CN108977715A - It is a kind of suitable for high pressure-hydride hydrogen-storing hydrogen bearing alloy and preparation method thereof - Google Patents
It is a kind of suitable for high pressure-hydride hydrogen-storing hydrogen bearing alloy and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of suitable for high pressure-hydride hydrogen-storing hydrogen bearing alloy and preparation method thereof, the alloy such as (TiZrx)yCrzFeuMn(2‑z‑u)Shown in formula, wherein 0.05≤x≤0.15,1.05≤y≤1.15,1≤z≤1.4,0.2≤u≤0.6, structure are C14 type Laves phase structure.Hydrogen release Ping Tai of such hydrogen bearing alloy under the conditions of 298K is pressed between 1-25MPa, and maximum hydrogen storage capability can reach 1.85%, and alloy is very easy to activation.
Description
Technical field
The present invention relates to a kind of alloys, and in particular to a kind of height suitable for the storage of the new energy complementary energy such as wind-powered electricity generation, solar energy
Pressure-metal hydride composite hydrogen occluding hydrogen bearing alloy.
Background technique
Wind energy is a kind of reproducible energy, and for the utilization of wind energy, there is huge wastes at present.Wind-electricity integration master
Have that the problem of following three aspect is urgently to be resolved, first, during wind-power electricity generation, voltage, frequency and phase have violent fluctuation
Property, lead to 10% of electric power grid connection capacity no more than total amount；Second, wind-powered electricity generation generates electricity apart from electricity consumption region farther out；Third, wind-powered electricity generation
Wave crest and wave trough demodulate peak character, in low power consumption, power generation is in wave crest state, this just needs to store extra generated energy
Get up, simultaneously because the fluctuation of wind-powered electricity generation, improves the output characteristics of wind-powered electricity generation by energy storage technology, so that electric power is steady, Neng Goushun
Benefit is grid-connected.
Hydrogen is a kind of clean energy resource and a kind of good energy carrier.Hydrogen energy storage technology carrys out electrolysis water using wind-powered electricity generation,
Hydrogen and oxygen storage are obtained, stable electric energy is exported by burning hydrogen or fuel cell power generation, smoothly enters electricity
Net, has that storage time is long, the reaction time is fast, the advantages such as does not pollute.
The storing mode of hydrogen is the key that in hydrogen energy storage technology, and hydrogen storage technology mainly has physics hydrogen storage and chemical hydrogen storage 2
Major class, common mode include high-pressure hydrogen storing, liquid hydrogen storage, active carbon adsorption, hydride hydrogen-storing, organic liquid hydrogen storage and
Inorganic compound hydrogen storage.Wherein requirement of the high-pressure hydrogen storing especially super-pressure hydrogen storage to hydrogen container is high, and needs to consume a large amount of
Work done during compression, and there is the danger of leakage, the requirement to liquid hydrogen preparation is very strict, liquefies at high cost.Hydride hydrogen-storing
Including two kinds, one is low pressure-metal hydride composite hydrogen occluding, the hydrogen of storage is difficult to release, and hydrogen discharging speed is slow；One is height
Pressure-metal hydride composite hydrogen occluding, hydrogen storage weight density with higher, and it is easy to release hydrogen at normal temperature.
In the hydrogen bearing alloy of existing different series, TiFe alloy manufacturing cost is lower, but its hydrogen storage content is low, and difficult living
Change, is easy to be poisoned, and TiCr2Alloy suction hydrogen release Ping Tai pressure with higher is reasonably designed to by adding different elements
Divide the alloy that can obtain different Ping Tai pressures, to adapt to the requirement of different occasions.
Summary of the invention
In order to solve the problems, such as that existing TiFe hydrogen bearing alloy hydrogen storage content is low, be difficult to activate, the present invention provides one kind to be applicable in
In high pressure-hydride hydrogen-storing hydrogen bearing alloy, which is easy activation, and hydrogen storage content is high.
Realize that the technical solution of the object of the invention is as follows:
It is a kind of suitable for high pressure-hydride hydrogen-storing hydrogen bearing alloy, the hydrogen bearing alloy such as (TiZrx)yCrzFeuMn(2-z-u)It is shown:
Wherein 0.05≤x≤0.15,1.05≤y≤1.15,1≤z≤1.6,0.2≤u≤0.6, z+u≤2.
