CN101899639B - Method for improving corrosion resistance of hydrogen storage alloy by surface boronising method - Google Patents
Method for improving corrosion resistance of hydrogen storage alloy by surface boronising method Download PDFInfo
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- CN101899639B CN101899639B CN2010101379197A CN201010137919A CN101899639B CN 101899639 B CN101899639 B CN 101899639B CN 2010101379197 A CN2010101379197 A CN 2010101379197A CN 201010137919 A CN201010137919 A CN 201010137919A CN 101899639 B CN101899639 B CN 101899639B
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- hydrogen storage
- storage alloy
- boronising
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000000956 alloy Substances 0.000 title claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 64
- 238000003860 storage Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000007797 corrosion Effects 0.000 title claims abstract description 21
- 238000005260 corrosion Methods 0.000 title claims abstract description 21
- 229910052796 boron Inorganic materials 0.000 claims abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000005271 boronizing Methods 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 5
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 10
- 229910052987 metal hydride Inorganic materials 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 230000036541 health Effects 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 75
- 239000011777 magnesium Substances 0.000 description 70
- 239000011232 storage material Substances 0.000 description 23
- 239000011575 calcium Substances 0.000 description 21
- 238000001994 activation Methods 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910020191 CeNi Inorganic materials 0.000 description 6
- 229910018007 MmNi Inorganic materials 0.000 description 6
- 229910008340 ZrNi Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000001996 bearing alloy Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- -1 nickel metal hydride Chemical class 0.000 description 4
- 239000003961 penetration enhancing agent Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910006176 NixCo Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Powder Metallurgy (AREA)
Abstract
The invention relates to a method for modifying hydrogen storage alloy, which aims at providing a method for improving the corrosion resistance of hydrogen storage alloy in an alkaline solution by a surface boronising method. The surface of the hydrogen storage alloy is treated by the surface boronising method in the method, and a compound comprising the elements of nitrogen and the hydrogen storage alloy is formed on the surface layer. A boronising agent and an activating agent used by the method are nontoxic and harmless, so that no toxic gas is generated during boronising process, the environment and the health can not be harmed, and the boron supplying agent and the activating agent are applicable to mass production. The corrosion resistance of the boronised hydrogen storage alloy in an alkaline solution or a saline solution can be obviously improved. When the boronised hydrogen storage alloy is applied to a nickel-metal hydride battery, the capacity or the energy density of the battery can be greatly increased, and the cost is reduced. When the boronised hydrogen storage alloy is applied to an air battery, the self discharge speed of the battery can be greatly reduced, and the service life of the air battery is prolonged. Thus, the air battery can hopefully become a portable and movable power source for large-scale commercial application to be applied to electric automobiles, electronic products, military equipment and the like.
Description
Technical field
The present invention relates to the hydrogen storage alloy method of modifying, more particularly, the present invention relates to a kind of method of improving the corrosion resistance nature of hydrogen storage alloy in basic soln through surface boronizing.
Background technology
Hydrogen Energy is the secondhand energy of human future ideality.Hydrogen storage alloy forms metal hydride with the stores of atomic state with hydrogen in the atom gap of hydrogen storage alloy.Hydrogen storage alloy can be as the negative material of nickel metal hydride battery or metal hydride air battery.Nickel metal hydride battery adopts Ni oxyhydroxide as positive pole, and hydrogen storage metal is as negative pole, and alkali lye (being mainly KOH) is as electrolytic solution, and metal hydride air battery adopts air electrode as positive pole, and hydrogen storage metal is as negative pole, alkali lye or NH
4Cl is as electrolytic solution.Hydrogen storage material is often with general formula AB
xExpression, A be REE or lucium, calcium, titanium, zirconium, magnesium, vanadium etc. easily and the element of hydrogen evolution hydrogenate; B then is nickel, cobalt, manganese, and (perhaps) also has aluminium.With respect to (the AB of rare earth metal system
5Type), (AB of titanium system (AB type) and zirconium system
2Advantages such as hydrogen storage alloy type), Mg base hydrogen bearing alloy have that proportion is little, hydrogen storage capability is high, cheap, aboundresources.
