About 72, about 73, about 74, about 75, about 76, about 77, about 78, about 79, about 80, about 81 or about 82 atom%.

  E3: The metal oxide is based on the metal oxide, Cr ≧ 2 atomic%, Cr ≧ 3 atomic%, Cr ≧ 4 atomic%, or Cr ≧ 5 atomic%; or Cr about 2 atomic% About 8 atomic percent, Cr about 3 atomic percent to about 8 atomic percent, or Cr 4 atomic percent to about 7 atomic percent; or Cr about 2 atomic percent, about 3, about 4, about 5, about 6, Embodiment 3. The alloy of embodiment 1 or 2, comprising about 7 or about 8 atomic percent.

  E4: The alloy according to any one of embodiments 1 to 3, wherein the metal oxide contains about 2 to about 8 atomic% of Cr based on the metal oxide.

  E5: the metal oxide is based on the metal oxide, Ni ≧ 16 atomic%, Ni ≧ 17 atomic%, Ni ≧ 18 atomic%, or Ni ≧ 19 atomic%; or Ni about 16 atomic% To about 23 atom%, Ni to about 17 atom% to about 22 atom%, or Ni to 18 atom% to about 21 atom%; or Ni to about 16 atom%, about 17, about 18, about 19, about 20, Embodiment 5. The alloy of any of embodiments 1 to 4, containing about 21, about 22, or about 23 atomic percent.

  E6: The alloy according to any one of embodiments 1 to 5, wherein the metal oxide contains about 16 atomic% to about 23 atomic% of Ni based on the metal oxide.

  E7: the metal oxide is about 64 atomic percent to about 71 atomic percent oxygen, about 3 atomic percent to about 8 atomic percent Cr, and about 16 atomic percent to about 21 atomic percent Ni based on the metal oxide The alloy according to any one of Embodiments 1 to 6, which is contained.

  E8: The alloy according to any one of embodiments 1 to 7, wherein the metal oxide contains one or more elements selected from the group consisting of B, Al, Si, Sn, and a transition metal.

  E9: The alloy according to any one of embodiments 1 to 8, wherein the metal oxide contains one or more elements selected from the group consisting of Al, Ti, V, Mn, Co, and Zr.

  E10: The metal oxide has a total of about 1 or more elements selected from the group consisting of B, Si, Sn, Al, Ti, V, Mn, Co, and Zr, based on the metal oxide. Atom% to about 17 atom%, about 2 atom% to about 14 atom%, about 3 atom% to about 12 atom%, about 3 atom% to about 10 atom%, or about 4 atom% to about 9 atom% The alloy according to any one of Embodiments 1 to 9.

  E11: The alloy according to any one of embodiments 1 to 10, wherein the metal oxide is present in a boundary region adjacent to the metal region or in a boundary region separating the metal region.

  E12: The alloy according to any of embodiments 1 to 11, wherein the boundary region has at least one flow path having a length and an average width and running in the length direction in the boundary region.

  E13: Embodiment 11 or 12 wherein the boundary region has at least one flow path having an average width of about 4 nm to about 40 nm, about 5 nm to about 35 nm, about 7 nm to about 30 nm, or about 8 nm to about 25 nm. Alloy.

  E14: Embodiments 11 to 13 wherein the boundary region has a length and an average width and has a transition oxide zone adjacent to the metal region, the transition zone running in the length direction in the boundary region Any alloy described.

  E15: the transition region has a transition oxide zone adjacent to the metal region, the transition oxide zone being about 4 nm to about 30 nm, about 5 nm to about 25 nm, about 7 nm to about 20 nm, or about 8 nm to about Embodiment 15. The alloy of any of embodiments 11 to 14 having an average width of 17 nm.

  E16: The alloy according to any one of embodiments 11 to 15, wherein the boundary region has a length and an average width, and has a metal oxide zone that runs in a length direction in the boundary region.

  E17: The boundary region has a metal oxide zone having an average width of about 5 nm to about 500 nm, about 6 nm to about 400 nm, about 7 nm to about 300 nm, about 8 nm to about 200 nm, or about 8 nm to about 100 nm The alloy according to any one of Forms 11 to 16.

  E18: the boundary region has a first transition oxide zone, a metal oxide zone, and a second transition oxide zone that have a length and an average width, and that run parallel to each other over the width; The alloy according to any one of Embodiments 11 to 17.

  E19: Embodiment in which the boundary region has a first transition oxide zone, a flow path, and a second transition oxide zone that have a length and an average width, and that run parallel to each other over the width. The alloy according to any one of 11 to 18.

  E20: a first transition oxide zone, a metal oxide zone, a flow path, and a second transition oxide zone in which the boundary region has a length and an average width, and runs parallel to each other over the width Embodiment 21. An alloy according to any of embodiments 11 to 19, wherein

  E21: the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times, or ≧ 24 times the average width Or the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times the average width, or Embodiment 21. The alloy of any of embodiments 11 through 20, wherein ≧ 24 times and the width is substantially uniform along the length.

  E22: the boundary region is about 12 nm to about 1100 nm, about 17 to about 1000 nm, about 20 nm to about 1000 nm, about 20 nm to about 900 nm, about 20 nm to about 800 nm, about 20 nm to about 700 nm, about 17 nm to about 600 nm, about Embodiment 22. The alloy of any of embodiments 11 to 21 having an average width of 20 nm to about 500 nm, about 25 nm to about 400 nm, about 30 nm to about 300 nm, about 35 nm to about 200 nm, or about 40 nm to about 100 nm.

  E23: about 0.1 atomic% to about 10.0 atomic%, about 0.7 to about 8.0 atomic%, about 1.0 to about 7.0 atomic%, about 1. 5 to about 6.0 atomic percent, or about 2.0 to about 5.5 atomic percent of one or more rare earth elements, or about 1.5 to about 2 of one or more rare earth elements. 0.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7 Embodiment 24. The alloy of any of embodiments 1 to 22, containing 0.0, about 7.5, or about 8.0 atomic percent, and levels in between.

  E24: The alloy according to any of embodiments 1 to 23, having at least one main phase and at least one secondary phase.

  E25: The alloy according to any one of Embodiments 1 to 24, which has at least one main phase and a secondary phase, wherein the secondary phase contains one or more rare earth elements.

  E26: The alloy according to any one of embodiments 1 to 25, having at least one main phase and a secondary phase, wherein the secondary phase contains Ni.

E27: i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) V, Cr, Mn, Ni, Sn, Al, Co, Cu, Mo, W, Fe, Si And one or more elements selected from the group consisting of rare earth elements, or i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni, Cr And one or more elements selected from the group consisting of B, Al, Si, Sn, other transition metals and rare earth elements, or i) selected from the group consisting of Ti, Zr, Nb and Hf Ii) Ni, Cr, and one or more elements selected from the group consisting of V, Mn, Sn, Al, Co, Cu, Mo, W, Fe, Si, and rare earth elements Including And,
28. The alloy according to any of embodiments 1-27, wherein, for example, the atomic ratio of ii) to i) is about 2.02 to about 2.45. The atomic ratio of ii) to i) is, for example, from about 2.04 to about 2.40, from about 2.10 to about 2.38, from about 2.20 to about 2.36, or from about 2.20 to about 2. .36.

  E28: The alloy according to any of embodiments 1-27, having a C14 or C15 Laves main phase, or having a C14 and C15 Laves main phase.

E29: C14 or C15 Laves main phase, or 14 and C15 Laves main phase,
An electrochemically active occlusion secondary phase containing La and Ni> 0.5 wt%, and a catalyst secondary phase containing Ti and Ni, about 0.3 wt% to about 15 wt%,
Embodiment 29. An alloy according to any of embodiments 1-28.

E30: Ti, Zr, V, Ni, Cr and one or more rare earth elements, or Ti, Zr, Ni, Mn, Cr and one or more rare earth elements, or Ti, Cr, V, Ni and one or more rare earth elements Rare earth elements, or one or more elements selected from the group consisting of Ti, Zr, V, Ni, Cr, and B, Al, Si, Sn, and other transition metals, or Ti, Zr, V, Ni Cr, one or more rare earth elements, and one or more elements selected from the group consisting of Mn, Sn, Al, Cu, Mo, W, Fe, Si and Co, or Ti, Zr, V, Ni, Cr, one or more rare earth elements, and one or more elements selected from the group consisting of Mn and Al, or Ti, Zr, V, Ni, Cr, Mn, Al, Co and one or more rare earth elements , Other Ti, Zr, V, Ni, Cr, Mn, Al, Co and La
Embodiment 30. An alloy according to any of embodiments 1 to 29, comprising

E31: about 0.1 to about 60% Ti, about 0.1 to about 40% Zr, 0 <V <60%, about 1% to about 56% Cr, about 5 to about 22% Mn, About 0.1 to about 57% Ni, 0 to about 3% Sn, about 0.1 to about 10% Al, about 0.1 to about 11% Co, and about one or more rare earth elements 0.1 to about 10%, or Ti about 5 to about 15%, Zr about 18 to about 29%, V about 3.0 to about 13%, Cr about 1 to about 10%, Mn about 6 to about 18%, Ni about 29 to about 41%, Al about 0.1 to about 0.7%, Co about 2 to about 11%, and one or more rare earth elements about 0.7 to about About 8%, or Ti about 11 to about 13%, Zr about 21 to about 23%, V about 9 to about 11%, Cr about 6 to about 9%, Mn about 6 to about 9%, About 31 to about 34% of Ni and about 0.3 to about 0 of Al 6%, from about 2 to about 8% Co, and one or more rare earth elements from about 1 to about 7%
Embodiment 31. An alloy according to any of embodiments 1 to 30, comprising, wherein the percentages are atomic percent and equal to 100% in total.