Preferably, 0.05≤x≤0.15,1.08≤y≤1.15,1≤z≤1.6,0.2≤u≤0.6.
Preferably, 0.08≤x≤0.12,1.08≤y≤1.15,1≤z≤1.3,0.4≤u≤0.6.
Preferably, 0.08≤x≤0.12,1.08≤y≤1.12,1.2≤z≤1.3,0.45≤u≤0.55.
A kind of preparation method of alloy as described in claim 1, which is characterized in that described method includes following steps:
(1) metal Ti, Zr, Cr, Fe and excessive Mn for preparing in the ratio of chemical formula are subjected to melting under an ar atmosphere
Turn-over 4 times altogether；
(2) it takes out and weighs quality, if quality is more than standard volume, then carry out melting, turn-over 1 time；
(3) alloy after melting carries out mechanical grinding and is crushed to 5~100 μm of partial size.
Preferably, each raw metal is metal simple-substance, Ti > 99.5%, Zr > 99%, Cr > 99%, Fe in the step 1
> 99%, Mn > 99%.
Preferably, the additive amount of Mn is to add 110-120% according to the ratio of the formula in the step (1).
Preferably, the smelting time in the step (1) is 1.5min.
Preferably, the fusion process twice carries out in electric arc furnaces.
Preferably, according to how much determinations smelting time of weighing gained surplus in step (2).
Preferably, the shattering process in the step (3) carries out under hypoxemia, low nitrogen, the environment of low water or argon atmosphere.
Compared with the latest prior art, technical solution provided by the invention has following excellent effect:
Hydrogen bearing alloy provided by the invention have easily-activated, the high feature of hydrogen storage capability, inhale hydrogen pressure between 1-25MPa it
Between, maximum hydrogen storage capability reaches 1.85%, and alloy is easy activation, is suitable for wind energy complementary energy energy storage high pressure-hydride hydrogen-storing
Use hydrogen bearing alloy.
The preparation method simple process of hydrogen bearing alloy provided by the invention, it is easy to produce.
Detailed description of the invention:
Fig. 1 is the XRD of the hydrogen bearing alloy prepared in embodiment 1.
Fig. 2 is the XRD of the hydrogen bearing alloy prepared in embodiment 2.
Fig. 3 is the XRD of the hydrogen bearing alloy prepared in embodiment 3.
Fig. 4 is the XRD of the hydrogen bearing alloy prepared in embodiment 4.
Fig. 5 is the PCT curve graph of the hydrogen bearing alloy prepared in embodiment 1.
Fig. 6 is the PCT curve graph of the hydrogen bearing alloy prepared in embodiment 2.
Fig. 7 is the PCT curve graph of the hydrogen bearing alloy prepared in embodiment 3.
Fig. 8 is the PCT curve graph of the hydrogen bearing alloy prepared in embodiment 4.
Specific embodiment
The present invention is described in detail in explanation and specific example with reference to the accompanying drawing.
Embodiment 1
Molten alloy (TiZr0.1)1.05Cr1.1Fe0.6Mn0.3Alloy, and test its PCT curve
(1) raw material Ti:1.117g, Zr:0.238g, Cr:1.413g, Fe:0.829g, Mn:0.511g are taken, wherein Mn mistake
Amount, mixes and is put into electric arc furnaces, be evacuated down to 10-3For Pa hereinafter, being passed through 0.9atm argon gas, beginning melting is total to turn-over 4
It is secondary, each melting 1.5min.
(2) alloy after melting is taken out and weighs its quality, guarantee that the quality of alloy at this time is greater than the quality of subject alloy,
Weight alloy is 4.036g at this time.
(3) alloy after melting is put into electric arc furnaces, repeats arc melting operating process, according to alloy surplus,
Alloy turn-over melting is each primary, and each melting 1min obtains subject alloy, 3.990g.
The alloy obtained after above-mentioned three step, phase structure are C14 type Laves structure, and XRD diagram is shown in attached drawing 1, PCT
Curve is shown in Fig. 5.