The main method of improving the hydrogen storage alloy charge-discharge performance at present has the alloying element of interpolation, controls size, carries out anneal, processes matrix material, carries out the surface coating, controls the electric charge input, uses inhibiter and improve preparation technology etc.Wherein, Mg base hydrogen bearing alloy is a kind of very promising alloy material storing hydrogen, but very easily corrosion in alkaline electrolyte, charge-discharge performance is relatively poor, thereby has limited its application aspect electrochemistry.Therefore, adopt different methods its charge and discharge circulation life to be improved a research focus that becomes in recent years.As utilize solid phase diffusion method to prepare the alternative magnesiumalloy Mg of aluminum portions
2- xAl
xNi is along with the increase discharge stability of aluminium content be improved [J.Alloys Compd, 307 (2000) 240-244].Think that mechanism is owing to add aluminium, can form fine and close protective membrane, strengthened the solidity to corrosion of alloy at alloy surface.Method with mechanical alloying obtains Mg
1.95Y
0.05Ni
0.92Al
0.08, need not its capacity of activation and promptly reach 470mAh g
-1, and charge and discharge cycles stability is fine, and 150 times circulation back capability retention still reaches 98%.The Magnuminium that adds at Pr, Ce imposes melt-spun, and setting rate reaches 105～106K s
-1, can make the excellent Pr of cyclical stability
5Co
19Type or Ce
5Co
19The high temperature of type structure part mutually keeps, itself and Ce
2Ni
7Type or Gd
2Co
7Type acts synergistically mutually and makes rare earth and magnesium-based hydrogen storage alloy have heavy body and long lifetime [CN101624660] simultaneously.
Boronising is a kind of process for treating surface of development after traditional carburizing, nitriding are handled, and only is used for the surface treatment of iron and steel usually.Surface hardness, wear resistance, erosion resistance and the red hardness that can significantly improve steel-iron components usually handled in boronising.But traditional boronising all has its shortcoming.Like Gaseous State Boronization the danger of blast is arranged, its gas is also toxic.Liquid boriding then also need carry out certain surface treatment to the part after the boronising, could be practical.Pack boriding is compared with other boriding process has many advantages.Powder boriding technology particularly, it has does not need specific installation, adopt common electrical, gas, coal process furnace all can, technological operation is simple, osmosis work-piece need not clean, the penetration enhancer reusability is good, cost is lower and alloying layer thickness and organize advantages such as easy to control.
The boron supplying agent that pack boriding generally adopts has two kinds, and a kind of is norbide, and a kind of is ferro-boron.Be generally in the existing technology and restore the boron atom, in penetration enhancer, all add potassium fluoborate as acvator, its chemical reaction is following:
(1) reaction of norbide, potassium fluoborate penetration enhancer:
2KBF
4+B
4C+O
2→K
2O+4BF
2↑+2[B]+CO↑
BF wherein
2Be unstable gas, parse the boron atom and form stable BF through branch
3Gas:
3BF
2＝[B]+2BF
3↑
(2) reaction of ferro-boron, potassium fluoborate penetration enhancer:
4KBF
4+4B+O
2→2K
2O+8BF
2↑
BF wherein
2Branch takes place parse boron atom generation BF
3Gas.
BF
3Be toxic gas, stronger corrodibility is arranged, environment is worked the mischief.Handle if adopt existing technology that hydrogen storage material is carried out boronising, not only can bring environmental problem, the BF that is produced
3The plain Mg of hydrogen storage element in gas meeting and the hydrogen storage material, La etc. form MgF
2, LaF
3Deng compound, cause the remarkable decline of hydrogen storage material hydrogen storage ability.
Summary of the invention
The technical problem that the present invention will solve is to overcome deficiency of the prior art, and a kind of method of improving corrosion resistance of hydrogen storage alloy by surface boronising method is provided.