  E32: The alloy according to any of embodiments 1-31, wherein the metal oxide is a Ni and / or Cr metal oxide, such as a Ni / Cr oxide.

E33: a discharge capacity measured at 50MAg ^-1, and defined as the ratio to the discharge capacity measured in 4MAg ^-1, third time cycle of about 93%, about 94%, about 95%, about 96%, or about High rate discharge performance of 97%, or high rate discharge performance of ≧ 93%, ≧ 94%, ≧ 95%, ≧ 96%, or ≧ 97%, apply alkali pretreatment before half-cell measurement Rather, measured with a liquid cell design on a partially precharged Ni (OH) ₂ positive electrode, where each sample electrode was charged at a constant current density of 50 mAg ⁻¹ for 10 hours and then 50 mAg ^−. discharged at a ^first current density, 12 and 4MAg ^-1 twice pull continues, and / or ≦ 10, ≦ 9, ≦ 8 , ≦ 7, ≦ 6, of ≦ 5 or ≦ 4ohm · g,, or About 2 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 3 Exhibit charge transfer resistance (R) at −40 ° C. for a main phase or phases of about 6, about 3 to about 5, or about 3 to about 4 Ω · g, and / or about 5 to about Exhibit a charge transfer resistance (R) at −40 ° C. of about 20, about 7 to about 18, about 9 to about 16, about 10 to about 15, or about 11 to about 15 Ω · g, and / or about 1 to about 5, about 1 to about 4, about 1 to about 3 or about 1.5 to about 2.5 seconds, or ≦ 4, ≦ 3 or ≦ 2 seconds of one main phase or a plurality of main phases −40 Embodiment 33. An alloy according to any of embodiments 1 to 32, which exhibits surface catalyst performance at 0C.

  The following is another set of embodiments.

  E1: Hydrogen storage alloy, for example a hydrogen storage alloy with improved low temperature electrochemical properties, having a bulk metal region adjacent to the metal oxide boundary region, for example a bulk metal separated by a metal oxide boundary region A hydrogen storage alloy having a region, the boundary region having at least one flow channel, for example, wherein the flow channel allows the transport of electrolyte to the bulk metal region.

  E2: The hydrogen storage alloy according to embodiment 1, wherein the boundary region contains a metal oxide, such as Ni and / or Cr metal oxide, such as Ni / Cr metal oxide.

  E3: Oxygen ≧ 60 atomic%, oxygen ≧ 62 atomic%, oxygen ≧ 64 atomic%, oxygen ≧ 66 atomic%, or oxygen ≧ 68 atomic%, based on metal oxide, or oxygen About 60 atom% to about 82 atom%, oxygen about 63 to about 77 atom%, oxygen about 64 atom% to about 75 atom%, oxygen about 65 atom% to about 72 atom%, or oxygen about 66 About 60 atomic%, about 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69, about 70, about 71. The alloy of embodiment 2, comprising 71, about 72, about 73, about 74, about 75, about 76, about 77, about 78, about 79, about 80, about 81 or about 82 atomic%.

  E4: The metal oxide is based on the metal oxide, Cr ≧ 2 atomic%, Cr ≧ 3 atomic%, Cr ≧ 4 atomic%, or Cr ≧ 5 atomic%; or Cr about 2 atomic% About 8 atomic percent, Cr about 3 atomic percent to about 8 atomic percent, or Cr 4 atomic percent to about 7 atomic percent; or Cr about 2 atomic percent, about 3, about 4, about 5, about 6, The alloy of embodiment 2 or 3, comprising about 7 or about 8 atomic%.

  E5: the metal oxide is based on the metal oxide, Ni ≧ 16 atomic%, Ni ≧ 17 atomic%, Ni ≧ 18 atomic%, or Ni ≧ 19 atomic%; or Ni about 16 atomic% To about 23 atom%, Ni to about 17 atom% to about 22 atom%, or Ni to 18 atom% to about 21 atom%; or Ni to about 16 atom%, about 17, about 18, about 19, about 20, Embodiment 5. The alloy of any of embodiments 2 to 4, containing about 21, about 22, or about 23 atomic percent.

  E6: the metal oxide is about 64 atomic% to about 71 atomic% oxygen, about 3 atomic% to about 8 atomic% Cr, and about 16 atomic% to about 21 atomic% Ni based on the metal oxide The alloy according to any one of Embodiments 2 to 5, which is contained.

  E7: The metal oxide contains, based on the metal oxide, one or more elements selected from the group consisting of oxygen, Ni, Cr, and Al, Ti, V, Mn, Co, and Zr. The alloy according to any one of Embodiments 2 to 6.

  E8: The alloy according to any of embodiments 1 to 7, wherein the boundary region has a length and an average width and has at least one flow path running along the length of the boundary region.

  E9: Embodiments 1 to 8 wherein the boundary region has at least one flow path having an average width of about 4 nm to about 40 nm, about 5 nm to about 35 nm, about 7 nm to about 30 nm, or about 8 nm to about 25 nm An alloy according to any one of the above.

  E10: Embodiments 1 to 9 wherein the boundary region has a length and an average width and further has a transition oxide zone adjacent to the metal region, the transition zone running along the length of the boundary region Any alloy up to.

  E11: The alloy of embodiment 10, wherein the transition oxide zone has an average width of about 4 nm to about 30 nm, about 5 nm to about 25 nm, about 7 nm to about 20 nm, or about 8 nm to about 17 nm.

  E12: The alloy according to any of embodiments 1 to 11, wherein the boundary region has a length and an average width and has a metal oxide zone that runs along the length of the boundary region.

  E13: The embodiment of embodiment 12, wherein the metal oxide band has an average width of about 5 nm to about 500 nm, about 6 nm to about 400 nm, about 7 nm to about 300 nm, about 8 nm to about 200 nm, or about 8 nm to about 100 nm. alloy.

  E14: a first transition oxide zone, a metal oxide zone, and a second transition, wherein the boundary region has a length and an average width, and runs along the length of the boundary region, respectively, over the width Any of Embodiments 1-13, having an oxide zone, or having a first transition oxide zone, a metal oxide zone, and a second transition oxide zone each running parallel to each other across said width. The described alloy.

  E15: a first transition oxide zone, a flow path, and a second transition oxide, wherein the boundary region has a length and an average width, and runs along the length of the boundary region over the width, respectively Embodiment 15. The alloy of any of embodiments 1 through 14, having a zone or having a first transition oxide zone, a flow path, and a second transition oxide zone each running parallel to each other across the width.

  E16: the first transition oxide zone, the metal oxide zone, the flow path, and the first zone having a length and an average width, and running along the length of the boundary region, respectively, over the width Embodiment 1 having two transition oxide zones, or having a first transition oxide zone, a metal oxide zone, a flow path, and a second transition oxide zone, each running parallel to each other across the width. 15. The alloy according to any one of 15 to 15.

  E17: the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times, or ≧ 24 times the average width Or the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times the average width, or Embodiment 17. An alloy according to any of embodiments 1 to 16, wherein ≧ 24 times and the width is substantially uniform along the length.

  E18: the boundary region is about 12 nm to about 1100 nm, about 17 to about 1000 nm, about 20 nm to about 1000 nm, about 20 nm to about 900 nm, about 20 nm to about 800 nm, about 20 nm to about 700 nm, about 17 nm to about 600 nm, about Embodiment 18. The alloy of any of embodiments 1 to 17, having an average width of 20 nm to about 500 nm, about 25 nm to about 400 nm, about 30 nm to about 300 nm, about 35 nm to about 200 nm, or about 40 nm to about 100 nm.

  E19: about 0.1 atomic% to about 10.0 atomic%, about 0.7 to about 8.0 atomic%, about 1.0 to about 7.0 atomic%, about 1. 5 to about 6.0 atomic percent, or about 2.0 to about 5.5 atomic percent of one or more rare earth elements, or about 1.5 to about 2 of one or more rare earth elements. 0.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7 The alloy of any of embodiments 1-18, containing 0.0, about 7.5, or about 8.0 atomic percent, and levels in between.

  E20: The alloy according to any of embodiments 1-19, having at least one main phase and at least one secondary phase.

  E21: The alloy according to any one of Embodiments 1 to 20, which has at least one main phase and a secondary phase, wherein the secondary phase contains one or more rare earth elements.

  E22: The alloy according to any one of embodiments 1 to 21, which has at least one main phase and a secondary phase, wherein the secondary phase contains Ni.

  E23: The alloy according to any one of Embodiments 1 to 22, which has at least one main phase and a secondary phase, wherein the secondary phase contains La and Ni.

E24: i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) V, Cr, Mn, Ni, Sn, Al, Co, Cu, Mo, W, Fe, Si And one or more elements selected from the group consisting of rare earth elements, or i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni, Cr And one or more elements selected from the group consisting of B, Al, Si, Sn, other transition metals and rare earth elements, or i) selected from the group consisting of Ti, Zr, Nb and Hf Ii) Ni, Cr, and one or more elements selected from the group consisting of V, Mn, Sn, Al, Co, Cu, Mo, W, Fe, Si, and rare earth elements Including And,
For example, the alloy according to any of embodiments 1 to 23, wherein the atomic ratio of ii) to i) is about 2.02 to about 2.45. The atomic ratio of ii) to i) is, for example, from about 2.04 to about 2.40, from about 2.10 to about 2.38, from about 2.20 to about 2.36, or from about 2.20 to about 2. .36.

  E25: The alloy according to any of embodiments 1 to 24, comprising a C14 or C15 Laves main phase, or a C14 and C15 Laves main phase.