Embodiment 2
Molten alloy (TiZr0.1)1.1Cr1.1Fe0.6Mn0.3Alloy, and test its PCT curve
(1) raw material Ti:1.154g, Zr:0.246g, Cr:1.390g, Fe:0.816g, Mn:0.493g are taken, wherein Mn mistake
Amount, mixes and is put into electric arc furnaces, be evacuated down to 10-3For Pa hereinafter, being passed through 0.9atm argon gas, beginning melting is total to turn-over 4
It is secondary, each melting 1.5min.
(2) alloy after melting is taken out and weighs its quality, the quality of alloy is greater than the quality of subject alloy at this time, at this time
Weight alloy is 4.003g.
(3) third step melting is skipped.
The alloy obtained after above-mentioned three step, phase structure are C14 type Laves structure, and XRD diagram is shown in attached drawing 2, PCT
Curve is shown in Fig. 6.
Embodiment 3
Molten alloy (TiZr0.1)1.15Cr1.1Fe0.6Mn0.3Alloy, and test its PCT curve
(1) raw material Ti:1.186g, Zr:0.251g, Cr:1.369g, Fe:0.803g, Mn:0.510g are taken, wherein Mn mistake
Amount, mixes and is put into electric arc furnaces, is evacuated down to 10-3Pa hereinafter, being passed through 0.9atm argon gas, starts melting, altogether turn-over 4
It is secondary, each melting 1.5min.
(2) alloy after melting is taken out and weighs its quality, guarantee that the quality of alloy at this time is greater than the quality of subject alloy,
Weight alloy is 4.045g at this time.
(3) alloy after melting is put into electric arc furnaces, repeats arc melting operating process, according to alloy surplus,
Alloy turn-over melting is each primary, and each smelting time is 1min, obtains subject alloy 4.009g.
The alloy obtained after above-mentioned three step, phase structure are C14 type Laves structure, and XRD diagram is shown in attached drawing 3, PCT
Curve is shown in Fig. 7.
Embodiment 4
Molten alloy (TiZr0.1)1.15Cr1.1Fe0.2Mn0.3Alloy, and test its PCT curve
(1) raw material Ti:1.197g, Zr:0.254g, Cr:1.884g, Fe:0.271g, Mn:0.587g are taken, wherein Mn mistake
Amount, mixes and is put into electric arc furnaces, be evacuated down to 10-3For Pa hereinafter, being passed through 0.9atm argon gas, beginning melting is total to turn-over 4
It is secondary, each melting 1.5min.
(2) alloy after melting is taken out and weighs its quality, guarantee that the quality of alloy at this time is greater than the quality of subject alloy,
Weight alloy is 4.058g at this time.
(3) alloy after melting is put into electric arc furnaces, repeats arc melting operating process, according to alloy surplus,
Alloy turn-over melting is each primary, and each melting 1min obtains subject alloy 4.011g.
The alloy obtained after above-mentioned three step, phase structure are C14 type Laves structure, and XRD diagram is shown in attached drawing 4, PCT
Curve is shown in Fig. 8.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, the common skill of fields
Art personnel should be appreciated that referring to above-described embodiment can with modifications or equivalent substitutions are made to specific embodiments of the invention,
These are applying for pending claim protection model without departing from any modification of spirit and scope of the invention or equivalent replacement
Within enclosing.
Claims (11)
1. a kind of suitable for high pressure-hydride hydrogen-storing hydrogen bearing alloy, which is characterized in that the hydrogen bearing alloy is such as
(TiZrx)yCrzFeuMn(2-z-u)It is shown:
Wherein 0.05≤x≤0.15,1.05≤y≤1.15,1≤z≤1.6,0.2≤u≤0.6, z+u≤2.
2. alloy according to claim 1, which is characterized in that 0.05≤x≤0.15,1.08≤y≤1.15,1≤z≤
1.6,0.2≤u≤0.6.
3. alloy according to claim 1, which is characterized in that 0.08≤x≤0.12,1.08≤y≤1.15,1≤z≤
1.3,0.4≤u≤0.6.