For solving the problems of the technologies described above, the invention provides a kind of method of improving corrosion resistance of hydrogen storage alloy by surface boronising method, adopt the surface boronizing method that the hydrogen storage alloy surface is handled, in its upper layer, form the compound that nitrogen and hydrogen storage alloy constitute element.
Among the present invention, this method comprises: the selection granularity is that any section in 50～100 purpose Peng Qinghuanas, POTASSIUM BOROHYDRIDE 97MIN, anhydrous metaboric acid, anhydrous sodium metaborate, the anhydrous potassium metaborate is a boron supplying agent; When using anhydrous metaboric acid, anhydrous sodium metaborate, anhydrous potassium metaborate as boron supplying agent, need with Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN as acvator, Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN need not acvator during as boron supplying agent; After hydrogen storage alloy is crushed to 200 orders～400 orders, by hydrogen storage alloy: boron supplying agent: the mass ratio of acvator 1: 0.01～0.2: 0～0.6 mixes and is placed in the gas shield stove; Under argon shield, 1～10 ℃/min of control heat-up rate, 500～800 ℃ of calcining temperatures, calcination time 1～12h carry out surface boronizing and handle, and cooling gets final product.
Relevant reaction mechanism is:
(1) when adopting Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN as boron supplying agent, its chemical reaction is following:
2Na(K)BH
4→2Na(K)H+2[B]+3H
2↑
The hydrogen that produces will be absorbed by hydrogen storage material.
(2) be boron supplying agent when adopting anhydrous metaboric acid, anhydrous sodium metaborate, anhydrous potassium metaborate, when Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN were made acvator, its chemical reaction was following:
2Na(K)BH
4+2HBO
2→2Na(K)H+4[B]+4H
2O↑
2Na(K)BH
4+Na(K)BO
2→3Na(K)H+3[B]+2H
2O↑+
1/
2H
2↑
The hydrogen that produces will be absorbed by hydrogen storage material.
Among the present invention; Though since its oxidation capacity of boronising water byproduct steam very a little less than; But at high temperature also can form thin oxide layer on the hydrogen storage material surface; Therefore after surface boronizing is handled, also comprise and carry out hot alkali treatment or pickling is removed zone of oxidation with activation hydrogen storage alloy surface as subsequent disposal.
Among the present invention, said hot alkali treatment is: the hydrogen storage alloy that will pass through the surface boronizing processing is 2～6M L in concentration
-1KOH or NaOH solution in flood 0.5～5h, 50～90 ℃ of dipping temperatures filter and take out hydrogen storage alloy; After the deionized water wash filtration, 70～90 ℃ of following vacuum-drying 6～12h.
Among the present invention, the treatment step of described pickling is following: the hydrogen storage alloy that at room temperature will pass through the surface boronizing processing is 0.01～0.5M L in concentration
-1Flood 0.5～5h in oxalic acid, Glacial acetic acid min. 99.5 or the hydrochloric acid soln, filter and take out hydrogen storage alloy; Spend and left after water washing filters 70～90 ℃ of following vacuum-drying 6～12h.
Among the present invention, the composition of said hydrogen storage alloy can be by formula M g
aR
bNi
cCo
dAl
eExpression, R is zirconium, calcium, rare earth or mishmetal, each atomic component variation range: 0≤a≤16; 0≤b≤2; 0＜c≤5; 0≤d≤1; 0≤e≤0.5; But a and b must not be zero simultaneously.