E26: C14 or C15 Laves main phase, or 14 and C15 Laves main phase,
An electrochemically active occlusion secondary phase containing La and Ni> 0.5 wt%, and a catalyst secondary phase containing Ti and Ni, about 0.3 wt% to about 15 wt%,
The alloy according to any of embodiments 1 to 25, having:

E27: Ti, Zr, V, Ni, Cr and one or more rare earth elements, or Ti, Zr, Ni, Mn, Cr and one or more rare earth elements, or Ti, Cr, V, Ni and one or more rare earth elements A rare earth element, or one or more elements selected from the group consisting of Ti, Zr, V, Ni, Cr, and B, Al, Si, Sn, and other transition metals, or Ti, Zr, V, Ni, Cr, one or more rare earth elements, and one or more elements selected from the group consisting of Mn, Sn, Al, Cu, Mo, W, Fe, Si and Co, or Ti, Zr, V, Ni, Cr One or more rare earth elements and one or more elements selected from the group consisting of Mn and Al, or Ti, Zr, V, Ni, Cr, Mn, Al, Co and one or more rare earth elements, Ma Is Ti, Zr, V, Ni, Cr, Mn, Al, Co and La
Embodiment 27. An alloy according to any of embodiments 1 to 26, comprising

E28: about 0.1 to about 60% Ti, about 0.1 to about 40% Zr, 0 <V <60%, about 1% to about 56% Cr, about 5% to about 22% Mn, About 0.1 to about 57% Ni, 0 to about 3% Sn, about 0.1 to about 10% Al, about 0.1 to about 11% Co, and about one or more rare earth elements 0.1 to about 10%, or Ti about 5 to about 15%, Zr about 18 to about 29%, V about 3.0 to about 13%, Cr about 1 to about 10%, Mn about 6 to about 18%, Ni about 29 to about 41%, Al about 0.1 to about 0.7%, Co about 2 to about 11%, and one or more rare earth elements about 0.7 to about About 8%, or Ti about 11 to about 13%, Zr about 21 to about 23%, V about 9 to about 11%, Cr about 6 to about 9%, Mn about 6 to about 9%, About 31 to about 34% of Ni and about 0.3 to about 0 of Al 6%, from about 2 to about 8% Co, and one or more rare earth elements from about 1 to about 7%,
Embodiment 28. An alloy according to any of embodiments 1 to 27, comprising, wherein the percentages are atomic%, totaling 100%.

E29: a discharge capacity measured at 50MAg ^-1, and defined as the ratio to the discharge capacity measured in 4MAg ^-1, third time cycle of about 93%, about 94%, about 95%, about 96%, or about High rate discharge performance of 97%, or high rate discharge performance of ≧ 93%, ≧ 94%, ≧ 95%, ≧ 96%, or ≧ 97%, apply alkali pretreatment before half-cell measurement Rather, measured with a liquid cell design on a partially precharged Ni (OH) ₂ positive electrode, where each sample electrode was charged at a constant current density of 50 mAg ⁻¹ for 10 hours and then 50 mAg ^−. discharged at a ^first current density, 12 and 4MAg ^-1 twice pull continues, and / or ≦ 10, ≦ 9, ≦ 8 , ≦ 7, ≦ 6, of ≦ 5 or ≦ 4ohm · g,, or About 2 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 3 Exhibit charge transfer resistance (R) at −40 ° C. for a main phase or phases of about 6, about 3 to about 5, or about 3 to about 4 Ω · g, and / or about 5 to about Exhibit a charge transfer resistance (R) at −40 ° C. of about 20, about 7 to about 18, about 9 to about 16, about 10 to about 15, or about 11 to about 15 Ω · g, and / or about 1 to about 5, about 1 to about 4, about 1 to about 3 or about 1.5 to about 2.5 seconds, or ≦ 4, ≦ 3 or ≦ 2 seconds of one main phase or a plurality of main phases −40 29. An alloy according to any of embodiments 1 to 28, which exhibits surface catalyst performance at 0 ° C.

  The following is another set of embodiments.

  E1: a hydrogen storage alloy having a metal region adjacent to the boundary region, for example a metal region separated by the boundary region, for example a hydrogen storage alloy having improved low temperature properties, wherein the boundary region has a length And having an average width of about 12 nm to about 1100 nm, about 17 to about 1000 nm, about 20 nm to about 1000 nm, about 20 nm to about 900 nm, about 20 nm to about 800 nm, about 20 nm to about 700 nm, about 17 nm to A hydrogen storage alloy that is about 600 nm, about 20 nm to about 500 nm, about 25 nm to about 400 nm, about 30 nm to about 300 nm, about 35 nm to about 200 nm, or about 40 nm to about 100 nm.

  E2: The hydrogen storage alloy according to embodiment 1, wherein the boundary region contains a metal oxide, such as Ni and / or Cr metal oxide, such as Ni / Cr metal oxide.

  E3: on the basis of metal oxide, on the basis of metal oxide, the metal oxide has oxygen of ≧ 60 atomic%, oxygen of ≧ 62 atomic%, oxygen of ≧ 64 atomic%, oxygen of ≧ 66 atomic%, Or about 68 atomic percent to about 82 atomic percent oxygen, about 63 to about 77 atomic percent oxygen, about 64 atomic percent to about 75 atomic percent oxygen, about 65 atomic percent oxygen From about 66 atomic percent to about 70 atomic percent, or from about 60 atomic percent, about 61, about 62, about 63, about 64, about 65, about 66, About 67, about 68, about 69, about 70, about 71, about 72, about 73, about 74, about 75, about 76, about 77, about 78, about 79, about 80, about 81 or about 82 atomic% The alloy according to embodiment 2.

  E4: The metal oxide is based on the metal oxide, Cr ≧ 2 atomic%, Cr ≧ 3 atomic%, Cr ≧ 4 atomic%, or Cr ≧ 5 atomic%; or Cr about 2 atomic% About 8 atomic percent, Cr about 3 atomic percent to about 8 atomic percent, or Cr 4 atomic percent to about 7 atomic percent; or Cr about 2 atomic percent, about 3, about 4, about 5, about 6, The alloy of embodiment 2 or 3, comprising about 7 or about 8 atomic%.

  E5: the metal oxide is based on the metal oxide, Ni ≧ 16 atomic%, Ni ≧ 17 atomic%, Ni ≧ 18 atomic%, or Ni ≧ 19 atomic%; or Ni about 16 atomic% To about 23 atomic percent, Ni from about 17 atomic percent to about 22 atomic percent, or Ni from 18 to about 21 atomic percent; or Ni from about 16 atomic percent, about 17, about 18, about 19, about 20, about 21 Embodiment 5. An alloy according to any of embodiments 2 to 4, containing about 22 or about 23 atomic percent.

  E6: Ni / Cr oxide is about 64 atomic percent to about 71 atomic percent oxygen, about 3 atomic percent to about 8 atomic percent Cr, and about 16 atomic percent to about 21 atomic percent Ni based on the metal oxide The alloy according to any one of Embodiments 2 to 5, which contains:

  E7: The embodiments 2 to 6 wherein the Ni / Cr oxide contains one or more elements selected from the group consisting of oxygen, Ni, Cr and Al, Ti, V, Mn, Co and Zr Any alloy described.

  E8: the boundary region has at least one flow path having a length and an average width and running along the length of the boundary area, wherein the flow path is electrolyte transport to the bulk metal region Embodiment 8. An alloy according to any of embodiments 1 to 7, which can enable

  E9: Embodiments 1 to 8 wherein the boundary region has at least one flow path having an average width of about 4 nm to about 40 nm, about 5 nm to about 35 nm, about 7 nm to about 30 nm, or about 8 nm to about 25 nm An alloy according to any one of the above.

  E10: The alloy of any of embodiments 1-9, wherein the boundary region has a transition oxide zone adjacent to the metal region.

  E11: Embodiments 1 to 10 wherein the boundary region has a length and an average width and has a transition oxide zone adjacent to the metal region, the transition zone running along the length of the boundary region An alloy according to any one of the above.

  E12: the boundary region has a transition oxide zone adjacent to the metal region, the transition oxide zone being about 4 nm to about 30 nm, about 5 nm to about 25 nm, about 7 nm to about 20 nm, or about 8 nm to about Embodiment 12. The alloy of any of embodiments 1 to 11 having an average width of 17 nm.

  E13: The alloy according to any one of embodiments 1 to 12, wherein the boundary region has a metal oxide zone.

  E14: The alloy according to any of embodiments 1-13, wherein the boundary region has a length and an average width and has a metal oxide zone that runs along the length of the boundary region.

  E15: The boundary region has a metal oxide zone having an average width of about 5 nm to about 500 nm, about 6 nm to about 400 nm, about 7 nm to about 300 nm, about 8 nm to about 200 nm, or about 8 nm to about 100 nm 15. The alloy according to any one of forms 1 to 14.

  E16: a first transition oxide zone, a metal oxide zone, and a second transition, wherein the boundary region has a length and an average width, and runs along the length of the boundary region, respectively, over the width Embodiments having an oxide zone or having a first transition oxide zone, a metal oxide zone, and a second transition oxide zone across the width, wherein each runs parallel to each other The alloy according to any one of 1 to 15.

  E17: a first transition oxide zone, a flow path, and a second transition oxide, wherein the boundary region has a length and an average width, and runs along the length of the boundary region, respectively, over the width Embodiment 17. The alloy of any of embodiments 1 to 16, having a zone or having a first transition oxide zone, a flow path, and a second transition oxide zone each running parallel to each other across the width.

