CN103031480B - A kind of containing accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel and preparation method thereof - Google Patents
A kind of containing accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel and preparation method thereof Download PDFInfo
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- CN103031480B CN103031480B CN201210552733.7A CN201210552733A CN103031480B CN 103031480 B CN103031480 B CN 103031480B CN 201210552733 A CN201210552733 A CN 201210552733A CN 103031480 B CN103031480 B CN 103031480B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 96
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 96
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000011232 storage material Substances 0.000 title claims abstract description 81
- -1 aluminium sodium titanium vanadium nickel Chemical compound 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 28
- 239000000956 alloy Substances 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 16
- 238000011068 loading method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 239000013079 quasicrystal Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000005551 mechanical alloying Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910017488 Cu K Inorganic materials 0.000 description 4
- 229910017541 Cu-K Inorganic materials 0.000 description 4
- BUUNILCKFRLOQJ-UHFFFAOYSA-N [Ti].[V].[Ni] Chemical compound [Ti].[V].[Ni] BUUNILCKFRLOQJ-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910004688 Ti-V Inorganic materials 0.000 description 1
- 229910010968 Ti—V Inorganic materials 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of containing accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel and preparation method thereof, belong to hydrogen storage material field.This hydrogen storage material expression formula is Ti
1.4v
0.6ni? +? x? wt%? NaAlH
4, wherein, 1 & lt; X & lt; 5.The present invention also provides a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and the method is by Ti, V and Ni metal, puts into vacuum arc furnace melting and becomes alloy pig, by the casting integrated machine of vacuum chilling, prepares the Ti containing I phase
1.4v
0.6the accurate brilliant composite diphase material strip of Ni; Then through grinding, put into ball grinder ball milling and obtain together with sodium alanate, described ball material weight ratio is (20 ~ 10): 1, does is Ball-milling Time 10 ~ 30? min.Of the present invention containing the Entropy Changes increase in the process of discharge and recharge of the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, improve battery cycle life and loading capacity.<!--1-->
Description
Technical field
The invention belongs to hydrogen storage material technical field, be specifically related to a kind of containing accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel and preparation method thereof.
Background technology
The storage volumetric hydrogen density of hydrogen storage material is large, security is high, convenient transportation, processing ease, is to expect as the material of clean energy, and gets most of the attention as the new storage of energy and transition material.
Icosahedral phases (I phase) containing icosahedron type, a large amount of tetrahedron spaces is there is in its structure, hydrogen atom is more prone to enter in tetrahedral coordination field, therefore the accurate crystalline substance of I phase possesses Large Copacity hydrogen storage property in theory, in addition, the chemical element that Ti based Quasi-crystals comprises and hydrogen have good avidity, provide favourable hydrogen-metallochemistry environment, and excellent in stability, so far with Ti, Zr and Ni is that the TiZrNi system alloy of constitution element is widely used, but hydrogen balance presses through the hydrogen storage property that low feature governs TiZrNi alloy always, its performance in electrochemical hydrogen storage performance is unsatisfactory, TiVNi system alloy and TiZrNi system alloy phase ratio, dynamic effect (activity) is higher, hydrogen releasing ability is more excellent, this at least with Ti, V and Ni is in the Ti system quasicrystal material of constitution element, preferred use Ti
1.4v
0.6alloy (WenHuetal., the Electrochemicalhydrogenstoragein (Ti of Ni composition
1-xv
x)
2ni (x=0.05-0.3) alloyscomprisingicosahedralquasicrystallinephase [J], ElectrochimicaActa, 2009, Vol.54, P2770-2773).
Exercise question disclosed on December 21st, 2005 Patent Office of the People's Republic of China is the CN1709564A patent of " a kind of regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and preparation method thereof ", the invention provides the single icosahedron quasicrystal material with hydrogen-storage function, the accurate brilliant Forming ability of this alloy is strong, Thermodynamically stable, there is excellent hydrogen sucking function and excellent electrochemical discharge capacity, can be applicable to gaseous state hydrogen storage material and cell negative electrode material, but single icosahedron Icosahedral phases preparation difficulty, in the long-time ma process of 100 ~ 200h, the Icosahedral phases produced is easy to be partially converted to solid solution phase, its storage stabilized hydrogen is not high, obstacle is brought in practical application.