Adopt the surface boronizing technology to carry out the hydrogen storage alloy surface alloying, can be through changing upper layer stress distribution and hydrogen storage alloy surface composition, the corrosion resistance nature to hydrogen storage alloy on atomic scale is improved.For example, boron can form gap MgB mutually with magnesium
2, MgB
4And MgB
7, form RB with calcium, rare earth
4, RB
6, RB
9, R is calcium, rare earth or mishmetal, can form gap ZrB mutually with zirconium
2, ZrB
12, can form Ni with nickel
3B, Ni
2B, Ni
4B
3And NiB.After boron and zirconium, calcium, rare earth and magnesium form compound; Effectively with the unbound electron of zirconium, calcium, rare earth and magnesium be attracted to the B atom around and be difficult to lose; Cause the localization of unbound electron, thereby suppress the oxidation of zirconium, calcium, rare earth and magnesium, improve the corrosion resistance of hydrogen storage alloy.Form compound with other elements, disperse is distributed in the upper layer of hydrogen storage alloy, and the oxide compound of zirconium, calcium, rare earth and magnesium or the growth of oxyhydroxide are played inhibition, thereby improves the corrosion resistance of hydrogen storage alloy.
Compared with prior art, the invention has the beneficial effects as follows:
Boron supplying agent and acvator that the present invention adopts all are nontoxic, can not produce toxic gas in the boronizing process, can not endanger environment, can not health risk, can be mass-produced.The erosion resistance of hydrogen storage alloy in alkalescence or salt solution after boronising is handled is greatly improved.Be applied to capacity or energy density that nickel metal hydride battery can increase substantially battery; Reduce cost; Be applied to the speed that gas battery can slow down self-discharge significantly, increase the duration of service of gas battery, get a good chance of becoming the portable and portable power supply of large-scale commercial applications application; Be applied to electromobile, electronic product and military equipment etc.
Figure of description
Fig. 1 is 0.1M L
-1Surface boronizing is handled Mg behind the oxalic acid solution
1.6La
0.4The electronic photo of Ni powder.
Fig. 2 is that the present invention is to AB
5The design sketch that the type hydrogen storage alloy corrosion resistance nature improves.
Among the figure: 1. LaNi
4.25Co
0.25Al
0.5The charge and discharge cycles decline curve of electrode; 2. LaNi is handled in boronising
4.25Co
0.25Al
0.5The charge and discharge cycles decline curve of electrode; 3. LaNi is handled in activated back boronising
4.25Co
0.25Al
0.5The charge and discharge cycles decline curve of electrode; Charging and discharging currents 100mA g under the room temperature
-1
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment 1: the preparation of hydrogen-bearing alloy powder
Table 1Mg
aR
bNi
cCo
dAl
eThe composition of hydrogen storage alloy is given an example
| Mg 2Ni | Mg 2Ni 0.5Co 0.5 | Mg 2Ni 0.5Co 0.25Al 0.25 | Mg 2Ni 0.25Co 0.25Al 0.5 |
| ZrNi 2 | ZrNi 1.5Co 0.5 | ZrNi 1.5Co 0.25Al 0.25 | ZrNi 1.25Co 0.25Al 0.5 |
| CaNi 5 | CaNi 4.5Co 0.5 | CaNi 4.5Co 0.25Al 0.25 | CaNi 4.25Co 0.25Al 0.5 |