  E18: the first transition oxide zone, the metal oxide zone, the flow path, and the first zone having a length and an average width, and running along the length of the boundary region, respectively, over the width Embodiment 1 having two transition oxide zones, or having a first transition oxide zone, a metal oxide zone, a flow path, and a second transition oxide zone, each running parallel to each other across the width. 18. An alloy according to any one of 17 to 17.

  E19: the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times, or ≧ 24 times the average width Or the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times the average width, or Embodiment 19. The alloy of any of embodiments 1 through 18, wherein ≧ 24 times and the width is substantially uniform along the length.

  E20: The alloy of any of embodiments 1-19, wherein the boundary region has an average width of about 20 nm to about 500 nm.

  E21: about 0.1 atomic% to about 10.0 atomic%, about 0.7 to about 8.0 atomic%, about 1.0 to about 7.0 atomic%, about 1. 5 to about 6.0 atomic percent, or about 2.0 to about 5.5 atomic percent of one or more rare earth elements, or about 1.5 to about 2 of one or more rare earth elements. 0.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7 Embodiment 21. The alloy of any of embodiments 1 to 20, containing 0.0, about 7.5, or about 8.0 atomic percent, and levels in between.

  E22: The alloy according to any of embodiments 1-21, having at least one main phase and at least one secondary phase.

  E23: The alloy according to any one of Embodiments 1 to 22, which has at least one main phase and a secondary phase, wherein the secondary phase contains one or more rare earth elements.

  E24: The alloy according to any one of embodiments 1 to 23, which has at least one main phase and a secondary phase, wherein the secondary phase contains Ni.

  E25: The alloy according to any one of embodiments 1 to 24, which has at least one main phase and a secondary phase, wherein the secondary phase contains La and Ni.

E26: i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) V, Cr, Mn, Ni, Sn, Al, Co, Cu, Mo, W, Fe, Si And one or more elements selected from the group consisting of rare earth elements, or i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni, Cr And one or more elements selected from the group consisting of B, Al, Si, Sn, other transition metals and rare earth elements, or i) selected from the group consisting of Ti, Zr, Nb and Hf Ii) Ni, Cr, and one or more elements selected from the group consisting of V, Mn, Sn, Al, Co, Cu, Mo, W, Fe, Si, and rare earth elements Including And,
Embodiment 26. The alloy of any of embodiments 1 through 25, wherein, for example, the atomic ratio of ii) to i) is from about 2.02 to about 2.45. The atomic ratio of ii) to i) is, for example, from about 2.04 to about 2.40, from about 2.10 to about 2.38, from about 2.20 to about 2.36, or from about 2.20 to about 2. .36.

  E27: An alloy according to any of embodiments 1 to 26, having a C14 or C15 Laves main phase or having a C14 and C15 Laves main phase.

E28: C14 or C15 Laves main phase, or 14 and C15 Laves main phase,
An electrochemically active occlusion secondary phase containing La and Ni> 0.5 wt%, and a catalyst secondary phase containing Ti and Ni, about 0.3 wt% to about 15 wt%,
Embodiment 28. An alloy according to any of embodiments 1 to 27, having

E29: Ti, Zr, V, Ni, Cr and one or more rare earth elements, or Ti, Zr, Ni, Mn, Cr and one or more rare earth elements, or Ti, Cr, V, Ni and one or more rare earth elements A rare earth element, or one or more elements selected from the group consisting of Ti, Zr, V, Ni, Cr, and B, Al, Si, Sn, and other transition metals, or Ti, Zr, V, Ni, Cr, one or more rare earth elements, and one or more elements selected from the group consisting of Mn, Sn, Al, Cu, Mo, W, Fe, Si and Co, or Ti, Zr, V, Ni, Cr One or more rare earth elements and one or more elements selected from the group consisting of Mn and Al, or Ti, Zr, V, Ni, Cr, Mn, Al, Co and one or more rare earth elements, Ma Is Ti, Zr, V, Ni, Cr, Mn, Al, Co and La
The alloy according to any of embodiments 1-28, comprising

E30: about 0.1 to about 60% Ti, about 0.1 to about 40% Zr, 0 <V <60%, about 1% to about 56% Cr, about 5 to about 22% Mn, About 0.1 to about 57% Ni, 0 to about 3% Sn, about 0.1 to about 10% Al, about 0.1 to about 11% Co, and about one or more rare earth elements 0.1 to about 10%, or Ti about 5 to about 15%, Zr about 18 to about 29%, V about 3.0 to about 13%, Cr about 1 to about 10%, Mn about 6 to about 18%, Ni about 29 to about 41%, Al about 0.1 to about 0.7%, Co about 2 to about 11%, and one or more rare earth elements about 0.7 to about About 8%, or Ti about 11 to about 13%, Zr about 21 to about 23%, V about 9 to about 11%, Cr about 6 to about 9%, Mn about 6 to about 9%, About 31 to about 34% of Ni and about 0.3 to about 0 of Al 6%, from about 2 to about 8% Co, and one or more rare earth elements from about 1 to about 7%
30. An alloy according to any of embodiments 1 to 29, wherein the percentage is atomic%, and equals a total of 100%.

E31: a discharge capacity measured at 50MAg ^-1, and defined as the ratio to the discharge capacity measured in 4MAg ^-1, third time cycle of about 93%, about 94%, about 95%, about 96%, or about High rate discharge performance of 97%, or high rate discharge performance of ≧ 93%, ≧ 94%, ≧ 95%, ≧ 96%, or ≧ 97%, apply alkali pretreatment before half-cell measurement Rather, measured with a liquid cell design on a partially precharged Ni (OH) ₂ positive electrode, where each sample electrode was charged at a constant current density of 50 mAg ⁻¹ for 10 hours and then 50 mAg ^−. discharged at a ^first current density, 12 and 4MAg ^-1 twice pull continues, and / or ≦ 10, ≦ 9, ≦ 8 , ≦ 7, ≦ 6, of ≦ 5 or ≦ 4ohm · g,, or About 2 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 3 Exhibit charge transfer resistance (R) at −40 ° C. for a main phase or phases of about 6, about 3 to about 5, or about 3 to about 4 Ω · g, and / or about 5 to about Exhibit a charge transfer resistance (R) at −40 ° C. of about 20, about 7 to about 18, about 9 to about 16, about 10 to about 15, or about 11 to about 15 Ω · g, and / or about 1 to about 5, about 1 to about 4, about 1 to about 3 or about 1.5 to about 2.5 seconds, or ≦ 4, ≦ 3 or ≦ 2 seconds of one main phase or a plurality of main phases −40 Embodiment 31. The alloy of any of embodiments 1 to 30, which exhibits surface catalyst performance at 0C.

  The following is another set of embodiments.

  E1: a hydrogen storage alloy having one or more bulk metal regions and a metal oxide zone containing a metal oxide, eg, a hydrogen storage alloy having improved low temperature properties, wherein the oxide zone is , Parallel to at least one flow path, wherein the flow path is capable of allowing electrolyte transport to the bulk region.

  E2: The hydrogen storage alloy according to embodiment 1, wherein the metal oxide is a Ni and / or Cr metal oxide, for example, a Ni / Cr metal oxide.

  E3: the metal oxide is based on the metal oxide, oxygen ≧ 60 atomic%, oxygen ≧ 62 atomic%, oxygen ≧ 64 atomic%, oxygen ≧ 66 atomic%, or oxygen ≧ 68 atomic% Or about 60 atom% to about 82 atom%, oxygen about 63 to about 77 atom%, oxygen about 64 atom% to about 75 atom%, oxygen about 65 atom% to about 72 atom% Or about 66 atomic percent to about 70 atomic percent of oxygen, or about 60 atomic percent, about 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69, about 70, about 71, about 72, about 73, about 74, about 75, about 76, about 77, about 78, about 79, about 80, about 81 or about 82 atomic%, Embodiment 1 or 2 The described alloy.

  E4: The alloy according to any of embodiments 1 to 3, wherein the metal oxide contains about 60 atomic% to about 82 atomic% of oxygen based on the metal oxide.

  E5: the metal oxide is based on metal oxide, Cr ≧ 2 atomic%, Cr ≧ 3 atomic%, Cr ≧ 4 atomic%, or Cr ≧ 5 atomic%; or Cr about 2 atomic% About 8 atomic percent, Cr about 3 atomic percent to about 8 atomic percent, or Cr 4 atomic percent to about 7 atomic percent; or Cr about 2 atomic percent, about 3, about 4, about 5, about 6, Embodiment 5. An alloy according to any of embodiments 1 to 4, containing about 7 or about 8 atomic%.

  E6: the metal oxide is based on the metal oxide, Ni ≧ 16 atomic%, Ni ≧ 17 atomic%, Ni ≧ 18 atomic%, or Ni ≧ 19 atomic%; or Ni about 16 atomic% To about 23 atom%, Ni to about 17 atom% to about 22 atom%, or Ni to 18 atom% to about 21 atom%; or Ni to about 16 atom%, about 17, about 18, about 19, about 20, Embodiment 6. The alloy of any of embodiments 1 to 5, containing about 21, about 22, or about 23 atomic percent.

  E7: The metal oxide contains about 64 atomic% to about 71 atomic% oxygen, about 3 atomic% to about 8 atomic% Cr, and about 16 to about 21 atomic% Ni based on the metal oxide The alloy according to any one of Embodiments 1 to 6.

  E8: The metal oxide contains one or more elements selected from the group consisting of oxygen, Ni, Cr, and Al, Ti, V, Mn, Co, and Zr, for example, where Al, Ti, V One or more elements selected from the group consisting of Mn, Co, and Zr, based on the metal oxide, total about 1 atom% to about 17 atom%, about 2 atom% to Embodiment 8. The alloy of any of embodiments 1 to 7, wherein the alloy is present from about 14 atom%, from about 3 atom% to about 12 atom%, from about 3 atom% to about 10 atom%, or from about 4 atom% to about 9 atom%. .

