CN1037280C - Method for storage of hydrogen and chemical constitution of hydride materials as electrode - Google Patents
Method for storage of hydrogen and chemical constitution of hydride materials as electrode Download PDFInfo
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Abstract
The present invention relates to a hydrogen storage material of the following four families, an electrochemical application thereof, the chemical composition of a specific hydride electrode material and a simple and effective method for selecting a hydride electrode. A first family comprises Tia, Zrb, Nic, Crd and Mx; a second family comprises Tia, Crb, Zrc, Nid and V3-a-b-c-d, a third family comprises Tia, Zrb, Nic and V3-a-b-c, and a fourth family comprises Tia, Mnb, Vc and Nid, wherein the suffixes of a, b, c and d and the meaning of x are disclosed in the specification.
Description
The present invention relates to select and make the method for the multicomponent alloy material that hydrogen storage electrode material uses and this material that is obtained.
More particularly, the present invention is relevant a kind of hydrogen-storage material and their electrochemical applications, more specifically, the present invention is that multiple store battery is used, the chemical ingredients and the composition of the relevant a kind of special hydride electrode material of system, the present invention also further provides simply a kind of but effective means very, in order to select useful hydride electrode material.
The hydrogen at room temperature steel cylinder of common available heaviness stores at the high pressure gas state, or stores with the cryogenic liquid state.The steel cylinder storing method has the problem on the safety because of the high pressure relation, and its gas-storing capacity seldom, is lower than 1% weight percent.Liquid storage rule relates to very low temperature, needs the cryogenic liquefaction process through difficulty, wastes many energy.And owing to can't guarantee thermal isolation, liquid hydrogen meeting nature gasifies and escapes, and therefore can't store for a long time.
A kind of more feasible storing method is with alloy material storing hydrogen hydrogen adsorption to be become this process of solid-state hydride not only simply but also safety.A kind of task of reaching of available following two reversible chemical reactions.
In last two formulas, M is solid-state hydrogen storage material.MH is its solid-state hydride.e
-Be electronics, OH
-Be hydroxide ion.Equation (1) is a kind of chemical reaction of solids-gases, has the function of heat energy storage.Equation (2) then is a kind of electrochemical reaction, can do electric power storage and use.In these two equations, fill hydrogen or when charging, hydrogen can be stored, and when putting hydrogen or discharge in its reversed reaction, hydrogen can be disengaged.
Be not any metal, alloy can storage of hydrogen.But the material that is not any mat equation (1) storage of hydrogen on the other hand goes for equation (2) method storage of hydrogen and electric power storage.For example United States Patent (USP) the 4th, 160, No. 014 disclosed material: though the applicable equation of Ti-Zr-Mn-Cr-V alloy (1) storage hydrogen can not be applicable to that electrochemical action is made for battery and uses.Another example is the material that is published in the clear 55-91950 of Japanese Patent number: (V1-xTix) 3Ni1-y My, M=Cr, Mn, Fe in the formula, and 0.05≤x≤0.8,0≤y≤0.2.Its chemical constitution atomic ratio of these materials limitations is: Ni+M=25%, and the atomic percent of M needs below 5% Ti+V=75%.This restriction causes causing in the hydride of these hydrogen storage materials, and some is too stable so that can not releasing hydrogen gas at normal temperature or low temperature, and price is too high or have by the worry of solution etch, so these materials can not be applicable to electrochemical applications.
