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US4728586A Expired / Lapsed US ⏱️ 0.0 years remaining

Enhanced charge retention electrochemical hydrogen storage alloys and an enhanced charge retention electrochemical cell

Assignee: Chevron Technology Ventures LLC
•
Filing: 1986-12-29
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Granted: 1988-03-01
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Expires: 2006-12-29
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Abstract

Abstract A high charge retention, reversible, multicomponent, multiphase, electrochemical hydrogen storage alloy comprising titanium, vanadium, zirconium, nickel, and chromium. The hydrogen storage alloy is capable of electrochemically charging and discharging hydrogen in alkaline aqueous media. In one preferred exemplification the hydrogen storage alloy comprises (Ti.sub.2-x Zr.sub.x V.sub.4-y Ni.sub.y).sub.1-z Cr.sub.z where 0.0 is less than x is less than 1.5, 0.6 is less than y is less than 3.5, and z is an effective amount less than 0.20. Also disclosed is a rechargeable, electrochemical cell utilizing a negative electrode formed of the alloy.

Inventors

  • 👤 Srini Venkatesan
  • 👤 Benjamin Reichman
  • 👤 Michael A. Fetcenko

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-06 13:45
CPC Classifications
C; C22; C22C; C22C38/00; C22C38/18; C22C38/40; C22C38/50; C01; C01B; C01B3/00; C01B3/0005; C01B3/001; C01B3/0078; C01B3/0018; C01B3/0031; H; H01; H01M; H01M10/00; H01M10/24; H01M10/26; H01M10/34; H01M10/345; H01M4/00; H01M4/02; H01M4/24; H01M4/242; H01M4/36; H01M4/38; H01M4/383; Y; Y02; Y02E; Y02E60/00; Y02E60/10; Y02E60/30; Y02E60/32; Y02P; Y02P70/00; Y02P70/50; Y10; Y10S; Y10S420/00; Y10S420/90