| LaNi 5 | LaNi 4.5Co 0.5 | LaNi 4.5Co 0.25Al 0.25 | LaNi 4.25Co 0.25Al 0.5 |
| MlNi 5 | MlNi 4.5Co 0.5 | MlNi 4.5Co 0.25Al 0.25 | MlNi 4.25Co 0.25Al 0.5 |
| CeNi 5 | CeNi 4.5Co 0.5 | CeNi 4.5Co 0.25Al 0.25 | CeNi 4.25Co 0.25Al 0.5 |
| MmNi 5 | MmNi 4.5Co 0.5 | MmNi 4.5Co 0.25Al 0.25 | MmNi 4.25Co 0.25Al 0.5 |
| Mg 1.6La 0.4Ni | Mg 1.6La 0.4NixCo 0.5 | Mg 1.6La 0.4Ni 0.5Co 0.25Al 0.25 | Mg 1.6La 0.4Ni 0.25Co 0.25Al 0.5 |
| Mg 1.6Ml 0.4Ni | Mg 1.6Ml 0.4Ni 0.5Co 0.5 | Mg 1.6Ml 0.4Ni 0.5Co 0.25Al 0.25 | Mg 1.6Ml 0.4Ni 0.25Co 0.25Al 0.5 |
| Mg 1.6Ce 0.4Ni | Mg 1.6Ce 0.4Ni 0.5Co 0.5 | Mg 1.6Ce 0.4Ni 0.5Co 0.25Al 0.25 | Mg 1.6Ce 0.4Ni 0.25Co 0.25Al 0.5 |
| Mg 1.6Mm 0.4Ni | Mg 1.6Mm 0.4Ni 0.5Co 0.5 | Mg 1.6Mm 0.4Ni 0.5Co 0.25Al 0.25 | Mg 1.6Mm 0.4Ni 0.25Co 0.25Al 0.5 |
| Mg 1.6Ca 0.4Ni | Mg 1.6Ca 0.4Ni 0.5Co 0.5 | Mg 1.6Ca 0.4Ni 0.5Co 0.25Al 0.25 | Mg 1.6Ca 0.4Ni 0.25Co 0.25Al 0.5 |
| Mg 16La 2Ni | Mg 16La 2Ni 0.5Co 0.5 | Mg 16La 2Ni 0.5Co 0.25Al 0.25 | Mg 16La 2Ni 0.25Co 0.25Al 0.5 |
| Mg 16Ml 2Ni | Mg 16Ml 2Ni 0.5Co 0.5 | Mg 16Ml 2Ni 0.5Co 0.25Al 0.25 | Mg 16Ml 2Ni 0.25Co 0.25Al 0.2 |
| Mg 16Ce 2Ni | Mg 16Ce 2Ni 0.5Co 0.5 | Mg 16Ce 2Ni 0.5Co 0.25Al 0.25 | Mg 16Ce 2Ni 0.25Co 0.25Al 0.5 |
| Mg 16Mm 2Ni | Mg 16Mm 2Ni 0.5Co 0.5 | Mg 16Mm 2Ni 0.5Co 0.25Al 0.25 | Mg 16Mm 2Ni 0.25Co 0.25Al 0.5 |
| Mg 16Ca 2Ni | Mg 16Ca 2Ni 0.5Co 0.5 | Mg 16Ca 2Ni 0.5Co 0.25Al 0.25 | Mg 16Ca 2Ni 0.25Co 0.25Al 0.5 |
Press the atomic ratio of metallic element in each alloy of table 1, weigh respective metal, put into crucible.For the hydrogen storage alloy of calcic, magnesium, place in the tube furnace of argon shield, under argon shield, be warming up to 800 ℃, keep 2 hours postcooling to room temperatures down at 800 ℃, obtain corresponding block calcium base or magnesium-base hydrogen storage material.Carry out fragmentation with the Mechanical Crushing method,, place stainless steel reactor, be warming up to 350 ℃, be evacuated to reactor pressure 10 through the particle of screening acquisition particle diameter less than 2 millimeters
-3Below the Torr, hydrogenation boosts to 40 normal atmosphere and carries out hydrogenation then, when hydrogen pressure in the reactor drum no longer descends, is warming up to 450 ℃ of dehydrogenations of reducing pressure.The cooling back is taken out from reactor drum and is obtained hydrogen storage material powder, grain size screening 200 orders～400 orders.
For the hydrogen storage alloy of calcic, magnesium not, place in the induction furnace, under argon shield, be warming up to 2000 ℃, keep 0.2 hour postcooling to room temperature, obtain block hydrogen storage material.Carry out fragmentation with the Mechanical Crushing method,, place stainless steel reactor, be warming up to 350 ℃, be evacuated to reactor pressure 10 through the hydrogen storage material particle of screening acquisition particle diameter less than 2 millimeters
-3Below the Torr, hydrogenation boosts to 40 normal atmosphere and carries out hydrogenation then, when hydrogen pressure in the reactor drum no longer descends, is warming up to 100 ℃ of dehydrogenations of reducing pressure.The cooling back is taken out from reactor drum and is obtained the hydrogen storage material powder.