  E9: the flow path has a length and an average width, wherein the length is ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times, or ≧ 24 times the average width; The alloy according to any one of Embodiments 1 to 8.

  E10: Any of embodiments 1-9, wherein the at least one flow path has an average width of about 4 nm to about 40 nm, about 5 nm to about 35 nm, about 7 nm to about 30 nm, or about 8 nm to about 25 nm. Alloy.

  E11: The flow path is adjacent to a transition oxide zone adjacent to the metal region, the transition oxide zone being about 4 nm to about 30 nm, about 5 nm to about 25 nm, about 7 nm to about 20 nm, or about 8 nm. Embodiment 11. The alloy of any of embodiments 1 to 10, having an average width of about 17 nm.

  E12: Embodiments 1-11 wherein the metal oxide band has an average width of about 5 nm to about 500 nm, about 6 nm to about 400 nm, about 7 nm to about 300 nm, about 8 nm to about 200 nm, or about 8 nm to about 100 nm Any alloy up to.

  E13: The alloy according to any one of Embodiments 1 to 12, having a transition oxide zone, wherein the transition zone runs parallel to the metal oxide zone.

  E14: about 0.1 atomic% to about 10.0 atomic%, about 0.7 to about 8.0 atomic%, about 1.0 to about 7.0 atomic%, about 1. 5 to about 6.0 atomic percent, or about 2.0 to about 5.5 atomic percent of one or more rare earth elements, or about 1.5 to about 2 of one or more rare earth elements. 0.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7 The alloy of any of embodiments 1-13, containing 0.0, about 7.5, or about 8.0 atomic percent, and levels in between.

  E15: The alloy according to any of embodiments 1 to 14, having at least one main phase and at least one secondary phase.

  E16: The alloy according to any one of Embodiments 1 to 15, which has at least one main phase and a secondary phase, wherein the secondary phase contains one or more rare earth elements.

  E17: The alloy according to any one of Embodiments 1 to 16, which has at least one main phase and a secondary phase, wherein the secondary phase contains Ni.

  E18: The alloy according to any one of embodiments 1 to 17, which has at least one main phase and a secondary phase, wherein the secondary phase contains La and Ni.

E19: i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) V, Cr, Mn, Ni, Sn, Al, Co, Cu, Mo, W, Fe, Si And one or more elements selected from the group consisting of rare earth elements, or i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni, Cr And one or more elements selected from the group consisting of B, Al, Si, Sn, other transition metals and rare earth elements, or i) selected from the group consisting of Ti, Zr, Nb and Hf Ii) Ni, Cr, and one or more elements selected from the group consisting of V, Mn, Sn, Al, Co, Cu, Mo, W, Fe, Si, and rare earth elements Including And,
For example, an alloy according to any of embodiments 1 to 18, wherein the atomic ratio of ii) to i) is from about 2.02 to about 2.45. The atomic ratio of ii) to i) is, for example, from about 2.04 to about 2.40, from about 2.10 to about 2.38, from about 2.20 to about 2.36, or from about 2.20 to about 2. .36.

  E20: The alloy according to any of embodiments 1-19, having a C14 or C15 Laves main phase, or having a C14 and C15 Laves main phase.

E21: C14 or C15 Laves main phase, or 14 and C15 Laves main phase,
An electrochemically active occlusion secondary phase containing La and Ni> 0.5 wt%, and a catalyst secondary phase containing Ti and Ni, about 0.3 wt% to about 15 wt%,
Embodiment 21. An alloy according to any of embodiments 1 to 20 having

E22: Ti, Zr, V, Ni, Cr and one or more rare earth elements, or Ti, Zr, Ni, Mn, Cr and one or more rare earth elements, or Ti, Cr, V, Ni and one or more rare earth elements A rare earth element, or one or more elements selected from the group consisting of Ti, Zr, V, Ni, Cr, and B, Al, Si, Sn, and other transition metals, or Ti, Zr, V, Ni, Cr, one or more rare earth elements, and one or more elements selected from the group consisting of Mn, Sn, Al, Cu, Mo, W, Fe, Si and Co, or Ti, Zr, V, Ni, Cr One or more rare earth elements and one or more elements selected from the group consisting of Mn and Al, or Ti, Zr, V, Ni, Cr, Mn, Al, Co and one or more rare earth elements, Ma Is Ti, Zr, V, Ni, Cr, Mn, Al, Co and La
The alloy according to any one of embodiments 1 to 21, which contains

E23: about 0.1 to about 60% Ti, about 0.1 to about 40% Zr, 0 <V <60%, about 1% to about 56% Cr, about 5 to about 22% Mn, About 0.1 to about 57% Ni, 0 to about 3% Sn, about 0.1 to about 10% Al, about 0.1 to about 11% Co, and about one or more rare earth elements 0.1 to about 10%, or Ti about 5 to about 15%, Zr about 18 to about 29%, V about 3.0 to about 13%, Cr about 1 to about 10%, Mn about 6 to about 18%, Ni about 29 to about 41%, Al about 0.1 to about 0.7%, Co about 2 to about 11%, and one or more rare earth elements about 0.7 to about About 8%, or Ti about 11 to about 13%, Zr about 21 to about 23%, V about 9 to about 11%, Cr about 6 to about 9%, Mn about 6 to about 9%, About 31 to about 34% of Ni and about 0.3 to about 0 of Al 6%, from about 2 to about 8% Co, and one or more rare earth elements from about 1 to about 7%
Embodiment 24. An alloy according to any of embodiments 1 to 22, comprising, wherein the percentages are atomic%, and equal to 100% in total.

E24: a discharge capacity measured at 50MAg ^-1, and defined as the ratio to the discharge capacity measured in 4MAg ^-1, third time cycle of about 93%, about 94%, about 95%, about 96%, or about High rate discharge performance of 97%, or high rate discharge performance of ≧ 93%, ≧ 94%, ≧ 95%, ≧ 96%, or ≧ 97%, apply alkali pretreatment before half-cell measurement Rather, measured with a liquid cell design on a partially precharged Ni (OH) ₂ positive electrode, where each sample electrode was charged at a constant current density of 50 mAg ⁻¹ for 10 hours and then 50 mAg ^−. discharged at a ^first current density, 12 and 4MAg ^-1 twice pull continues, and / or ≦ 10, ≦ 9, ≦ 8 , ≦ 7, ≦ 6, of ≦ 5 or ≦ 4ohm · g,, or About 2 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 3 Exhibit charge transfer resistance (R) at −40 ° C. for a main phase or phases of about 6, about 3 to about 5, or about 3 to about 4 Ω · g, and / or about 5 to about Exhibit a charge transfer resistance (R) at −40 ° C. of about 20, about 7 to about 18, about 9 to about 16, about 10 to about 15, or about 11 to about 15 Ω · g, and / or about 1 to about 5, about 1 to about 4, about 1 to about 3 or about 1.5 to about 2.5 seconds, or ≦ 4, ≦ 3 or ≦ 2 seconds of one main phase or a plurality of main phases −40 Embodiment 24. The alloy of any of embodiments 1 to 23, which exhibits surface catalyst performance at 0C.

  Some further embodiments of the invention are described below.

  E1: Hydrogen storage alloys containing Ni and / or Cr metal oxides, such as Ni / Cr metal oxides, eg hydrogen storage alloys with improved low temperature properties, for example Ni / Cr containing Ni / Cr Hydrogen storage alloys that contain Cr metal oxides, each of which is present in a higher atomic percentage than any other respective metal (any other metal or metalloid).

  E2: the metal oxide is based on the metal oxide, oxygen ≧ 60 atomic%, oxygen ≧ 62 atomic%, oxygen ≧ 64 atomic%, oxygen ≧ 66 atomic%, or oxygen ≧ 68 atomic% Or about 60 atom% to about 82 atom%, oxygen about 63 to about 77 atom%, oxygen about 64 atom% to about 75 atom%, oxygen about 65 atom% to about 72 atom% Or about 66 atomic percent to about 70 atomic percent of oxygen, or about 60 atomic percent, about 61, about 62, about 63, about 64, about 65, about 66, about 67, about 68, about 69, about 70, about 71, about 72, about 73, about 74, about 75, about 76, about 77, about 78, about 79, about 80, about 81 or about 82 atomic%. alloy.

  E3: The alloy according to embodiment 1 or 2, wherein the metal oxide contains about 60 atomic% to about 82 atomic% of oxygen based on the metal oxide.

  E4: The metal oxide is based on the metal oxide, Cr ≧ 2 atomic%, Cr ≧ 3 atomic%, Cr ≧ 4 atomic%, or Cr ≧ 5 atomic%; or Cr about 2 atomic% About 8 atomic percent, Cr about 3 atomic percent to about 8 atomic percent, or Cr 4 atomic percent to about 7 atomic percent; or Cr about 2 atomic percent, about 3, about 4, about 5, about 6, Embodiment 4. The alloy of any of embodiments 1 to 3 containing about 7 or about 8 atomic percent.

  E5: The alloy according to any one of embodiments 1 to 4, wherein the metal oxide contains about 2 atomic% to about 8 atomic% of Cr based on the metal oxide.