In many disclosed Recent Progress in Hydrogen Storage Materials, only there is a little once to be done the test of electrochemical applications.These examples comprise United States Patent (USP) the 3rd, 824,131,4,112,199 and 4,551, and No. 400.Wherein, the present inventor is the 4th, 551, relevant hydrogen storage and hydride electrode material part contriver in No. 400 patents.Disclosed material is much better than cited person in above-mentioned other patents at aspect of performance in this patent.The present inventor invents and is published in United States Patent (USP) the 4th, 551, and No. 400 material comprises following three groups:
The Ti V2-x Nix of family (a), 0.2≤x in the formula≤1.0
The Yi2-x Zrx V4-y Niy of family (b), 0≤x in the formula≤1.50,0.6≤y≤3.50
This formula can be rewritten as follows:
Ti1-x ' Zrx ' V2-y ' Niy ', 0≤x ' in the formula≤0.75,0.3≤y '≤1.75
The Ti1-x Crx V2-y Niy of family (c), 0.2≤x in the formula≤0.75,0.3≤y≤1.0
Though these material properties are better than other previous inventions, it all is by TiV on the one hand
2The type alloy develops and the next visual TiV that is as the criterion
2The type alloy, and their chemical ingredients atomic percent has following restriction on the other hand:
Family (a): Ti=33.3%, V+Ni=66.7%
Family (b): Ti+Zr=33.3%, V+Ni=66.7%
Family (c): Ti+Cr=33.3%, V+Ni=66.7%
Above-mentioned all restrictions cause these materials to have one or multinomial weakness, comprise expensive, short life, low electricity capacity or low generating rate.
Developing good Recent Progress in Hydrogen Storage Materials and being suitable for electrochemical applications is not a simple task that is easy to.Up to the present, do not have one piece of scientific paper or patent documentation once proposed to deliver one simple and easy and effective means goes to guide relevant research in this respect.So for a long time, people have to continue to use trial and error and do test always.The result has wasted countless human and material resources, financial resources and the time, and its progress is extremely limited.
A kind of good Recent Progress in Hydrogen Storage Materials can supply hydride electrode application person, need possess following character at least:
. the storage of hydrogen amount is good.
. good catalyzer is oxidized easily in electrode for hydrogen.
. in basic solution, the resistance to corrosion height.
. the move about rate height of hydrogen in this material structure.
. the scope of its hydrogen equilibrium pressure is fit to.
. cost of manufacture can not be too expensive.
Purpose of the present invention is exactly the multicomponent alloy material of propose selecting and making the method for the multicomponent alloy material that hydrogen storage electrode material with above-mentioned performance uses and provide the hydrogen storage electrode material made like this to use.
In order to be fit to above-mentioned condition, the present invention provides a simple and easy method according to thermodynamics, kinetics and electrochemical principle, in order to choose the good preservation hydrogen material that chemistry uses of can powering again.Chemical constitution of the hydride electrode material that the also open simultaneously novelty of the present invention is good and preparation method thereof.
Select and make the method for many metal alloy compositions that hydrogen-storage electrode uses to comprise the following steps: according to the present invention
(1) select one group to comprise 5 kinds or above quantitative elements A, B, C at least ... make it to become and consist of AaBbCc ... alloy, wherein, elements A, B, C ... system is by selecting in the Mg of element group, Ti, V, Cr, Mn, Fe, Co, Ni, Al, Y, Zr, Nb, Pd, Mo, Ca and the rare earth metal;
(2) in the above-mentioned quantitative element, the content of Ni is greater than 5%, but is less than 85% atomic percent;
(3) this quantitatively forms many metal alloys AaBbCc ... hydride generate heat between-3.5 to-9.0Kcal/mole H, wherein hydride generates hot Hh and can be calculated by following formula:
Hh＝[aHh(A)+bHh(B)+cHh(C)+…]/(a+b+c+…)+k
Hh in the following formula (A), Hh (B), Hh (C) ... be respectively elements A, B, C ... Deng hydride generate heat (unit: Kcal/mole H), its value is:
Hh(Mg)＝-9.0，Hh(Ti)＝-15.0，Hh(V)＝-7.0，
Hh(Cr)＝-1.81，Hh(Mn)＝-2.0，Hh(Fe)＝4.0，
Hh(Co)＝4.0，Hh(Ni)＝2.0，Hh(Al)＝-1.38，
Hh(Y)＝-27.0，Hh(Zr)＝-1.95，Hh(Nb)＝-9.0，
Hh(Pd)＝-4.0，Hh(Mo)=-1.0，Hh(Ca)＝-21.0，
Hh (rare earth element)=-25.0;
And k is a constant in the following formula, its value be 0.5 ,-0.2 and-1.5Kcal/mole H, correspond respectively to a+b+c ...=2,3 or 6;
(4) with above-mentioned atomic ratio a, b, c ... metallic element group A, B, C ... according to arc process, heating and melting and make alloy A aBbCc under protection of inert gas such as inductive method or electric slurry method ...