Disclosed on September 1st, 2010 Patent Office of the People's Republic of China, exercise question is " the icosahedral quasicrystal hydrogen storage material containing amorphous and quenching production method thereof " CN101816915A patent, the advantage of this invention is: prepared the icosahedral quasicrystal hydrogen storage material containing amorphous, meet hydrogen storage material at chemical hydrogen-storaging, gaseous state storage hydrogen is to the demand of hydrogen storage material diversification of varieties, it stores hydrogen 250 times at gaseous state, reversible hydrogen adsorption and desorption amount is close to 2.3mass%, but the potential that TiZrNi Icosahedral phases shows at gaseous state storage hydrogen does not extend on electrochemical hydrogen storage completely, and the palladium metal in alloy system, higher cost makes its possibility in production application limited.
The super Entropy Changes elements such as magnesium, lithium, potassium, sodium and zinc are added in hydrogen storage material, promote hydrogen storage material loading capacity, multiplying power discharging ability in the effective way of interior chemical property, representative invention for: disclosed on May 2nd, 2012 Patent Office of the People's Republic of China, exercise question is " AB
4.7the super Entropy Changes method of non-stoichiometric hydrogen storage material " CN102437317A patent.This invention advantage be by system of elementss such as the magnesium, lithium, potassium, sodium and the zinc that add in prior art and preliminary theoryization to the height of " super Entropy Changes ", but do not expand to accurate crystal class hydrogen storage material.
On December 15th, 2010, Patent Office of the People's Republic of China disclosed the CN101914699A patent of invention that exercise question is " adding the fused salt electrosynthesis method of magnesium, lithium, sodium and potassium in hydrogen storage material ".The advantage of this invention is super for four kinds, magnesium, lithium, sodium and potassium Entropy Changes element, by same fused-salt bath with electric osmose with electrolysis interaction mode is safe and effective joins in hydrogen storage material; But its shortcoming with: this kind of Adding Way is all relatively high for the equipment requirements of degree of being skilled in technique requirement and fused salt electrosynthesis indispensability, show slightly not enough in the practicality such as simple and equipment investment is little in technique, its galvanic deposit matrix selected also is the common hydrogen storage material of non-accurate crystal class.
The usual chemically reactives of its simple substance of these elements such as magnesium, lithium, potassium, sodium are all very strong, and except fused salt electrosynthesis method joins hydrogen storage material China and foreign countries, another kind of effective means is mechanical alloying.List in table 1 and join in high-energy ball milling tank by the simple substance of these super Entropy Changes elements such as magnesium, lithium, potassium, sodium or compound, synthesize hydrogen storage material by mechanical alloying method, its representative patents disclosed in Patent Office of the People's Republic of China is in table 1.
Table 1
Listed by table 1, the simple substance of these elements such as magnesium, lithium, potassium, sodium or compound are joined in high-energy ball milling tank the invention utilizing mechanical alloying method to synthesize hydrogen storage material, Common advantages is simple to operate, practical.
To sum up: take sodium alanate as aluminium, the carrier that adds of sodium, and carry out mechanical alloying with the Ti-V-based alloy containing icosahedral quasicrystal phase, obtain the hydrogen storage material with super Entropy Changes performance and manufacture method thereof and have no the open and article of patent and report.
Summary of the invention
The object of the invention is to provide a kind of containing accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel and preparation method thereof.Cycle life and the loading capacity of battery should be effectively raised containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel.
First the present invention provides a kind of containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and its expression formula is Ti
1.4v
0.6ni+xwt%NaAlH
4, wherein, 1<x<5.
The present invention also provides a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, comprises the steps:
Step one: according to Ti
1.4v
0.6ni is accurate, and brilliant complex phase hydrogen storage material composition expression formula takes Ti metal, V metal and Ni metal, puts into vacuum arc furnace melting and becomes alloy pig, by the casting integrated machine of vacuum chilling, prepare the Ti containing I phase
1.4v
0.6the accurate brilliant composite diphase material strip of Ni;
Step 2: the Ti that step one is obtained
1.4v
0.6the accurate brilliant composite diphase material strip grinding of Ni, obtains Ti
1.4v
0.6the accurate brilliant composite diphase material powder of Ni;
Step 3: take the Ti that sodium alanate and step 2 obtain respectively
1.4v
0.6the accurate brilliant composite diphase material powder of Ni, puts into ball grinder ball milling, and obtain a kind of containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, described ball material weight ratio is (20 ~ 10): 1, and Ball-milling Time is 10 ~ 30min.