  E6: the metal oxide is based on the metal oxide, Ni ≧ 16 atomic%, Ni ≧ 17 atomic%, Ni ≧ 18 atomic%, or Ni ≧ 19 atomic%; or Ni about 16 atomic% To about 23 atom%, Ni to about 17 atom% to about 22 atom%, or Ni to 18 atom% to about 21 atom%; or Ni to about 16 atom%, about 17, about 18, about 19, about 20, Embodiment 6. The alloy of any of embodiments 1 to 5, containing about 21, about 22, or about 23 atomic percent.

  E7: The alloy according to any one of embodiments 1 to 6, wherein the metal oxide contains about 16 atomic% to about 23 atomic% of Ni based on the metal oxide.

  E8: The metal oxide contains about 64 atom% to about 71 atom% oxygen, about 3 atom% to about 8 atom% Cr, and about 16 to about 21 atom% Ni based on the metal oxide The alloy according to any one of Embodiments 1 to 7.

  E9: The alloy according to any one of embodiments 1 to 8, wherein the metal oxide contains one or more elements selected from the group consisting of B, Al, Si, Sn, and a transition metal.

  E10: The alloy according to any one of embodiments 1 to 9, wherein the metal oxide contains one or more elements selected from the group consisting of Al, Ti, V, Mn, Co, and Zr.

  E11: The metal oxide comprises a total of about 1 atomic% to about 17 atomic% of one or more elements selected from the group consisting of B, Si, Sn, Al, Ti, V, Mn, Co, and Zr From about 2 atom% to about 14 atom%, from about 3 atom% to about 12 atom%, from about 3 atom% to about 10 atom%, or from about 4 atom% to about 9 atom% An alloy according to any one of the above.

  E12: the metal oxide is present in a boundary region adjacent to the metal region, for example in a boundary region separating the metal region, for example, the metal oxide is present in a metal oxide zone present in the boundary region The alloy according to any one of 1 to 11.

  E13: The alloy of embodiment 12, wherein the boundary region has at least one flow path having a length and an average width and running in a length direction in the boundary region.

  E14: In embodiment 12 or 13, wherein the boundary region has at least one flow path having an average width of about 4 nm to about 40 nm, about 5 nm to about 35 nm, about 7 nm to about 30 nm, or about 8 nm to about 25 nm The described alloy.

  E15: Embodiments 12 to 14 wherein the boundary region has a length and an average width and has a transition oxide zone adjacent to the metal region, the transition zone running in the length direction in the boundary region Any alloy described.

  E16: the boundary region has a transition oxide zone adjacent to the metal region, the transition oxide zone being about 4 nm to about 30 nm, about 5 nm to about 25 nm, about 7 nm to about 20 nm, or about 8 nm to about Embodiment 16. The alloy of any of embodiments 12 through 15 having an average width of 17 nm.

  E17: The alloy according to any of embodiments 12 to 16, wherein the boundary region has a length and an average width and has a metal oxide zone running in the length direction in the boundary region.

  E18: The boundary region has a metal oxide zone having an average width of about 5 nm to about 500 nm, about 6 nm to about 400 nm, about 7 nm to about 300 nm, about 8 nm to about 200 nm, or about 8 nm to about 100 nm The alloy according to any one of forms 12 to 17.

  E19: Does the boundary region have a first transition oxide zone, a metal oxide zone, and a second transition oxide zone that have a length and an average width and that run parallel to each other over the width? Or any one of embodiments 12-18, having a first transition oxide zone, a metal oxide zone, and a second transition oxide zone, each running along the length of the boundary region over the width. The described alloy.

  E20: the boundary region has a first transition oxide zone, a flow path, and a second transition oxide zone each having a length and an average width and running parallel to each other over the width; or Embodiment 20. The alloy of any of embodiments 12-19, having a first transition oxide zone, a flow path, and a second transition oxide zone, each running along the length of the boundary region across the width.

  E21: a first transition oxide zone, a metal oxide zone, a flow path, and a second transition oxide zone in which the boundary region has a length and an average width, and runs parallel to each other over the width Or a first transition oxide zone, a metal oxide zone, a flow path, and a second transition oxide zone, each running along the length of the boundary region over the width. 21 to 20 alloys.

  E22: the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times, or ≧ 24 times the average width Or the boundary region has a length and an average width, wherein the length is ≧ 4 times, ≧ 8 times, ≧ 12 times, ≧ 16 times, ≧ 20 times the average width, or Embodiment 22. The alloy of any of embodiments 12 through 21, wherein ≧ 24 times and the width is substantially uniform along the length.

  E23: the boundary region is about 12 nm to about 1100 nm, about 17 to about 1000 nm, about 20 nm to about 1000 nm, about 20 nm to about 900 nm, about 20 nm to about 800 nm, about 20 nm to about 700 nm, about 17 nm to about 600 nm, about Embodiment 23. The alloy of any of embodiments 12 to 22 having an average width of 20 nm to about 500 nm, about 25 nm to about 400 nm, about 30 nm to about 300 nm, about 35 nm to about 200 nm, or about 40 nm to about 100 nm.

  E24: about 0.1 atomic% to about 10.0 atomic%, about 0.7 to about 8.0 atomic%, about 1.0 to about 7.0 atomic%, about 1. 5 to about 6.0 atomic percent, or about 2.0 to about 5.5 atomic percent of one or more rare earth elements, or about 1.5 to about 2 of one or more rare earth elements. 0.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7 Embodiment 24. The alloy of any of embodiments 1 to 23, containing 0.0, about 7.5, or about 8.0 atomic percent, and levels in between.

  E25: Alloy according to any of embodiments 1 to 24, having at least one main phase and at least one secondary phase.

  E26: The alloy according to any one of Embodiments 1 to 25, which has at least one main phase and a secondary phase, wherein the secondary phase contains one or more rare earth elements.

  E27: The alloy according to any one of embodiments 1 to 26, which has at least one main phase and a secondary phase, wherein the secondary phase contains Ni.

E28: i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni and / or Cr, and B, Al, Si, Sn, other transition metals and rare earth elements Contains one or more elements selected from the group consisting of: i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni and / or Cr, and V , Mn, Sn, Al, Co, Cu, Mo, W, Fe, Si, and one or more elements selected from the group consisting of rare earth elements, for example, here ii) atoms for i) 28. The alloy according to any of embodiments 1-27, wherein the ratio is from about 2.02 to about 2.45. The atomic ratio of ii) to i) is, for example, from about 2.04 to about 2.40, from about 2.10 to about 2.38, from about 2.20 to about 2.36, or from about 2.20 to about 2. .36.

  E29: The alloy according to any of embodiments 1-28, having a C14 or C15 Laves main phase or having a C14 and C15 Laves main phase.

E30: C14 or C15 Laves main phase, or 14 and C15 Laves main phase,
An electrochemically active occlusion secondary phase containing La and Ni> 0.5 wt%, and a catalyst secondary phase containing Ti and Ni, about 0.3 wt% to about 15 wt%,
Embodiment 30. An alloy according to any of embodiments 1 to 29, having

E31: Ti, Zr, V, Ni, Cr and one or more rare earth elements, or Ti, Zr, Ni, Mn, Cr and one or more rare earth elements, or Ti, Cr, V, Ni and one or more rare earth elements A rare earth element, or one or more elements selected from the group consisting of Ti, Zr, V, Ni, Cr, and B, Al, Si, Sn, and other transition metals, or Ti, Zr, V, Ni, Cr, one or more rare earth elements, and one or more elements selected from the group consisting of Mn, Sn, Al, Cu, Mo, W, Fe, Si and Co, or Ti, Zr, V, Ni, Cr One or more rare earth elements and one or more elements selected from the group consisting of Mn and Al, or Ti, Zr, V, Ni, Cr, Mn, Al, Co and one or more rare earth elements, Ma Is Ti, Zr, V, Ni, Cr, Mn, Al, Co and La
The alloy according to any one of embodiments 1 to 30, comprising:

E32: about 0.1 to about 60% Ti, about 0.1 to about 40% Zr, 0 <V <60%, about 1% to about 56% Cr, about 5 to about 22% Mn, About 0.1 to about 57% Ni, 0 to about 3% Sn, about 0.1 to about 10% Al, about 0.1 to about 11% Co, and about one or more rare earth elements 0.1 to about 10%, or Ti about 5 to about 15%, Zr about 18 to about 29%, V about 3.0 to about 13%, Cr about 1 to about 10%, Mn about 6 to about 18%, Ni about 29 to about 41%, Al about 0.1 to about 0.7%, Co about 2 to about 11%, and one or more rare earth elements about 0.7 to about About 8%, or Ti about 11 to about 13%, Zr about 21 to about 23%, V about 9 to about 11%, Cr about 6 to about 9%, Mn about 6 to about 9%, About 31 to about 34% of Ni and about 0.3 to about 0 of Al 6%, from about 2 to about 8% Co, and one or more rare earth elements from about 1 to about 7%
32. An alloy according to any of embodiments 1-31, wherein the percentages are atomic percent and equal to a total of 100%.

  E33: The alloy according to any of embodiments 1-32, wherein the metal oxide is a Ni and / or Cr metal oxide, such as a Ni / Cr metal oxide.