Preferably, can adopt the inventive method to select a kind of many metal alloy compositions, wherein atomic percent nickel is between 15% to 45%, and this quantitatively forms many metal alloy compositions AaBbCc ... the generation heat of hydride between-3.5 to-9.0Kcal/mole H.
Method proposed by the invention is easy, easy to operate, and the hydrogen storage material of making has favourable character above-mentioned, does not have the shortcoming of the above current material simultaneously again.The hydrogen storage material of making according to the present invention chemistry of can powering is used.More particularly, can pass through gaseous state absorption hydrogen method and electrochemical process storage of hydrogen according to the hydrogen storage material that is suitable for hydride electrode that the present invention obtained.
The present invention discloses following four group family materials and uses for hydrogen storage and hydride electrode:
First family: Tia Zrb Nic Crb Mx,
Wherein M=Al, Si, Mn, Fe, Co, Cu, Nb, Ag, Pd and rare earth metal, and
0.1≤a≤1.4，0.1≤b≤1.3，0.25≤c≤1.95，0.1≤d≤1.4，a+b+c+d＝3，0≤x≤0.2，
Second family: Tia Crb Zrc Nid V3-a-b-c-d Mx,
Wherein M=Al, Si, V, Mn, Fe, Co, Cu, Nb, Ag, Pd and rare earth metal, and
0.1≤a≤1.3，0.1≤b≤1.2，0.1≤c≤1.3，0.2≤d≤1.95，0.4≤a+b+c+d≤2.9，0≤x≤0.2，
Three races: Tia Zrb Nic V3-a-b-c Mx,
Wherein M=Al, Si, Cr, Mn, Fe, Co, Cu, Nb, Ag, Pd and rare earth metal, and
0.1≤a≤1.3，0.1≤b≤1.3，0.25≤c≤1.95，0≤x≤0.2，0.6≤a+b+c≤2.9，
The 4th family: Tia Mnb Vc Nid Mx, wherein
M=Al, Si, Cr, Fe, Co, Cu, Nb, Zr, Ag, Pd and rare earth metal, and
0.1≤a≤1.6，0.1≤b≤1.6，0.1≤c≤1.7，0.2≤d≤2.0，a+b+c+d＝3，0≤x≤0.2。
The disclosed material of foregoing invention can be used arc process, and heating and melting under protection of inert gas such as inductive method or electric slurry method is made it.The method of these material storage of hydrogen also is illustrated in the present invention.
The present invention also discloses a kind of method, stores and electrochemical applications in order to choose a kind of material hydrogen supply gas, and this method can illustrate with two steps:
This materials A of step 1. aBbCc ... at least contain the nickel metal of atomic percent between 5% to 85%.Atomic percent is preferably between 15% to 45%.
This materials A of step 2. aBbCc ... in, choose suitable atomicity than a, b, c ... make calculated value that the hydride of this alloy generates heat between-3.5 to-9.0Kcal/mole H; Preferably between-4.5 to-8.5Kcal/mole H, hydride generates heat (Hh) can calculate it according to following formula.
Hh＝[aHh(A)+bHh(B)+cHh(c)+…]/(a+b+c+…)+k-----------(3)
Metal element A, B, C in the formula (3) ... system is by selecting in the Mg of element group, Ti, V, Cr, Mn, Fe, Co, Ni, Al, Y, Zr, Nb, Pd, Mo, Ca, Hf and the rare earth metal;
Hh (A), Hh (B), Hh (c) ... be respectively metal A, B, C in system ... Deng the generation heat of hydride, be unit with Kcai/moleH.K is a constant again, its value and this metal alloy Aa, Bb, Cc ... generation heat itself, and each composition metal A, B, C ... mixture heat in hydride has substantial connection.In calculating, can make the k value equal 0.5 ,-0.2 respectively and reach-1.5 corresponding a+b+c+ ... equal 2,3 or 6.In practicality, the k value can be ignored it for zero.The hydride of metallic element generates heat and can be listed below by finding some representative persons in the scientific literature:
Mg：-9.0；Ti：-15.0；V：-7.0；Cr：-1.81；Mn：-2.0
Fe：4.0；Co：4.0；Ni：2.0；Al：-1.38；Y：-2.70
Zr：-1.95；Nb：-9.0；Pd：-4.0；Mo：-1.0；Ca：-21.0
Rare earth element :-25.0, be unit all with Kcal/mole H.