Claims Analysis

Total Claims: 63
Claim 1
Independent Claim 110 words
A reversible, multicomponent, multiphase, electrochemical hydrogen storage alloy capable of electrochemically changing and discharging hydrdogen in an alkaline media, said hydrogen storage alloy having the composition (Ti 2-x Zr x V 4-y Ni y ) z Cr 1-z where 0.0<x<1.5, 0.6<y<3.5, and z is an effective amount less then 0.20, and comprising multicomponent hydrogen storage phases capable of reversibly storing hydrogen, where at least one of the components in the said multicomponent hydrogen storage phase is soluble in the alkaline media, and wherein the said multicomponent, multiphase hydrogen storage alloy further includes chromium as a modifier to inhibit the corrosion of the soluble component into the strongly ionic aqueous media.
Claim 2
Dependent Claim 110 words
A reversible, multicomponent, multiphase, electrochemical hydrogen storage alloy capable of electrochemically changing and discharging hydrdogen in an alkaline media, said hydrogen storage alloy having the composition (Ti 2-x Zr x V 4-y Ni y ) z Cr 1-z where 0.0<x<1.5, 0.6<y<3.5, and z is an effective amount less then 0.20, and comprising multicomponent hydrogen storage phases capable of reversibly storing hydrogen, where at least one of the components in the said multicomponent hydrogen storage phase is soluble in the alkaline media, and wherein the said multicomponent, multiphase hydrogen storage alloy further includes chromium as a modifier to inhibit the corrosion of the soluble component into the strongly ionic aqueous media.
Claim 3
Dependent Claim 17 words
The reversible, multicomponent, multiphase, electrochemical hydrogen storage alloy of claim 1 wherein the soluble compoent is Vanadium.
Claim 4
Dependent Claim 91 words
A reversible, multicomponent, multiphase, electrochemical hydrogen storage alloy comprising titanium, vanadium, zirconium, nickel, and chromium, having the composition (Ti 2-x Zr x V 4-y Ni y ) 1-2 Cr z where 0.0<x<1.5, 0.6<y<3.5, and z is an effective amount less then 0.20; said hydrogen storage alloy being capable of electrochemically charging and discharging hydrogen in alkaline aqueous media, the vanadium in said multicomponent hydrogen storage phase normally being soluble in the alakline, aqueous media, and the chromium acting to inhibit the solubilization of the vanadium into the aqueous alkaline aqueous media.
Claim 5
Dependent Claim 91 words
A reversible, multicomponent, multiphase, electrochemical hydrogen storage alloy comprising titanium, vanadium, zirconium, nickel, and chromium, having the composition (Ti 2-x Zr x V 4-y Ni y ) 1-2 Cr z where 0.0<x<1.5, 0.6<y<3.5, and z is an effective amount less then 0.20; said hydrogen storage alloy being capable of electrochemically charging and discharging hydrogen in alkaline aqueous media, the vanadium in said multicomponent hydrogen storage phase normally being soluble in the alakline, aqueous media, and the chromium acting to inhibit the solubilization of the vanadium into the aqueous alkaline aqueous media.
Claim 6
Dependent Claim 24 words
The reversible, multicomponent, multiphase hydrogen storage alloy of claim 3 having the composition V 33 Ti 13 Zr 14 Ni 33 Cr 7 .
Claim 7
Dependent Claim 24 words
The reversible, multicomponent, multiphase hydrogen storage alloy of claim 3 having the composition V 27 Ti 17 Zr 16 Ni 35 Cr 5 .
Claim 8
Dependent Claim 24 words
The reversible, multicomponent, multiphase hydrogen storage alloy of claim 3 having the composition V 25 Ti 17 Zr 16 Ni 40 Cr 2 .
Claim 9
Dependent Claim 24 words
The reversible, multicomponent, multiphase hydrogen storage alloy of claim 3 having the composition V 23 Ti 17 Zr 16 Ni 40 Cr 4 .
Claim 10
Dependent Claim 24 words
The reversible, multicomponent multiphase hydrogen storage alloy of claim 3 having the composition V 22 Ti 16 Zr 16 Ni 39 Cr 7 .
Claim 11
Dependent Claim 30 words
The reversible, multicomponent, multiphase hydrogen storage alloy of claim 3 further comprising a second modifier chosen from the group consisting of at least one of copper, iron, manganese and cobalt.
Claim 12
Dependent Claim 33 words
The reversible, multicomponent, multiphase hydrogen storage alloy of claim 3 further comprising a hydrogen storage component chosen from the group consisting of at least one of magnesium, calcium, lanthanum, niobium, silicon, and hafnium.
Claim 13
Dependent Claim 105 words
A sealed, rechargeable electrochemical cell comprising: (a) a positive electrode; (b) a negative electrode comprising a body of modified multiphase, multicompoennt, reversible electrochemical hydrogen storage alloy comprising titanium, vanadium, zirconium, nickel, and chromium, having the composition (Ti 2-x Zr x V 4-y Ni y ) 1-2 Cr z where 0.0<x<0.5, 0.6<y<3.5, and z is a positive number less then 0.20; (c) a separator means positioned between the positive and negative electrodes; (d) electrolyte means in contact with the separator means and the positive and negative electrodes; and (e) sealed container means containing the positive and negative electrodes, spacer means, and electrolyte means in operative relationship.
Claim 14
Dependent Claim 105 words
A sealed, rechargeable electrochemical cell comprising: (a) a positive electrode; (b) a negative electrode comprising a body of modified multiphase, multicompoennt, reversible electrochemical hydrogen storage alloy comprising titanium, vanadium, zirconium, nickel, and chromium, having the composition (Ti 2-x Zr x V 4-y Ni y ) 1-2 Cr z where 0.0<x<0.5, 0.6<y<3.5, and z is a positive number less then 0.20; (c) a separator means positioned between the positive and negative electrodes; (d) electrolyte means in contact with the separator means and the positive and negative electrodes; and (e) sealed container means containing the positive and negative electrodes, spacer means, and electrolyte means in operative relationship.