Embodiment 2: the hydrogen storage alloy boronising is handled
Choosing among the embodiment 1 some alloys carries out boronising and handles; Get hydrogen-bearing alloy powder 100 grams, particle size range is 200 orders～400 orders, with boron supplying agent or boron supplying agent and acvator mechanically mixing; Place in the tube furnace of argon shield; 1～10 ℃/min of control heat-up rate is heated to 500～800 ℃, calcines 1～12 hour.Its boronising treatment process condition is listed in table 2.
Table 2 hydrogen storage alloy boronising treatment process condition
| Alloy (g) | Boron supplying agent (g) | Acvator (g) | Heat-up rate (℃/min) | Calcining temperature (℃) | Calcination time (h) |
| Mg 2Ni(100) | NaBH 4(1) | 1 | 500 | 12 | |
| ZrNi 2(100) | KBH 4(5) | 2 | 600 | 7 | |
| CaNi 4.5Co 0.25Al 0.25(100) | NaBH 4(10) | 5 | 700 | 3 | |
| LaNi 4.25Co 0.25Al 0.5(100) | KBH 4(20) | 10 | 800 | 1 | |
| MlNi 4.5Co 0.25Al 0.25(100) | HBH 4(1) | NaBH 4(5) | 1 | 500 | 12 |
| CeNi 4.5Co 0.25Al 0.25(100) | NaBO 2(5) | NaBH 4(15) | 2 | 600 | 7 |
| MmNi 4.5Co 0.5(100) | KBO 2(10) | KBH 4(20) | 5 | 700 | 3 |
| Mg 1.6La 0.4Ni 0.5Co 0.25Al 0.25(100) | HBH 4(1) | NaBH 4(40) | 10 | 600 | 1 |
| Mg 1.6Ml 0.4Ni 0.25Co 0.25Al 0.5(100) | NaBO 2(5) | NaBH 4(60) | 1 | 500 | 12 |
| Mg 1.6Ce 0.4Ni 0.5Co 0.25Al 0.25(100) | KBO 2(10) | KBH 4(40) | 2 | 600 | 7 |
| Mg 1.6Mm 0.4Ni 0.5Co 0.5(100) | HBH 4(1) | NaBH 4(60) | 5 | 500 | 3 |
| Mg 1.6Ca 0.4Ni 0.5Co 0.5(100) | NaBO 2(5) | NaBH 4(40) | 10 | 500 | 1 |
| Mg 16La 2Ni 0.5Co 0.25Al 0.25(100) | KBO 2(10) | KBH 4(20) | 1 | 500 | 12 |
| Mg 16Ml 2Ni 0.25Co 0.25Al 0.2(100) | KBO 2(10) | KBH 4(40) | 2 | 600 | 7 |
| Mg 16Ce 2Ni(100) | HBH 4(1) | NaBH 4(5) | 5 | 600 | 3 |
| Mg 16Mm 2Ni 0.5Co 0.5(100) | NaBO 2(5) | NaBH 4(10) | 10 | 600 | 1 |
| Mg 16Ca 2Ni 0.25Co 0.25Al 0.5(100) | KBO 2(10) | KBH 4(20) | 10 | 600 | 2 |
Embodiment 3: the activation treatment after the hydrogen storage alloy boronising is handled
It is 0.01～0.5M L that hydrogen storage material powder 10 grams of under the room temperature above-mentioned surface boronizing being handled place 200 ml concns
-1Hydrochloric acid, oxalic acid or glacial acetic acid solution in flood 0.5～5h under the room temperature, or to place 200 ml concns be 2～6M L
-1NaOH or KOH solution in, 50～90 ℃ of dipping 0.5～5h down filter and take out after the back filters with deionized water wash, 70～90 ℃ of down dry 6～12h of vacuum get final product.