Four group family hydrogen storage material--the material of-reversibility absorption/releasing hydrogen gas that the present invention disclosed, the chemistry of particularly can powering is used the material as battery terminal negative.
The first family material mainly is the alloy of titanium (Ti), nickel (Ni), zirconium (Zr), chromium four kinds of elements such as (Cr), in addition, this gang's material still can add other a little elements, and for example the chemical constitution of this group family material alloys such as aluminium (Al), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), niobium (Nb), silver (Ag), silicon (Si), palladium (Pd) and rare earth element can be expressed from the next:
Tia?Zrb?Nic?Crd?Mx
Wherein M=Al, Si, V, Mn, Fe, Co, Cu, Nb, Ag, Pb and rare earth metal, and
0.1≤a≤1.4，0.1≤b≤1.3，0.25≤c≤1.95，0.1≤d≤1.4，a+b+c+d＝3，0≤x≤0.2。
0.25≤a≤1.0,0.2≤b≤1.0,0.8≤c≤1.6,0.3≤d≤1.0 preferably.
The second family material mainly is the alloy of titanium (Ti), nickel (Ni), zirconium (Zr), chromium (Cr), vanadium five kinds of elements such as (V), in addition, this gang's material still can add other a little elements, for example aluminium (Al), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), niobium (Nb), silicon (Si), palladium (Pd), silver (Ag) rare earth element etc.The chemical constitution of this group of family's material alloys can be expressed from the next:
Tia?Crb?Zrc?Nid?V3-a-b-c-d?Mx
Wherein M=Al, Si, Mn, Fe, Co, Cu, Nb, Ag, Pb and rare earth metal, and
0.1≤a≤1.3，0.1≤b≤1.2，0.1≤c≤1.3，0.2≤d≤1.95，0.4≤a+b+c+d≤2.9，0≤x≤0.2。
0.15≤a≤1.0,0.15≤b≤1.0,0.2≤c≤1.0,0.4≤d≤1.7 and 1.5≤a+b+c+d≤2.3 preferably.
Three races's material mainly is the alloy of titanium (Ti), nickel (Ni), zirconium (Zr), vanadium four kinds of elements such as (V), still other a little elements be can add in addition, aluminium (Al), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), niobium (Nb), silicon (Si), palladium (Pd), silver (Ag) and rare earth element etc. comprised.The chemical constitution of this group of family's material alloys can be by following expression:
Tia?Zrb?Nic?V3-a-b-c?Mx
Wherein M=Al, Si, Mn, Fe, Co, Nb, Ag, Pd and rare earth element etc.;
0.1≤a≤1.3，0.1≤b≤1.3，0.25≤c≤1.95，0.6≤a+b+c≤2.9，0≤x≤0.2。
0.15≤a≤0.8,0.2≤b≤0.8,0.5≤c≤1.5,1.5≤a+b+c≤2.5 preferably.
And for example fruit is during x=0, a+b ≠ 1, and 0.24≤b≤1.3.
The 4th family's material mainly is the alloy of titanium (Ti), nickel (Ni), manganese (Mn), vanadium four kinds of elements such as (V) among the present invention.Still other a little elements be can add in addition, aluminium (Al), zirconium (Zr), iron (Fe), cobalt (Co), copper (Cu), niobium (Nb), silicon (Si), palladium (Pd), silver (Ag) and rare earth element etc. comprised.The chemical constitution of this group of family's material alloys can by following expression it.
Tia?Mnb?Vc?Nid?Mx
Wherein M=Al, Si, Fe, Cr, Co, Zr, Nb, Ag, Pd and rare earth element etc.
0.1≤a≤1.6,0.1≤b≤1.6,0.1≤c≤1.7,0.2≤d≤2.00 again, a+b+c+d=3,0≤x≤0.2.
0.5≤a≤1.3,0.3≤b≤1.0,0.6≤c≤1.5 and 1.4≤a+b+c≤2.7 preferably.