4. alloy according to claim 1, which is characterized in that 0.08≤x≤0.12,1.08≤y≤1.12,1.2≤z≤
1.3、0.45≤u≤0.55。
5. a kind of preparation method of alloy as described in claim 1, which is characterized in that described method includes following steps:
(1) metal Ti, Zr, Cr, Fe for preparing in the ratio of chemical formula and excessive Mn melting is carried out under an ar atmosphere to turn over altogether
Face 4 times；
(2) it takes out and weighs quality, if quality is more than standard volume, then carry out melting, turn-over 1 time；
(3) alloy after melting carries out mechanical grinding and is crushed to 5~100 μm of partial size.
6. method according to claim 5, which is characterized in that each raw metal is metal simple-substance in the step 1, Ti >
99.5%, Zr > 99%, Cr > 99%, Fe > 99%, Mn > 99%.
7. method according to claim 5, which is characterized in that the additive amount of Mn is according to the formula in the step (1)
Ratio adds 110-120%.
8. method according to claim 5, which is characterized in that the smelting time in the step (1) is 1.5min.
9. method according to claim 5, which is characterized in that the fusion process twice carries out in electric arc furnaces.
10. method according to claim 5, which is characterized in that according to how much determining institutes of weighing gained surplus in step (2)
State smelting time.
11. method according to claim 5, which is characterized in that shattering process in the step (3) is in hypoxemia, low nitrogen, low
It is carried out under water environment or argon atmosphere.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042304A (en) * | 2019-04-22 | 2019-07-23 | 宁夏大学 | A kind of high-pressure metal hydride composite hydrogen occluding tank high platform pressure hydrogen bearing alloy |
| CN112030054A (en) * | 2020-09-09 | 2020-12-04 | 中南大学 | TiZrMnFe quaternary getter alloy material and preparation method and application thereof |
| CN113215467A (en) * | 2021-04-28 | 2021-08-06 | 浙江大学 | Solid hydrogen storage material for hydrogen filling station and preparation method and application thereof |
| CN114671403A (en) * | 2022-04-06 | 2022-06-28 | 中国科学院长春应用化学研究所 | Ti-Mn-Fe hydrogen storage material and preparation method thereof |
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| CN101538673A (en) * | 2008-11-28 | 2009-09-23 | 复旦大学 | Under-measurement Laves phase hydrogen storage alloy and preparation method thereof |
| CN103320668A (en) * | 2013-06-04 | 2013-09-25 | 浙江大学 | Hydrogen-storing alloy used for metal-hydride and high-pressure combined hydrogen storage |
| CN103695754A (en) * | 2013-12-18 | 2014-04-02 | 浙江大学 | Easy-to-activate high-plateau pressure hydrogen storage alloy and preparation method thereof |
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2017
- 2017-05-31 CN CN201710400571.8A patent/CN108977715A/en active Pending
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|---|---|---|---|---|
| CN101538673A (en) * | 2008-11-28 | 2009-09-23 | 复旦大学 | Under-measurement Laves phase hydrogen storage alloy and preparation method thereof |
| CN103320668A (en) * | 2013-06-04 | 2013-09-25 | 浙江大学 | Hydrogen-storing alloy used for metal-hydride and high-pressure combined hydrogen storage |
| CN103695754A (en) * | 2013-12-18 | 2014-04-02 | 浙江大学 | Easy-to-activate high-plateau pressure hydrogen storage alloy and preparation method thereof |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042304A (en) * | 2019-04-22 | 2019-07-23 | 宁夏大学 | A kind of high-pressure metal hydride composite hydrogen occluding tank high platform pressure hydrogen bearing alloy |
| CN112030054A (en) * | 2020-09-09 | 2020-12-04 | 中南大学 | TiZrMnFe quaternary getter alloy material and preparation method and application thereof |
| CN113215467A (en) * | 2021-04-28 | 2021-08-06 | 浙江大学 | Solid hydrogen storage material for hydrogen filling station and preparation method and application thereof |
| CN114671403A (en) * | 2022-04-06 | 2022-06-28 | 中国科学院长春应用化学研究所 | Ti-Mn-Fe hydrogen storage material and preparation method thereof |
| CN114671403B (en) * | 2022-04-06 | 2024-01-30 | 中国科学院长春应用化学研究所 | Ti-Mn-Fe hydrogen storage material and preparation method thereof |
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