The poling processing technique condition of back hydrogen storage alloy is handled in table 3 boronising
Embodiment 4: the assessment of boronising treatment effect
Hydrogen storage material powder, nickel powder, the PVA aqueous solution (5wt.%) of boronising among the embodiment 3 being handled activation treatment front and back among front and back, the embodiment are coated in the nickel foam by 1: 0.5: 3 hybrid modulation form slurry of mass ratio; Compression moulding after the drying at room temperature is as comparing electrode.With LaNi
4.25Co
0.25Al
0.5Be example, Fig. 2 has provided these the three kinds relatively inducing capacity fading behaviors of electrode.As can be seen from the figure, eliminate LaNi through the oxalic acid solution activation
4.25Co
0.25Al
0.5Handle the deterioration of the electrode activation performance brought because of boronising, keep boronising to handle simultaneously LaNi
4.25Co
0.25Al
0.5The electrode charge and discharge cyclical stability.
Estimate the corrosion resistance nature of hydrogen storage material with the charge/discharge capacity retention of charge and discharge cycles 400 times, the capacity retention is high more, explains that the corrosion resistance nature of hydrogen storage material is good more.Table 4 has provided some hydrogen storage materials process surface boronizings processing among the embodiment 3, to the raising effect of hydrogen storage material corrosion resistance nature.
Capacity retention after table 4 hydrogen storage material process surface boronizing front and back and the surface activation process relatively
| Alloy | Before boronising is handled | After boronising is handled | After the activation treatment |
| ?Mg 2Ni | 11％ | 32％ | 50％ |
| ?ZrNi 2 | 30％ | 41％ | 86％ |
| ?CaNi 4.5Co 0.25Al 0.25 | 23％ | 51％ | 84％ |
| ?LaNi 4.25Co 0.25Al 0.5 | 41％ | 48％ | 82％ |
| ?MlNi 4.5Co 0.25Al 0.25 | 51％ | 75％ | 91％ |
| ?CeNi 4.5Co 0.25Al 0.25 | 52％ | 76％ | 92％ |
| ?MmNi 4.5Co 0.5 | 45％ | 79％ | 87％ |
| ?Mg 1.6La 0.4Ni 0.5Co 0.25Al 0.25 | 15％ | 36％ | 85％ |
| ?Mg 1.6Ml 0.4Ni 0.25Co 0.25Al 0.5 | 20％ | 45％ | 80％ |
| ?Mg 1.6Ce 0.4Ni 0.5Co 0.25Al 0.25 | 22％ | 48％ | 82％ |
| ?Mg 1.6Mm 0.4Ni 0.5Co 0.5 | 24％ | 51％ | 84％ |
| ?Mg 1.6Ca 0.4Ni 0.5Co 0.5 | 25％ | 50％ | 85％ |
| ?Mg 16La 2Ni 0.5Co 0.25Al 0.25 | 13％ | 49％ | 83％ |
| ?Mg 16Ml 2Ni 0.25Co 0.25Al 0.2 | 12％ | 47％ | 82％ |
| ?Mg 16Ce 2Ni | 11％ | 45％ | 81％ |
| ?Mg 16Mm 2Ni 0.5Co 0.5 | 14％ | 53％ | 84％ |
| ?Mg 16Ca 2Ni 0.25Co 0.25Al 0.5 | 16％ | 55％ | 85％ |
From table 4, can find out; After hydrogen storage material is handled through boronising; The charge/discharge capacity retention of hydrogen storage material is improved; After passing through activation treatment again, the charge/discharge capacity retention of hydrogen storage material is further improved, and explains that thus boronising handles the corrosion resistance nature that the activation treatment that continues can increase substantially hydrogen storage material.