The present invention and announces a method except that disclosing above-mentioned storage hydrogen and hydride electrode material, in order to choose the researchdevelopment chemical novel hydrogen storage material of powering.Basically, for example the positive and negative electrode etc. of brine electrolysis or fuel cell is very inequality at the chemical reaction mechanism of hydride electrode and general so-called catalysis electrode.Be made for the hydride electrode that battery is used, not only have electrochemical katalysis, itself also will undertake the effect of absorption or releasing hydrogen gas.Some investigators once used the attached outstanding principle in surface to want to strengthen the electrochemical catalysis ability of some hydride, and still, this method only can reach the minimum function of degree.
In addition, the attached work in this kind surface repetitiousness volume harmomegathus that is easy to produce because of discharging and recharging at hydride electrode is damaged.So want to promote the function of hydride electrode, essential method is exactly will be from the leadoff of hydride material own.Make hydrogen storage material itself that hydrogen storage ability not only be arranged, and electrochemical catalysis is arranged.But in the countless alloys that may make, how does leadoff go to select research for we? the invention provides a method is described as follows: according to the present invention, one by elements A, B, C, Deng the candidate's alloy A aBbCc that is formed ... should contain nickel atoms metal per-cent more than 5% but, make this alloy that suitable discharge capability and hydrogen-storage amount be arranged below 85%.Generally speaking, the amount of nickel is preferably between 15% and 45%.
Except the content restriction of above-mentioned relevant nickel metal, according to the present invention, this candidate's alloy need meet that aforementioned hydrogen balance of touching upon is pressed and hydrogen in the condition of the rate of moving about of metal inside.For this reason, the present invention derives a criterion, this promptly this alloy need have its hydride and generate the theory of heat value, Hh ,-3.5 and-9.0Kcal/mole H between, preferably between-4.5 and-8.5Kcal/mole H between.This candidate's alloy A aBbCc ... hydride generate hot Hh and can calculate it by following formula:
Wherein Hf is AaBbCc ... formation heat, H is AH, BH, CH ... mixture heat, be to generate heat, i.e. Hh (A) with respect to each hydrogenation of Hh (i), Hh (B), Hh (C) ... unit is Kcal/moleH, a+b+c+ again ...=n can know from above-mentioned thermal cycling and to learn alloy A aBbCc ... hydrogenation generates hot Hh:
Hh＝[aHh(A)+bHh(B)+cHh(C)+…]/(a+b+c+…)-Hf/(a+b+c…)+H
m
When metal hydride mixed, can be considered with hydrogen atom was the mixing mutually of each metal of common media.The process of metal mixed was similar with the common media of fluorion when this kind situation was mixed with metal fluoride.Infer from the material of fluorochemical, when two kinds or several metal hydride phase mixing effect produce a multielement metal hydride, its generate heat should between-2 and-5Kcal/mole H between.Accurate this, can make H
mEqual-2.5kcal/mole H.On the other hand, it generates hot Hf stabile metal alloy, normally-60 ± 3.0 Kcal/mole Alloy.H and Hf value are merged, then can get aforesaid equation (3).In other words, candidate's alloy A aBbCc ... the generation heat of hydride just can calculate it easily.
Discuss thus, previous two steps describing earlier of the present invention can provide an easy quantivative approach so that choose a kind of many metal alloy compositions, are made for the storage of hydrogen and the application of electrochemical hydride electrode.
According to this method then among the present invention the hydride of four family's material alloys generate heat, if omit a little influence of M, can calculate it by following all formulas.
First family Tia Zrb Nic Crd Mx
ΔHh＝-5.0a-6.5b+0.67c-0.67d?Kcal/moleH------------(4)
A+b+c+d=3 wherein
Second family Tia Crb Zrc Nid V3-a-b-d Mx
ΔHh＝-2.65a+1.66b-4.14c+2.98d-7.00?Kcal/moleH-----(5)
The Tia Zrb Nic V3-a-b-c Mx of three races
ΔHh＝-2.65a-4.14b+2.98c-7.00?Kcal/moleH-----------(6)
The 4th Tia Mnb Vc Nid Mx of family
ΔHh＝(-15a-2b+2c-7d)/(a+b+c+…)Kcal/moleH---------(7)
As previously mentioned, be suitable for the hydrogen storage material of hydride electrode, its hydride generates heat should be between-3.5 to-9.0Kcal/mole H, preferably-4.5 between-8.5Kcal/mole the H.