Preferably, described Ti
1.4v
0.6ni is accurate, and brilliant composite diphase material size of powder particles is 200 ~ 400 orders.
Preferably, described sodium alanate and Ti
1.4v
0.6the weight percent of the accurate brilliant composite diphase material powder of Ni is (1wt% ~ 5wt%): (99wt% ~ 95wt%).
Preferably, described ball grinder is stainless steel jar mill.
Preferably, the diameter of described stainless steel jar mill is 4 ~ 15mm.
Preferably, the vibrational frequency of described ball grinder is 200 ~ 1000 revs/min.
Preferably, described ball material weight ratio is 10:1.
Preferably, described Ball-milling Time is 15min.
Beneficial effect
(1) the present invention's one is containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, that super Entropy Changes element aluminum, sodium element are added in the accurate brilliant composite diphase material of titanium vanadium nickel, adding of aluminium, sodium element makes alloy Entropy Changes in the process of discharge and recharge increase, improve cycle life and the loading capacity of battery, in the accurate brilliant material complex phase material of titanium vanadium nickel after doping 1 % by weight sodium alanate, maximum discharge capacity is 299.2mAh/g, after 80 circulations, and Ti
1.4v
0.6ni+NaAlH
4the capacity of composite diphase material is all higher than Ti
1.4v
0.6the accurate brilliant composite diphase material of Ni;
(2) one of the present invention is containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, in the titanium vanadium nickel hydrogen storage material with I phase, be doped into the complex hydrides sodium alanate with tetrahedral structure form the composite hydrogen storage material containing aluminium, sodium, in the composite alloy of gained, sodium stripping in alkali lye (electrolyte solution), hydrogen storage material is made to form micropore, improve Ni/MH battery cathode electro catalytic activity, sodium is dissolved in alkali lye and forms NaOH simultaneously, serve the effect of protection anode, improve battery performance;
(3) the present invention passes through high energy ball mill, by the method for mechanical alloying, take sodium alanate as carrier, aluminium, sodium element are added in titanium vanadium nickel quasicrystal material, mechanical milling process is controlled, at guarantee Ti by adjusting the vibrational frequency of ball grinder, ratio of grinding media to material, the quality of ball and Ball-milling Time
1.4v
0.6successfully super entropy element aluminum, sodium are added and formed containing accurate brilliant complex phase hydrogen storage material under the prerequisite that in Ni, I phase is not destroyed, wherein a small amount of sodium, aluminium atom enter in the crystalline network of I phase, produce lattice distortion effect, improve crystalline-granular texture, increase diffusion of protons rate, improve battery cathode catalytic activity, and then improve the multiplying power discharging property of hydrogen storage material system.
Accompanying drawing explanation
Fig. 1 is NaAlH
4, Ti
1.4v
0.6the XRD figure containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel that Ni and embodiment 1 ~ 3 obtain;
Fig. 2 is Ti
1.4v
0.6ni and the scanning electron microscope image containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel obtained with embodiment 1;
Fig. 3 is with Ti
1.4v
0.6what Ni quasicrystalline alloy and embodiment 1 ~ 3 obtained contains simulated battery cycle index and the loading capacity graph of relation that the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel is negative electrode active material.
Embodiment
First the present invention provides a kind of containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and its expression formula is Ti
1.4v
0.6ni+xwt%NaAlH
4, wherein, 1<x<5, is preferably 1<x<3.