E34: a discharge capacity measured at 50MAg ^-1, and defined as the ratio to the discharge capacity measured in 4MAg ^-1, third time cycle of about 93%, about 94%, about 95%, about 96%, or about High rate discharge performance of 97%, or high rate discharge performance of ≧ 93%, ≧ 94%, ≧ 95%, ≧ 96%, or ≧ 97%, apply alkali pretreatment before half-cell measurement Rather, measured with a liquid cell design on a partially precharged Ni (OH) ₂ positive electrode, where each sample electrode was charged at a constant current density of 50 mAg ⁻¹ for 10 hours and then 50 mAg ^−. discharged at a ^first current density, 12 and 4MAg ^-1 twice pull continues, and / or ≦ 10, ≦ 9, ≦ 8 , ≦ 7, ≦ 6, of ≦ 5 or ≦ 4ohm · g,, or About 2 to about 10, about 3 to about 9, about 3 to about 8, about 3 to about 7, about 3 Exhibit charge transfer resistance (R) at −40 ° C. for a main phase or phases of about 6, about 3 to about 5, or about 3 to about 4 Ω · g, and / or about 5 to about Exhibit a charge transfer resistance (R) at −40 ° C. of about 20, about 7 to about 18, about 9 to about 16, about 10 to about 15, or about 11 to about 15 Ω · g, and / or about 1 to about 5, about 1 to about 4, about 1 to about 3 or about 1.5 to about 2.5 seconds, or ≦ 4, ≦ 3 or ≦ 2 seconds of one main phase or a plurality of main phases −40 34. The alloy of any of embodiments 1-33, which exhibits surface catalyst performance at 0 ° C.

  In the following, further embodiments of the present invention will be described.

  E1: a metal hydride battery, a solid hydrogen storage medium, an alkaline fuel cell, containing a hydrogen storage alloy according to any of the previously mentioned embodiments (embodiments of any of the previous five sets of embodiments), Or metal hydride air battery.

  E2: at least one anode capable of reversibly storing and releasing hydrogen, at least one cathode capable of reversible oxidation, a casing in which the anode and the cathode are disposed, a separator separating the cathode and anode, and A metal hydride battery having an electrolyte in contact with both the anode and the cathode, wherein the anode contains a hydrogen storage alloy as described in any of the previous five sets of embodiments. .

  E3: An alkaline fuel cell having at least one hydrogen electrode, at least one oxygen electrode, and at least one gas diffusion material, wherein the hydrogen electrode is as described in any of the previous five sets of embodiments An alkaline fuel cell containing a hydrogen storage alloy.

  E4: a metal hydride air cell having at least one air permeable cathode, at least one anode, at least one air intake, and an electrolyte in contact with both the anode and the cathode, wherein the anode A metal hydride air battery having a hydrogen storage alloy according to any one of the previous five sets of embodiments.

  E5: Use of an alloy according to any of the previous five sets of embodiments in electrodes in metal hydride cells, fuel cells, or metal hydride air cells.

  E6: Use of an alloy according to any of the previous five sets of embodiments as a hydrogen storage medium.

The result of SEM / EDS is shown about the alloy 0 of Example 1. FIG. The result of SEM / EDS is shown about the alloy 5 of Example 1. FIG. 2 is a dark-field transmission electron micrograph (TEM) of the boundary region of Alloy 0 of Example 1. The oxide interface is dark and the metal region is bright. 4a and 4b are a pair of bright / dark field TEM images of the grain boundary region for Alloy 5 according to the invention of Example 1. In bright field 4a, the oxide interface is white and the metal region is dark. It is a bright-field TEM about the single flow-path boundary area | region of the alloy 5 of Example 1. FIG. The oxide interface is bright and the metal region is dark. 6 is an enlarged TEM for a single flow path boundary region in FIG. 5. FIG. 4 shows Cole-Cole plots for alloys 0-5 of Example 1, showing that two semicircles appear with increasing La content. This shows two distinct phases involved in electrochemistry. FIG. 5 is a circuit diagram used to identify charge transfer resistance (R2 and R4) and double layer capacitance (C1 and C2) for each phase from the Cole-Cole plot. Base alloy 0 only shows one semicircle in the Cole-Cole plot, so only R4 and C2 are calculated for alloy 0. 1 is a schematic diagram showing a narrow boundary region according to the present invention over a bulk metal alloy (metal), having a transition oxide zone (transition amorphous oxide), a metal oxide zone (oxide layer), and an open channel. Nickel hydroxide and nanoporous oxide layers are conventional metal oxides.

Example 1: La-modified Ti-Zr-V-Cr-Mn-Ni-Al-Co alloy An arc using a non-consumable tungsten electrode and water-cooled copper tray under continuous argon flow Melt. Before each run, the titanium sacrificial pieces are passed through several melting / cooling cycles to reduce the residual oxygen concentration in the system. Each 12 g ingot is redissolved and turned over several times to ensure chemical composition uniformity. The chemical composition of each sample is tested using a Varian LIBERTY 100 of an inductively coupled plasma optical emission spectrometer (ICP-OES).

The following alloys were designed and described with the actual composition found by ICP.

  Alloys 2-5 are in accordance with the present invention. Alloys 0-1 are for comparison.

In addition to the C14 and C15 main phases, two additional phases are identified by Philips X'PERT PRO of the X-ray diffractometer (XRD). The abundance of C14, C15, catalytic secondary TiNi phase, and occlusion secondary LaNi phase is shown below (analyzed by XRD, software JADE 9). All alloys are dominated by C14. The abundance is mass% based on the alloy.

  A scanning electron microscope (SEM) JEOL-JSM6320F with energy dispersive spectrometer (EDS) function is used to study the phase distribution and corresponding composition. Although the crystal structure of the TiNi phase contains a considerable amount of Zr, it shows a TiNi (B2) structure according to XRD. Alloys 2-5 according to the present invention have Ti 21.6-27.5 atomic%, Ni 43.5-45.3 atomic%, Zr 13.5-20.6 atomic%, and (Ti + Zr) It has a TiNi phase containing 40.1 to 42.6 atomic%.

The SEM / EDS spectrum for Alloy 0 is shown in FIG. The results are shown below for the indicated position.

The SEM / EDS spectrum for alloy 5 according to the invention is shown in FIG. The results are shown below for the indicated position.

  Transmission electron microscope (TEM) results show that in alloy 0, only random Ni / Ti / Zr oxides are found and somewhat oxidized. In Alloy 5, both random Ni / Cr oxide (large grain boundary gap) and side-by-side Ni / Cr oxide (small grain boundary gap) are found and severely oxidized. TEM analysis is performed on a TECNAI TF-30 Super-Twin TEM with an electron energy loss spectrometer (EELS) from Oxford X-MAX EDS and Gatan QUANTUM SE (963).

FIG. 3 is a dark field TEM for the boundary region of alloy 0. FIG. The oxide composition of alloy 0 is specified by EDS and is as follows.

FIGS. 4a and 4b are a pair of bright / dark field TEM images for the grain boundary region of alloy 5 according to the invention. The nanoscale boundary region separating the metal regions is visible. A transition zone adjacent to the metal region is visible. In the dark field 4b, the metal region is bright and the metal oxide is dark. The energy loss spectrometer shows that the nickel in the metal region and the transition zone is in the zero oxidation state (Ni ⁰ ), and that the nickel in the oxide region is oxidized (Ni ²⁺ / ^{3 +} ) Yes. The oxide composition of the alloy 5 is specified by EDS as follows.

  FIG. 5 is a bright field TEM of Alloy 5 according to the present invention, showing a single channel boundary region between metal regions. The border area is bright and the metal area is dark. The nanoscale boundary region has a transition zone adjacent to the metal region, a Ni / Cr oxide zone, and a parallel flow path. The width of the border region is substantially uniform along the length. The transition zone, flow path and oxide zone run along the length of the boundary region.

  FIG. 6 is an enlarged TEM for the single channel boundary region of FIG.

  The results of the low temperature electrochemical properties are as follows. FIG. 7 shows that in the Cole-Cole plot, two semicircles appear as the La content increases. This shows two distinct phases involved in electrochemistry. The charge transfer resistance (R2 and R4) and double layer capacitance (C1 and C2) of each phase are calculated from the Cole-Cole plot using the circuit diagram shown in FIG. Base alloy 0 only shows one semicircle in the Cole-Cole plot, so only R4 and C2 are calculated for alloy 0.

The values of R and C are calculated from the Cole-Cole plot of AC impedance measurement. AC impedance measurement is performed using a SOLARTRON 1250 frequency characteristic analyzer in a sine wave with an amplitude of 10 mV and a frequency range of 0.1 mHz to 10 kHz. Prior to measurement, the electrode was subjected to one full charge / discharge cycle using a battery test galvanostat of SOLARTRON 1470 at a rate of 0.1 C, charged to 100% SOC, discharged to 80% SOC, and then − Cool to 40 ° C.

  The charge transfer resistance R is represented by Ω · g. The double layer capacity C is expressed in farads / g. R and C values are calculated from Cole-Cole plots of AC impedance measurements performed at -40 ° C.

  It can be seen that La-modified alloys 2-5 have significantly improved charge transfer resistance (R2 + R4) compared to the comparative alloys (lower values are desirable).

A high percentage of discharge performance results are shown below.

The half-cell HRD is defined as the ratio of the discharge capacity measured at 50 mAg ⁻¹ to the discharge capacity measured at 4 mg ⁻¹ . The discharge capacity of the alloy is measured with a liquid cell design against a partially precharged Ni (OH) ₂ positive electrode. No pretreatment with alkali is applied before half-cell measurement. Each sample electrode, 10 hours at a constant current density of 50MAg ^-1, charged, then discharged at a current density of 50MAg ^-1, this two pull continues at 12 and 4mAg ^-1. Capacity and HRD are measured in the third cycle.

The BET (Brunauer Emmet Teller) surface area for Alloy 0 is 1.89 m ² / g. The BET surface area for Alloy 5 is specified as 4.92 m ² / g. The BET surface area is measured by a liquid nitrogen immersion type BET method.

Example 2: Ti-Zr-V-Cr-Mn-Ni-Al-Co alloy modified with Sc, Y, or Misch metal Example 1 is repeated, replacing La with Sc, Y and Misch metal.