Material alloys of the present invention can heat high-temperature fusion with arc process, inductive method and electric slurry method etc. and make it under protection of inert gas.Slightly high temperature reaches the raising that repeatedly repetitiousness fusion helps the uniformity coefficient of alloy composition.Basic metal of a little or alkaline-earth metal can add as oxygen scavenger in addition.
Hydrogen storage material of the present invention can be used gaseous state absorption hydrogen method and electrochemical process storage of hydrogen.In the gaseous state method, the vacuum available system vacuumizes earlier, then with 3 * 10
5Pa to 15 * 10
5Hydrogen and the alloy material effect of Pa (3 to 15 normal atmosphere).Low-grade fever, 100 to 200 ℃ reach the raising that higher hydrogen pressure will help speed of reaction, and accelerated material adsorbs hydrogen and produces hydride.In addition, alloy material helps speed of reaction too if be crushed to fritter or powder earlier.After material absorption hydrogen generated hydride, available heating or degassing method were emitted hydrogen.After for several times inhaling hydrogen/hydrogen discharge reaction, material can be activated, and can be applied to storage of hydrogen or purifying hydrogen at any time and use.
Electrochemistry storage of hydrogen method is exactly that electrochemical applications is in electric power storage in the practicality.In this method, the electrode based on the alloy material that the present invention was announced is produced earlier.Generally speaking, its process is earlier with material grind into powder of the present invention, is pressed into the nickel wire net at normal temperatures or scribbles on the woven wire of nickel dam and become a rectangular sheet electrode.Can add nickel powder, aluminium powder, copper powder or other sticking work agent in case of necessity.Thereafter under the protection gas-bearing formation with 600 ℃ to 1100 ℃ of high temperature sintering in addition, with the structure of intensifier electrode.Last electrode just can be used for storage of hydrogen again through charging (suction hydrogen) for several times and discharge (putting hydrogen) process, or for example anodal merging of nickel made store battery with positive pole.
One, the first group of its chemical constitution of family's material of example by the following formula table it:
Tia?Zrb?Nic?Crd?Mx
Wherein M=Al, Si, V, Mn, Fe, Co, Cu, Nb, Ag, Pd and rare earth metal, and
0.1≤a≤1.4，0.1≤b≤1.3，0.25≤c≤1.95，0.1≤d≤1.4，a+b+c+d＝3，0≤x≤0.2。
In Table 1, list some alloys with this family chemical constitution.Form relevant elemental metalpowder or fritter after weighing according to it; Mix, and be pressed into bulk.Place Reaktionsofen then, under protection of inert gas, with arc process or inductive method heating and melting and make alloy.After the cooling crushing; The alloy sample of one small pieces about about 100 to 300mg heavily can be used for doing electrochemical test.These small pieces at first are positioned in the nickel screen bag, place the KOH basic solution of 4M solubility again, are to be an electrode, regard another utmost point with the nickel utmost point or platinum wire during experiment.After several times discharge and recharge, the electricity capacity of alloy sample can be measured it.Common available 100ma/g strength of current charging and discharge.During discharge system put to voltage for-0.7V with respect to the Hg/HgO electrode till.Table one is listed the electricity capacity of some family's materials.This family material has high electricity capacity, long lifetime and good generating rate.And for example table 1 is listed, hydride that this family drew materials generate heat system between-4.5 and-8.5Kcal/mole H between, meet the criterion that the present invention states.
Two, the second groups of its chemical constitutions of family's material of example by the following formula table it:
Tia?Crb?Zrc?Nid?V3-a-b-c-d?Mx
Wherein M=Al, Si, Mn, Fe, Co, Cu, Nb, Ag, Pd and rare earth metal, and
0.1≤a≤1.3，0.1≤b≤1.2，0.1≤c≤1.3，0.2≤d≤1.95，0.4≤a+b+c+d≤2.9，0≤x≤0.2。
Table one is listed the alloy material of some second group of families, and these alloys mix after weighing according to its element atomic ratio.And make alloy, and electrochemical test in addition according to the method in the similar example one.Its electricity capacity is the result also list on table one.The hydride of these alloys generates heat really in the listed scope of the present invention again, promptly-4.5 and-8.5Kcal/mole H between.This family alloy material has good electricity capacity, discharging rate and permanent life-span.