The present invention also provides a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, comprises the steps:
Step one: according to Ti
1.4v
0.6ni is accurate, and brilliant complex phase hydrogen storage material composition expression formula takes Ti metal, V metal and Ni metal, puts into vacuum arc furnace melting and becomes alloy pig, by the casting integrated machine of vacuum chilling, prepare the Ti containing I phase
1.4v
0.6the accurate brilliant composite diphase material strip of Ni;
Step 2: the Ti that step one is obtained
1.4v
0.6the accurate brilliant composite diphase material strip grinding of Ni, forms Ti
1.4v
0.6the accurate brilliant composite diphase material powder of Ni;
Step 3: take the Ti that sodium alanate and step 2 obtain respectively
1.4v
0.6the accurate brilliant composite diphase material powder of Ni, puts into ball grinder ball milling, and obtain a kind of containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, described ball material weight ratio is (20 ~ 10): 1, and Ball-milling Time is 10 ~ 30min.
The present invention is first according to Ti
1.4v
0.6ni is accurate, and brilliant complex phase hydrogen storage material composition expression formula takes Ti metal (purity is 99.7%), V metal (purity 99.9%) and Ni metal (purity 99.5%), put into non-consumable arc furnace and be smelted into alloy pig, by the casting integrated machine of vacuum chilling, prepare the Ti containing I phase
1.4v
0.6the accurate brilliant composite diphase material strip of Ni, described strip thickness is preferably 25 ~ 45 μm, and be more preferably 35 μm, width is preferably 2 ~ 3mm, is more preferably 2.5mm.
Described vacuum arc furnace melting raw material is the method that this area is commonly used, and is specially: vacuum arc melting furnace is evacuated to 10
-3high-purity argon gas to 0.5 ± 0.1 normal atmosphere is filled with after Pa, the purity of described argon gas is 99.999%(percent by volume), Ti metal, V metal and Ni metal are put into vacuum arc fumace and carries out melting, melting 2-4 time, each melting 1-3min, be preferably 2min, flame current is 250 ~ 300A, come out of the stove after naturally cooling, obtain alloy pig.
Above-mentioned alloy pig is manufactured all-in-one by vacuum chilling, prepares the Ti containing I phase
1.4v
0.6the accurate brilliant composite diphase material strip of Ni, concrete technology is: open in bottom in the silica tube of an about 0.3-0.5mm aperture and put into above-mentioned alloy pig, be placed in the casting integrated machine of vacuum chilling, be evacuated to 1 × 10
-3mPa-5 × 10
-3mPa, is preferably 3.0 × 10
-3mPa, is filled with high-purity argon gas to 0.5 ± 0.1 normal atmosphere, and utilize induction heating by the alloy pig fusing in silica tube under 2000 ± 100 DEG C of conditions, spraying pressure 0.1-0.2MPa, copper roller linear velocity is 20-40m/s, is preferably 34m/s, obtains the Ti containing I phase
1.4v
0.6the accurate brilliant composite diphase material strip of Ni.
By Ti obtained above
1.4v
0.6the accurate brilliant composite diphase material strip grinding of Ni, preferably grinds with porcelain alms bowl, forms Ti
1.4v
0.6the accurate brilliant composite diphase material powder of Ni, then by sifter device by Ti
1.4v
0.6the accurate brilliant composite diphase material powder of Ni divides makes different size, preferred Ti
1.4v
0.6the accurate brilliant composite diphase material size of powder particles of Ni is between 200 ~ 400 orders.
By Ti obtained above
1.4v
0.6the accurate brilliant composite diphase material powder of Ni and sodium alanate, transfer in ball grinder in high-purity argon atmosphere and carry out ball milling, described ball material weight ratio is (20 ~ 10): 1, be preferably 10:1, Ball-milling Time is 10 ~ 30min, be preferably 15min, described ball grinder is preferably stainless steel jar mill, the diameter of stainless steel jar mill is preferably 4 ~ 15mm, the vibrational frequency of ball grinder is preferably 200 ~ 1000 revs/min, ball grinder is taken off from ball mill, in high-purity argon atmosphere glove box, open ball grinder obtains a kind of containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and sealing is placed in preservation in moisture eliminator.Described sodium alanate and Ti
1.4v
0.6the weight percent of the accurate brilliant composite diphase material powder of Ni is (1wt% ~ 5wt%): (99wt% ~ 95wt%).