Claim 15
Dependent Claim 13 words
The electrochemical cell of claim 11 wherein the positive electrode comprises nickel hydroxide.
Claim 16
Dependent Claim 12 words
The electrochemical cell of claim 11 wherein the separator is nonwoven nylon.
Claim 17
Dependent Claim 18 words
The electrochemical cell of claim 13 wherein the nonwoven nylon separator has a thickness of about 0.0085 inch.
Claim 18
Dependent Claim 14 words
The electrochemical cell of claim 11 wherein the electrolyte is aqueous alkali metal hydroxide.
Claim 19
Dependent Claim 12 words
The electrochemical cell of claim 15 wherein the electrolyte comprises potassium hydroxide.
Claim 20
Dependent Claim 16 words
The electrochemical cell of claim 16 wherein the electrolyte comprises approximately 30 weight percent potassium hydroxide.
Claim 21
Dependent Claim 13 words
The electrochemical cell of claim 16 wherein the electrolyte further comprises lithium hydroxide.
Claim 22
Dependent Claim 19 words
The electrochemical cell of claim 18 wherein the electrolyte comprises less than 15 grams per liter of lithium hydroxide.
Claim 23
Dependent Claim 24 words
The electrochemical cell of claim 11 wherein the positive electrode comprises nickel hydroxide and the electrolyte comprises nitrate and nitrite ions as an impurity.
Claim 24
Dependent Claim 24 words
The electrochemical cell of claim 20 wherein the concentration of the nitrate ion and nitrite ion is greater than about 200 parts per million.
Claim 25
Dependent Claim 24 words
The electrochemical cell of claim 21 wherein the concentration of the nitrate ion and nitrite ion is at least about 500 parts per million.
Claim 26
Dependent Claim 21 words
The electrochemical cell of claim 11 having an electrolyte volume high enough to permit fast gas recombination in a sealed cell.
Claim 27
Dependent Claim 13 words
The electrochemical cell of claim 11 having excess electrolyte volume for vented operation.
Claim 28
Dependent Claim 10 words
The electrochemical cell of claim 11 having a wound configuration.
Claim 29
Dependent Claim 43 words
The electrochemical cell of claim 11 wherein said negative electrode comprises a modified, multiphase, multicomponent, reversible electrochemical hydrogen storage alloy comprising titanium, vanadium, zirconium, nickel, and chromium, said hydrogen storage alloy being capable of electrochemically charging and discharging hydrogen in aqueous alkaline media.
Claim 30
Dependent Claim 28 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material has the composition V 33 Ti 13 Zr 14 Ni 33 Cr 7 .
Claim 31
Dependent Claim 28 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material has the composition V 27 Ti 17 Zr 16 Ni 35 Cr 5 .
Claim 32
Dependent Claim 28 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material has the composition V 25 Ti 17 Zr 16 Ni 40 Cr 2 .
Claim 33
Dependent Claim 28 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material has the composition V 23 Ti 17 Zr 16 Ni 40 Cr 4 .
Claim 34
Dependent Claim 28 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material has the composition V 22 Ti 16 Zr 16 Ni 39 Cr 7 .
Claim 35
Dependent Claim 34 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material further comprises a second modifier chosen from the group consisting of at least one of copper, iron, manganese, and cobalt.
Claim 36
Dependent Claim 37 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material further comprises a hydrogen storage component chosen from the group consisting of at least one of magnesium, calcium, lanthanum, niobium, silicon, and hafnium.
Claim 37
Dependent Claim 56 words
The electrochemical cell of claim 11 wherein the modified, multiphase, multicomponent, reversible electrochemical hydrogen storage alloy comprises hydrogen storage alloy multicomponent phases capable of reversibly storing hydrogen, wherein at least the vanadium is soluble in the electrolyte, and where in the chromium inhibits the loss of the soluble vanadium component into the strongly ionic, aqueous media.
Claim 38
Dependent Claim 15 words
The electrochemical cell of claim 34 having a reduced level of vanadium in the electrolyte.
Claim 39
Dependent Claim 28 words
The electrochemical cell of claim 35 having a reduced level of vanadium in the electrolyte whereby to substantially reduce the effects of vanadium redox shuttles self discharge mechanism.
Claim 40
Dependent Claim 32 words
The electrochemical cell of claim 35 having a reduced level of vanadium in the electrolyte whereby to substantially reduce the effects of vanadium corrosion on the chemical stability of the positive electrode.
Claim 41
Dependent Claim 13 words
The electrochemical cell of claim 11 having a reduced rate of self discharge.
Claim 42
Dependent Claim 24 words
The electrochemical cell of claim 11 wherein the surface of the negative electrode is substantially resistant to the effects of redox couple reduction mechanisms.
Claim 43
Dependent Claim 30 words
The electrochemical cell of claim 39 wherein the redox couple is one or more of: (a) NO 3 - NO 2 - , and (b) V +5 V +4 .
Claim 44
Dependent Claim 41 words
The electrochemical cell of claim 11 wherein the self discharge reaction is one of: (a) O 2 +2e - +H 2 O HO 2 - +OH - , and (b) O 2 +4e - +2H 2 O 4 OH - .
Claim 45
Dependent Claim 36 words
The electrochemical cell of claim 11 wherein the surface of the negative electrode of modified hydrogen storage alloy active material has less active surface than an unmodified electrode and is less active to self discharge reactions.