Three, the three groups of its chemical constitutions of family's material of example by the following formula table it:
Tia?Zrb?Nic?V3-a-b-c?Mx
Wherein M=Al, Si, Cr, Mn, Fe, Co, Cu, Nb, Ag, Pd and rare earth element etc.;
0.1≤a≤1.3，0.1≤b≤1.3，0.25≤c≤1.95，0.6≤a+b+c≤2.9，0≤x≤0.2。
(if x=0, a+b ≠ 1).
Table one is listed the alloy material of some the 3rd group of families, and similar described in the method for making of these alloys and testing sequence and the example one, its test-results is also listed on the table one.The hydride of these alloys generates heat really in the listed scope of the present invention again, promptly-4.5 and-8.5Kcal/mole H between.
Example four, the four group family its chemical constitutions of material by the following formula table it:
Tia?Mnb?Vc?Nid?Mx
Wherein M=Al, Si, Cr, Fe, Co, Cu, Nb, Zr, Ag, Pd and rare earth element etc., again
0.1≤a≤1.6，0.1≤b≤1.6，0.1≤c≤1.7，0.2≤d≤2.00，a+b+c+d＝3，0≤x≤0.2。
The material of chemical constitution in this family scope made and electrochemistry experiment according to described in the similar example one.Some experimental results are also tabulated in one.This family alloy has good discharging rate and electricity capacity.List in this family material of table one again, the calculated value that its hydride generates heat between-4.5 and-8.5Kcal/mole H between, meet the foregoing rule of the present invention.
Table one
The electrical capacity of some hydride and generation heat
Material constituent electrical capacity (mAH/g) generates heat
(Kcal/mole?H)
First family: Tia Zrb Nic Crd
Ti0.3?Zr1.0?Ni1.4?Cr0.3 280 -7.27
Ti0.4?Zr0.8?Ni1.4?Cr0.4 290 -6.53
Ti0.5?Zr1.0?Ni1.2?Cr0.5 300 -7.23
Ti0.5?Zr0.7?Ni1.3?Cr0.5 290 -6.52
Ti0.5?Zr0.6?Ni1.4?Cr0.5 275 -5.80
Ti0.3?Zr0.8?Ni1.1?Cr0.5Mn0.1 265 -7.37
Second family: Tia Crb Zrc Nid V3-a-b-c-d Mx ' Ti0.4 Cr0.4 Zr0.2 Ni0.6 V1.4 295-6.43Ti0.3 Cr0.3 Zr0.5 Ni1.45 V0.45 268-7.18Ti0.15 Cr0.15 Zr0.8 Ni1.0 V0.8 310-7.25Ti0.35 Cr0.35 Zr0.5 Ni1.0 V0.8 285-6.43Ti0.3 Cr0.3 Zr0.5 Ni0.7 V1.2 Cu0.1 310-7.28
Three races: Tia Zrb Nic V3-a-b-c Mx ' Ti0.6 Zr0.5 Ni1.1 V0.8 310-7.38Ti0.7 Zr0.6 Ni1.3 V0.4 290-7.47Ti0.7 Zr0.4 Ni1.3 V0.6 280-6.63Ti0.65 Zr0.35 Ni1.30 V0.70 305-6.38Ti0.3 Zr0.8 Ni1.3 V0.6 275-7.23Ti0.5 Zr0.5 Ni1.1 V0.7 Cu0.2 250-6.38
The 4th family: Tia Mnb Vc Nid Mx ' Ti1.0 Mn0.5 V0.6 Ni0.9 280-6.13Ti1.1 Mn0.5 V0.5 Ni0.9 300-6.40Ti1.2 Mn0.45 V0.45 Ni0.9 310-6.75Ti1.3 Mn0.39 V0.38 Ni0.93 315-7.03Ti1.1 Mn0.5 V0.5 Ni0.9 Co0.1 280-6.40
Claims (3)
1. method of selecting and making many metal alloy compositions that hydrogen-storage electrode uses, this method comprises the following steps:
(1) select one group to comprise 5 kinds or above quantitative elements A, B, C at least ... make it to become and consist of AaBbCc ... alloy, wherein, elements A, B, C ... system is by selecting in the Mg of element group, Ti, V, Cr, Mn, Fe, Co, Ni, Al, Y, Zr, Nb, Pd, Mo, Ca and the rare earth metal;
(2) in the above-mentioned quantitative element, the content of Ni is greater than 5%, but is less than 85% atomic percent;