A kind of phase structure containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel of the present invention uses X-ray diffraction method (XRD) to characterize, and adopt Cu-K α target during test, continuous sweep speed is 2 °/min, sweep limit 20 ° ~ 80 °.
The present invention's one adopts DC-5 type cell tester containing the accurate brilliant complex phase hydrogen storage material electrochemical hydrogen storage performance test of aluminium sodium titanium vanadium nickel, test process carries out in simulation ni-mh experimental cell, battery production method is specially: using the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel that contains of the present invention as the active substance in ni-mh experimental cell negative pole, this active substance is mixed with the carbonyl nickel powder of 5 times of weight as collector, tabletting machine is utilized to cool down the negative pole of the molded disk for diameter 10mm as battery, the lug of this negative pole is adopted the tweezer silk of diameter 1mm and is connected with negative plate by impulsed spot welding mode, the positive pole of experimental cell adopts the nickel hydroxide (Ni (OH) of commodity sintering
2/ NiOOH), the polypropylene-base barrier film of wettability and good air permeability then selected by the barrier film between positive and negative electrode, and ionogen is the KOH aqueous solution of concentration 6M.
In order to understand the present invention further, in further detail the present invention is described below in conjunction with embodiment, but the present invention has more than and is defined in these embodiments.
Sodium alanate used in embodiment is commercial, and purity is 99.3%.
Embodiment 1: containing accurate brilliant complex phase hydrogen storage material expression formula: the Ti of aluminium sodium titanium vanadium nickel
1.4v
0.6ni+1wt%NaAlH
4, this material preparation method is as follows:
(1) vacuum arc melting furnace is evacuated to 10
-3be filled with purity 99.999%(percent by volume after Pa) 0.5 normal atmosphere high-purity argon gas as shielding gas, 11gTi metal (purity is 99.7%), 5.016gV metal (purity 99.9%) and 9.632gNi metal (purity 99.5%) are put into vacuum arc fumace and carries out melting, flame current is 300A, melting 4 times, each melting 2min, naturally cooling is come out of the stove, and obtains alloy pig; Open in bottom in the silica tube of 0.5mm aperture and put into above-mentioned alloy pig, be placed in the casting integrated machine of vacuum chilling, be evacuated to 3.0 × 10
-3during MPa, be filled with high-purity argon gas to 0.5 normal atmosphere, utilize induction heating by the alloy nail fusing in silica tube at 2000 DEG C, spraying pressure 0.1MPa, copper roller linear velocity is 34m/s, and obtaining strip thickness is 35 μm, and width is the Ti containing I phase of 2.5mm
1.4v
0.6the accurate brilliant composite diphase material strip of Ni;
(2) by Ti that above-mentioned steps (1) obtains
1.4v
0.6ni is accurate, and brilliant composite diphase material strip porcelain alms bowl grinds, by sifter device by Ti
1.4v
0.6ni is accurate, and brilliant composite diphase material powder divides work 200 object powder;
(3) 9.9gTi that accurate weighing above-mentioned steps (2) obtains is distinguished
1.4v
0.6the accurate brilliant composite diphase material powder of Ni and 0.1g sodium alanate, load in the glove box being filled with high-purity argon atmosphere in stainless steel jar mill and carry out ball milling, steel ball size is 4mm, ratio of grinding media to material is 10:1, vibrational frequency 200 revs/min, Ball-milling Time 10min, takes off ball grinder from ball mill, in high-purity argon atmosphere glove box, open ball grinder obtain containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and sealing is placed in preservation in moisture eliminator.
As shown in Figure 1, adopt Cu-K α target during test, continuous sweep speed is 2 °/min to the XRD figure containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel that embodiment 1 obtains, sweep limit 20 ° ~ 80 °.
Fig. 2 is Ti
1.4v
0.6ni and the scanning electron microscope image containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel obtained with embodiment 1; A figure in Fig. 2 is Ti
1.4v
0.6the scanning electron microscopic picture of Ni quasicrystalline alloy, b figure in Fig. 2 is the scanning electron microscopic picture of doping massfraction 1% containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, as can be seen from the figure the hydrogen storage material sample surfaces of adulterated al sodium hydride has microvoid structure, and the appearance of microvoid structure improves Ni/MH battery cathode electro catalytic activity.