Claims (34)

A hydrogen storage alloy having improved low temperature electrochemical properties, comprising a metal oxide having oxygen> 60 atomic%, the alloy comprising:
≦ of 150 ohms · g, the discharge capacity was measured by the charge transfer resistance (R), and / or 50MAg ^-1 at -40 ° C., and defined as the ratio to the discharge capacity measured in 4mAg ^-1, third time cycle ≧ 93% discharge performance at ≧ 93%, measured with liquid cell design on partially precharged Ni (OH) ₂ positive electrode without applying alkali pretreatment before half-cell measurement, where each sample electrode is 10 hours at a constant current density of 50MAg ^-1, charged, then discharged at a current density of 50MAg ^-1, twice at 12 and 4MAg ^-1 pull continues, and / or ≦ 30 seconds Surface catalyst performance at −40 ° C. for one main phase or a plurality of main phases and / or charge transfer resistance (R) at −40 ° C. for one or more main phases ≦ 150 Ω · g
Hydrogen storage alloy showing. A hydrogen storage alloy having a bulk metal region adjacent to a metal oxide boundary region, the boundary region having at least one flow path that enables transport of electrolyte to the bulk metal region, the alloy ,
≦ of 150 ohms · g, the discharge capacity was measured by the charge transfer resistance (R), and / or 50MAg ^-1 at -40 ° C., and defined as the ratio to the discharge capacity measured in 4mAg ^-1, third time cycle ≧ 93% discharge performance at ≧ 93%, measured with liquid cell design on partially precharged Ni (OH) ₂ positive electrode without applying alkali pretreatment before half-cell measurement, where each sample electrode is 10 hours at a constant current density of 50MAg ^-1, charged, then discharged at a current density of 50MAg ^-1, twice at 12 and 4MAg ^-1 pull continues, and / or ≦ 30 seconds Surface catalyst performance at −40 ° C. for one main phase or a plurality of main phases and / or charge transfer resistance (R) at −40 ° C. for one or more main phases ≦ 150 Ω · g
Hydrogen storage alloy showing.   A hydrogen storage alloy having a metal region adjacent to a metal oxide boundary region, the boundary region having a length and an average width, wherein the average width is about 12 nm to about 1100 nm.   A hydrogen storage alloy having at least one bulk metal region and a metal oxide zone containing a metal oxide, the oxide zone having at least one flow path that enables transport of electrolyte to the bulk region Hydrogen storage alloy running in parallel. A hydrogen storage alloy containing a Ni / Cr metal oxide, the metal oxide containing Ni and Cr, each of which is present in a higher atomic percent than the other respective metal, Is
≦ of 150 ohms · g, the discharge capacity was measured by the charge transfer resistance (R), and / or 50MAg ^-1 at -40 ° C., and defined as the ratio to the discharge capacity measured in 4mAg ^-1, third time cycle ≧ 93% discharge performance at ≧ 93%, measured with liquid cell design on partially precharged Ni (OH) ₂ positive electrode without applying alkali pretreatment before half-cell measurement, where each sample electrode is 10 hours at a constant current density of 50MAg ^-1, charged, then discharged at a current density of 50MAg ^-1, twice at 12 and 4MAg ^-1 pull continues, and / or ≦ 30 seconds Surface catalyst performance at −40 ° C. for one main phase or a plurality of main phases and / or charge transfer resistance (R) at −40 ° C. for one or more main phases ≦ 150 Ω · g
Hydrogen storage alloy showing.   6. An alloy according to any one of claims 1 to 5, comprising a metal oxide having from about 60 atom% to about 82 atom% oxygen.   The alloy according to any one of claims 1 to 5, comprising a metal oxide having Cr> 2 atomic%.   The alloy according to any one of claims 1 to 5, comprising a metal oxide having Ni of ≧ 16 atomic%.   The alloy according to any one of claims 1 to 5, comprising a metal oxide having one or more elements selected from the group consisting of B, Al, Si, Sn, and a transition metal.   The alloy according to any one of claims 1 to 5, comprising a metal oxide having one or more elements selected from the group consisting of Al, Ti, V, Mn, Co, and Zr.   The alloy according to any one of claims 1 to 5, comprising a metal oxide existing in a boundary region adjacent to the metal region.   The alloy of claim 11, wherein the boundary region has at least one flow path having a length and an average width and running in a length direction in the boundary region.   The alloy of claim 11, wherein the boundary region has at least one flow path having an average width of about 4 nm to about 40 nm.   The alloy of claim 11, wherein the boundary region has a length and average width and has a transition oxide zone adjacent to the metal region, the transition zone running in a length direction in the boundary region.   The alloy of claim 11, wherein the boundary region has a transition oxide zone adjacent to the metal region, the transition zone having an average width of about 4 nm to about 30 nm.   The alloy of claim 11, wherein the boundary region has a metal oxide zone having a length and an average width and running in a length direction in the boundary region.   The alloy of claim 11, wherein the boundary region has a metal oxide zone having an average width of about 5 nm to about 500 nm.   The boundary region has a first transition oxide zone, a metal oxide zone, and a second transition oxide zone that have a length and an average width, and that run parallel to each other across the width. 11. Alloy according to 11.   12. The boundary region has a first transition oxide zone, a flow path, and a second transition oxide zone, each having a length and an average width, and running parallel to each other across the width. Alloy.   The boundary region has a first transition oxide zone, a metal oxide zone, a flow path, and a second transition oxide zone having a length and an average width, and running parallel to each other over the width. The alloy according to claim 11.   The alloy of claim 11, wherein the boundary region has a length and an average width, wherein the length is ≧ 4 times the average width.   The alloy of claim 11, wherein the boundary region has an average width of about 12 nm to about 1100 nm.   6. An alloy according to any one of claims 1 to 5, comprising from about 0.1 atomic% to about 10.0 atomic% of one or more rare earth elements.   6. An alloy according to any one of the preceding claims, having at least one main phase and at least one secondary phase.   The alloy according to any one of claims 1 to 5, which has at least one main phase and a secondary phase, wherein the secondary phase contains one or more rare earth elements.   The alloy according to any one of claims 1 to 5, which has at least one main phase and a secondary phase, wherein the secondary phase contains Ni. i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) V, Cr, Mn, Ni, Sn, Al, Co, Cu, Mo, W, Fe, Si, and Contains one or more elements selected from the group consisting of rare earth elements, or i) one or more elements selected from the group consisting of Ti, Zr, Nb and Hf, and ii) Ni, Cr, and Contains one or more elements selected from the group consisting of B, Al, Si, Sn, other transition metals and rare earth elements, or i) 1 selected from the group consisting of Ti, Zr, Nb and Hf Ii) Ni, Cr, and one or more elements selected from the group consisting of V, Mn, Sn, Al, Co, Cu, Mo, W, Fe, Si, and rare earth elements To Any one of claims alloy from Motomeko 1 to 5.   28. The alloy of claim 27, wherein the atomic ratio of ii) to i) is about 2.02 to about 2.45.   6. An alloy according to any one of claims 1 to 5, having a C14 or C15 Laves main phase, or having a C14 and C15 Laves main phase. C14 or C15 Laves main phase, or 14 and C15 Laves main phase,
Occluded secondary phase containing La and Ni> 0.5 wt%, and catalyst secondary phase containing Ti and Ni from about 0.3 wt% to about 15 wt%,
The alloy according to any one of claims 1 to 5, wherein: Ti, Zr, V, Ni, Cr and one or more rare earth elements, or Ti, Zr, Ni, Mn, Cr and one or more rare earth elements, or Ti, Cr, V, Ni and one or more rare earth elements Or one or more elements selected from the group consisting of Ti, Zr, V, Ni, Cr and B, Al, Si, Sn, and other transition metals, or Ti, Zr, V, Ni, Cr, One or more rare earth elements and one or more elements selected from the group consisting of Mn, Sn, Al, Cu, Mo, W, Fe, Si and Co, or Ti, Zr, V, Ni, Cr, 1 One or more rare earth elements and one or more elements selected from the group consisting of Mn and Al, or Ti, Zr, V, Ni, Cr, Mn, Al, Co and one or more rare earth elements, or Ti , Zr, V, Ni, Cr, Mn, Al, Co and La
The alloy according to any one of claims 1 to 5, comprising: About 0.1 to about 60% of Ti, about 0.1 to about 40% of Zr, 0 <V <60%, about 1% to about 56% of Cr, about 5 to about 22% of Mn, Ni About 0.1 to about 57%, Sn 0 to about 3%, Al about 0.1 to about 10%, Co about 0.1 to about 11%, and one or more rare earth elements about 0.1%. 1 to about 10%, or Ti about 5 to about 15%, Zr about 18 to about 29%, V about 3.0 to about 13%, Cr about 1 to about 10%, Mn about 6 to About 18%, Ni about 29 to about 41%, Al about 0.1 to about 0.7%, Co about 2 to about 11%, and one or more rare earth elements about 0.7 to about 8 %, Or Ti about 11 to about 13%, Zr about 21 to about 23%, V about 9 to about 11%, Cr about 6 to about 9%, Mn about 6 to about 9%, Ni About 31 to about 34%, Al about 0.3 to about 0.6%, o about 2 to about 8%, and one or more rare earth elements from about 1 to about 7%
6. An alloy according to any one of claims 1 to 5, containing, wherein the percentages are atomic% and total equal to 100%.   The alloy according to any one of claims 1 to 5, comprising a Ni / Cr metal oxide.   A metal hydride battery, a solid hydrogen storage medium, an alkaline fuel cell, or a metal hydride air battery containing the hydrogen storage alloy according to any one of claims 1 to 5.

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