(3) this quantitatively forms many metal alloys AaBbCc ... hydride generate heat between-3.5 to-9.0Kcal/mole H, wherein hydride generates hot Hh and can be calculated by following formula:
Hh＝[aHh(A)+bHh(B)+cHh(C)+…]/(a+b+c+…)+k
Hh in the following formula (A), Hh (B), Hh (C) ... be respectively elements A, B, C ... Deng hydride generate heat (unit: Kcal/mole H), its value is:
Hh(Mg)=-9.0，Hh(Ti)＝-15.0，Hh(V)＝-7.0，
Hh(Cr)＝-1.81，Hh(Mn)=-2.0，Hh(Fe)＝4.0，
Hh(Co)＝4.0，Hh(Ni)＝2.0，Hh(Al)＝-1.38，
Hh(Y)＝-27.0，Hh(Zr)＝-1.95，Hh(Nb)＝-9.0，
Hh(Pd)＝-4.0，Hh(Mo)＝-1.0，Hh(Ca)＝-21.0，
Hh (rare earth element)=-25.0;
And k is a constant in the following formula, its value be 0.5 ,-0.2 and-1.5Kcal/mole H, correspond respectively to a+b+c ...=2,3 or 6;
(4) with above-mentioned atomic ratio a, b, c ... metallic element group A, B, C ... according to arc process, heating and melting and make alloy A aBbCc under protection of inert gas such as inductive method or electric slurry method ...
2. the method that is used to select a kind of many metal alloy compositions as claimed in claim 1, wherein atomic percent nickel is between 15% to 45%, and this quantitatively forms many metal alloy compositions AaBbCc ... the generation heat of hydride between-3.5 to-9.0Kcal/mole H.
3. many metal alloy compositions that the hydrogen-storage electrode that makes according to claim 1 or 2 described methods is used.
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| CN88108621A CN1037280C (en) | 1988-12-12 | 1988-12-12 | Method for storage of hydrogen and chemical constitution of hydride materials as electrode |
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| CN88108621A CN1037280C (en) | 1988-12-12 | 1988-12-12 | Method for storage of hydrogen and chemical constitution of hydride materials as electrode |
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| CN95109006A Division CN1071940C (en) | 1995-07-21 | 1995-07-21 | Hydrogen storage method and chemical compounding method of hydride electrode material |
| CN95109005A Division CN1043060C (en) | 1995-07-21 | 1995-07-21 | Hydrogen storage method and chemical composition of hydride electrode material |
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| CN1037280C true CN1037280C (en) | 1998-02-04 |
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| JPH04176833A (en) * | 1990-11-09 | 1992-06-24 | Furukawa Battery Co Ltd:The | Hydrogen storage alloy electrode |
| CN1074171C (en) * | 1994-12-27 | 2001-10-31 | 洪国治 | Hydrogen storage material and nickel-hydrogenized compound battery |
| CN107226456B (en) * | 2017-07-18 | 2019-04-19 | 王立坤 | A kind of hydrogen source device and its manufacturing method and Hydrogen Atom Frequency Standard |
| CN107342768B (en) * | 2017-07-18 | 2020-08-11 | 上海新示方科技有限公司 | Hydrogen atom frequency scale |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5591950A (en) * | 1978-12-28 | 1980-07-11 | Agency Of Ind Science & Technol | Hydrogen storing metallic material |
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| JPS5591950A (en) * | 1978-12-28 | 1980-07-11 | Agency Of Ind Science & Technol | Hydrogen storing metallic material |
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