Embodiment 2: containing accurate brilliant complex phase hydrogen storage material expression formula: the Ti of aluminium sodium titanium vanadium nickel
1.4v
0.6ni+3wt%NaAlH
4, this material preparation method is as follows:
Step (1) and step (2) are with embodiment 1;
(3) the above-mentioned 9.7gTi of difference accurate weighing
1.4v
0.6the accurate brilliant composite diphase material powder of Ni and 0.3g sodium alanate, load in the glove box being filled with high-purity argon atmosphere in stainless steel jar mill and carry out ball milling, steel ball size is 10mm, ratio of grinding media to material is 10:1, vibrational frequency 800 revs/min, Ball-milling Time 15min, takes off ball grinder from ball mill, in high-purity argon atmosphere glove box, open ball grinder obtain containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and sealing is placed in preservation in moisture eliminator.
As shown in Figure 1, adopt Cu-K α target during test, continuous sweep speed is 2 °/min to the XRD figure containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel that embodiment 2 obtains, sweep limit 20 ° ~ 80 °.
Embodiment 3: containing accurate brilliant complex phase hydrogen storage material expression formula: the Ti of aluminium sodium titanium vanadium nickel
1.4v
0.6ni+5wt%NaAlH
4, this material preparation method is as follows:
Step (1) and step (2) are with embodiment 1;
(3) the above-mentioned 9.5gTi of difference accurate weighing
1.4v
0.6the accurate brilliant composite diphase material powder of Ni and 0.5g sodium alanate, load in the glove box being filled with high-purity argon atmosphere in stainless steel jar mill and carry out ball milling, steel ball size is 15mm, ratio of grinding media to material is 20:1, vibrational frequency 1000 revs/min, Ball-milling Time 30min, takes off ball grinder from ball mill, in high-purity argon atmosphere glove box, open ball grinder obtain containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and sealing is placed in preservation in moisture eliminator.
As shown in Figure 1, adopt Cu-K α target during test, continuous sweep speed is 2 °/min to the XRD figure containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel that embodiment 3 obtains, sweep limit 20 ° ~ 80 °.
Fig. 1 is NaAlH
4, Ti
1.4v
0.6the XRD figure containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel that Ni and embodiment 1 ~ 3 obtain; As can be seen from Figure 1, sodium alanate is primarily of the NaAlH with tetrahedral structure
4(spatial group I4
1/ a), have hexagonal simple structure (spatial group P63/mmc) Na and to have (spatial group Fm-3m) Al of face-centred cubic structure elementary composition.Ti
1.4v
0.6the XRD diffraction peak of Ni alloy contains I phase, Ti
2centroid cubic lattice structure (FCC) phase of Ni type and body centered structure structure (BCC) solid solution phase.By Ti
1.4v
0.6after the mixture of the sodium alanate of Ni alloy utilizes high energy ball mill mechanical alloying, make Ti
2the diffraction peak of Ni phase obviously broadens.
Embodiment 4
What embodiment 1 ~ 3 obtained respectively mixes with weight ratio 1: 5 containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel and carbonyl nickel powder, the powdered mixture of gained is applied to the pressure of 15MPa, etc. calm be pressed into diameter 10mm and the disk of thickness 1.5mm as negative pole, the lug of this negative pole is adopted the nickel wire of diameter 1mm and is connected with negative plate by impulsed spot welding mode, and the positive pole of ni-mh experimental cell adopts the nickel hydroxide (Ni (OH) of commodity sintering
2/ NiOOH), the polypropylene-base barrier film of wettability and good air permeability then selected by the barrier film between positive and negative electrode, and ionogen is the KOH aqueous solution of concentration 6M.
Will with Ti
1.4v
0.6what Ni quasicrystalline alloy and embodiment 1 ~ 3 obtained is negative electrode active material containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, and simulated battery carries out performance test, the Measurement and Computation method of cyclical stability is: be that 60mA/g charges with current density by battery, discharge with 30mA/g.Its formula is: S
n=(maximum discharge capacity of the loading capacity of same battery after the n-th charge and discharge cycles/same battery) × 100%.