At last, it is also to be noted that what more than enumerate only is specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. the method for an improving corrosion resistance of hydrogen storage alloy by surface boronising method is characterized in that, adopts the surface boronizing method that the hydrogen storage alloy surface is handled, and in its upper layer, forms the compound that boron and hydrogen storage alloy constitute element;
Said hydrogen storage alloy be following any one:
Mg
1.6La
0.4Ni Mg
1.6La
0.4Ni
0.5Co
0.25Al
0.25 Mg
1.6La
0.4Ni
0.25Co
0.25Al
0.5
Mg
1.6Ce
0.4Ni Mg
1.6Ce
0.4Ni
0.5Co
0.5 Mg
1.6Ce
0.4Ni
0.5Co
0.25Al
0.25 ?Mg
1.6Ce
0.4Ni
0.25Co
0.25Al
0.5
Mg
1.6Ca
0.4Ni Mg
1.6Ca
0.4Ni
0.5Co
0.5 Mg
1.6Ca
0.4Ni
0.5Co
0.25Al
0.25 ?Mg
1.6Ca
0.4Ni
0.25Co
0.25Al
0.5
Mg
16La
2Ni Mg
16La
2Ni
0.5Co
0.5 Mg
16La
2Ni
0.5Co
0.25Al
0.25 ?Mg
16La
2Ni
0.25Co
0.25Al
0.5
Mg
16Ce
2Ni Mg
16Ce
2Ni
0.5Co
0.5 Mg
16Ce
2Ni
0.5Co
0.25Al
0.25 ?Mg
16Ce
2Ni
0.25Co
0.25Al
0.5
Mg
16Ca
2Ni Mg
16Ca
2Ni
0.5Co
0.5 Mg
16Ca
2Ni
0.5Co
0.25Al
0.25 ?Mg
16Ca
2Ni
0.25Co
0.25Al
0.5
This method comprises: selecting granularity is that in 50～100 purpose Peng Qinghuanas, POTASSIUM BOROHYDRIDE 97MIN, anhydrous metaboric acid, anhydrous sodium metaborate, the anhydrous potassium metaborate any one is boron supplying agent; When using anhydrous metaboric acid, anhydrous sodium metaborate, anhydrous potassium metaborate as boron supplying agent, need with Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN as acvator, Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN need not acvator during as boron supplying agent; After hydrogen storage alloy is crushed to 200 orders～400 orders, by hydrogen storage alloy: boron supplying agent: the mass ratio of acvator 1: 0.01～0.2: 0～0.6 mixes and is placed in the gas shield stove; Under argon shield, 1～10 ℃/min of control heat-up rate, 500～800 ℃ of calcining temperatures, calcination time 1～12h carry out surface boronizing and handle, and cooling gets final product.
2. according to the method for the said improving corrosion resistance of hydrogen storage alloy by surface boronising method of claim 1, it is characterized in that, after surface boronizing is handled, also comprise carry out hot alkali treatment or pickling as subsequent disposal with activation hydrogen storage alloy surface.
3. according to the method for the said improving corrosion resistance of hydrogen storage alloy by surface boronising method of claim 2; It is characterized in that; Said hot alkali treatment is: will pass through hydrogen storage alloy that surface boronizing handles and in concentration is KOH or the NaOH solution of 2～6M, flood 0.5～5h; 50～90 ℃ of dipping temperatures filter and take out hydrogen storage alloy; After the deionized water wash filtration, 70～90 ℃ of following vacuum-drying 6～12h.
4. according to the method for the said improving corrosion resistance of hydrogen storage alloy by surface boronising method of claim 2; It is characterized in that; The treatment step of described pickling is following: the hydrogen storage alloy that at room temperature will pass through the surface boronizing processing is to flood 0.5～5h in 0.01～0.5M oxalic acid, Glacial acetic acid min. 99.5 or the hydrochloric acid soln in concentration, filters and takes out hydrogen storage alloy; After the deionized water wash filtration, 70～90 ℃ of following vacuum-drying 6～12h.
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| Title |
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| 东北输油管理局铁岭机械厂科研所.渗硼产生耐磨表层.《国外金属热处理》.1995,第16卷(第5期),56-64页. * |
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