Claim 46
Dependent Claim 25 words
The electrochemical cell of claim 42 wherein the modifier reduces the active surface area of the negative electrode of modified hydrogen storage alloy active material.
Claim 47
Dependent Claim 36 words
The electrochemical cell of claim 11 wherein the surface of the negative electrode of modified hydrogen storage alloy active material has less surface roughness than an unmodified electrode and is less active to self discharge reactions.
Claim 48
Dependent Claim 55 words
The electrochemical cell of claim 11 wherein the modified hydrogen storage alloy active material is less susceptible to corrosion in the electrolyte than unmodified hydrogen storage alloy active material, and the surface of the negative electrode of modified hydrogen storage alloy active material has less surface roughness than an unmodified electrode after repeated charge-discharge cycles.
Claim 49
Dependent Claim 31 words
The electrochemical cell of claim 11 wherein the surface of the negative electrode of modified hydrogen storage alloy active material is less catalytic to self discharge reactions than an unmodified electrode.
Claim 50
Dependent Claim 45 words
The electrochemical cell of claim 11 wherein the surface of the negative electrode of modified hydrogen storage alloy active material has a lower surface content of high conductivity material than an unmodified electrode and is less catalytic to self discharge reactions than an unmodified electrode.
Claim 51
Dependent Claim 30 words
The electrochemical cell of claim 47 wherein the high conductivity material is nickel, and the modified hydrogen storage alloy inhibits the increase of nickel in the surface of the electrode.
Claim 52
Dependent Claim 80 words
A reversible, negative, electrochemical hydrogen storage electrode adapted for use in a sealed, rechargeable hydrogen storage battery, said electrode comprising a modified, multiphase, multicomponent, reversible electrochemical hydrogen storage alloy formed of titanium, vanadium, zirconium, nickel, and chromium, having the composition (Ti 2-x Zr x V 4-y Ni y ) 1-z Cr z where 0.0<x<1.5, 0.6<y<3.5, and z is an effective amount less then 0.20, said hydrogen storage alloy being capable of electrochemically charging and discharging hydrogen in aqueous alkaline media.
Claim 53
Dependent Claim 80 words
A reversible, negative, electrochemical hydrogen storage electrode adapted for use in a sealed, rechargeable hydrogen storage battery, said electrode comprising a modified, multiphase, multicomponent, reversible electrochemical hydrogen storage alloy formed of titanium, vanadium, zirconium, nickel, and chromium, having the composition (Ti 2-x Zr x V 4-y Ni y ) 1-z Cr z where 0.0<x<1.5, 0.6<y<3.5, and z is an effective amount less then 0.20, said hydrogen storage alloy being capable of electrochemically charging and discharging hydrogen in aqueous alkaline media.
Claim 54
Dependent Claim 32 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified hydrogen storage alloy active material has the composition V 33 Ti 13 Zr 14 Ni 33 Cr 7 .
Claim 55
Dependent Claim 32 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified hydrogen storage alloy active material has the composition V 27 Ti 17 Zr 16 Ni 35 Cr 5 .
Claim 56
Dependent Claim 32 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified hydrogen storage alloy adtive material has the composition V 25 Ti 17 Zr 16 Ni 40 Cr 2 .
Claim 57
Dependent Claim 32 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified hydrogen storage alloy active material has the composition V 23 Ti 17 Zr 16 Ni 40 Cr 4 .
Claim 58
Dependent Claim 32 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified hydrogen storage alloy active material has the composition V 22 Ti 16 Zr 16 Ni 39 Cr 7 .
Claim 59
Dependent Claim 38 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified hydrogen storage alloy active material further comprises a second modifier chosen from the group consisting of at least one of copper, iron, manganese, and cobalt.
Claim 60
Dependent Claim 41 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified hydrogen storage alloy active material further comprises a hydrogen storage component chosen from the group consisting of at least one of magnesium, calcium, lanthanum, niobium, silicon, and hafnium.
Claim 61
Dependent Claim 66 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 49 wherein the modified, multiphase, multicomponent, reversible electrochemical hydrogen storage alloy comprises hydrogen storage alloy multicomponent phases capable of reversibly storing hydrogen, wherein at least one of the components of the multicomponent hydrogen storage phase is soluble in the electrolyte, and wherein the modifier inhibits the loss of the soluble component into the strongly ionic, aqueous media.
Claim 62
Dependent Claim 26 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 57 wherein the soluble component is chosen from the group consisting of vanadium, niobium, aluminum, and tantalum.
Claim 63
Dependent Claim 16 words
The reversible, negative, electrochemical hydrogen storage electrode of claim 58 wherein the soluble component is vanadium.

References Cited (Backward Citations)

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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1991-03-01 1991-08-31 1992-03-01 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1995-03-01 1995-08-31 1996-03-01 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1999-03-01 1999-08-31 2000-03-01 $7700.00 Window Closed / Lapsed

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