The Measurement and Computation method of multiplying power discharging property (HRD) is: charged with 60mA/g current density by the battery after activation, then discharge with different current densities, discharge current density is followed successively by 30mA/g, 60mA/g, 90mA/g, 120mA/g, 180mA/g and 240mA/g.Its formula is: the cell container of the same battery of HRD=(under the different discharge current density/cell container of same battery under 30mA/g discharge current density) × 100%.
Fig. 3 is with Ti
1.4v
0.6what Ni quasicrystalline alloy and embodiment 1 ~ 3 obtained contains simulated battery cycle index and the loading capacity graph of relation that the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel is negative electrode active material.In figure, curve 1 represents Ti
1.4v
0.6ni, curve 2 represents Ti
1.4v
0.6ni+1wt%NaAlH
4, curve 3 represents Ti
1.4v
0.6ni+3wt%NaAlH
4, curve 4 represents Ti
1.4v
0.6ni+5wt%NaAlH
4, as shown in Figure 3, all batteries all only need twice charge discharge circulation to reach activation, and loading capacity significantly improves because of the interpolation of sodium alanate, and concrete changing conditions is in shown in table 2, table 3:
Table 2
Table 3
Table 2 is with Ti
1.4v
0.6what Ni quasicrystalline alloy and embodiment 1 ~ 3 obtained contains the stable circulation performance data that the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel is the simulated battery of negative electrode active material, and table 3 is with Ti
1.4v
0.6the multiplying power discharging property data of what Ni quasicrystalline alloy and embodiment 1 ~ 3 obtained containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel the is simulated battery of negative electrode active material, as can be seen from table 2 and table 3, and comprise Ti
1.4v
0.6the negative pole of Ni quasicrystalline alloy is compared, and the simulated battery to be negative electrode active material containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel of the present invention has more excellent efficient discharge performance.
Claims (9)
1., containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, it is characterized in that, its expression formula is Ti
1.4v
0.6ni+xwt%NaAlH
4, wherein, 1<x<5.
2. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 1, is characterized in that, comprise the steps:
Step one: according to Ti
1.4v
0.6ni is accurate, and brilliant complex phase hydrogen storage material composition expression formula takes Ti metal, V metal and Ni metal, puts into vacuum arc furnace melting and becomes alloy pig, by the casting integrated machine of vacuum chilling, prepare the Ti containing I phase
1.4v
0.6the accurate brilliant composite diphase material strip of Ni;
Step 2: the Ti that step one is obtained
1.4v
0.6the accurate brilliant composite diphase material strip grinding of Ni, forms Ti
1.4v
0.6the accurate brilliant composite diphase material powder of Ni;
Step 3: take the Ti that sodium alanate and step 2 obtain respectively
1.4v
0.6the accurate brilliant composite diphase material powder of Ni, puts into ball grinder ball milling, and obtain a kind of containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel, described ball material weight ratio is (20 ~ 10): 1, and Ball-milling Time is 10 ~ 30min.
3. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 2, is characterized in that, described Ti
1.4v
0.6ni is accurate, and brilliant composite diphase material size of powder particles is 200 ~ 400 orders.
4. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 2, is characterized in that, described sodium alanate and Ti
1.4v
0.6the weight percent of the accurate brilliant composite diphase material powder of Ni is (1wt% ~ 5wt%): (99wt% ~ 95wt%).
5. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 2, it is characterized in that, described ball grinder is stainless steel jar mill.
6. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 5, it is characterized in that, the diameter of described stainless steel jar mill is 4 ~ 15mm.
7. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 2, it is characterized in that, the vibrational frequency of described ball grinder is 200 ~ 1000 revs/min.
8. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 2, it is characterized in that, described ball material weight ratio is 10:1.
9. a kind of preparation method containing the accurate brilliant complex phase hydrogen storage material of aluminium sodium titanium vanadium nickel according to claim 2, it is characterized in that, described Ball-milling Time is 15min.
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| Title |
|---|
| Electrochemical hydrogen storage in (Ti1−xVx)2Ni (x=0.05-0.3) alloys comprising icosahedral quasicrystalline phase;Hu Wen,et al.;《Electrochimica Acta》;20081028;第54卷(第10期);2770-2773 * |
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