CN104294084B - Lithium-containing high entropy change Ti standard crystal hydrogen storage alloy and preparation method thereof - Google Patents
Lithium-containing high entropy change Ti standard crystal hydrogen storage alloy and preparation method thereof Download PDFInfo
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- CN104294084B CN104294084B CN201410531941.8A CN201410531941A CN104294084B CN 104294084 B CN104294084 B CN 104294084B CN 201410531941 A CN201410531941 A CN 201410531941A CN 104294084 B CN104294084 B CN 104294084B
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Abstract
The invention provides lithium-containing high entropy change Ti standard crystal hydrogen storage alloy and a preparation method thereof, and relates to the technical field of hydrogen storage materials. The lithium-containing high entropy change Ti standard crystal hydrogen storage alloy has good electrochemical hydrogen absorption and desorption circulation stability and excellent rate discharge property. The preparation method comprises the following steps: putting metals Ti, V and Ni in a non-stoichiometric ratio of Ti55V10Ni35 into a non-self-consumption vacuum arc furnace, repeatedly smelting for 4 times to be alloy ingots, and subsequently putting the alloy ingots into a vacuum quenching casting integrated machine to prepare thin Ti55V10Ni35 standard multiphase material strips containing a phase I; respectively weighing potassium chloride and lithium chloride in a mass ratio of 4:6 into a graphite crucible, and melting at 400-480 DEG C to form molten salt; and putting the obtained thin Ti55V10Ni35 standard multiphase material strips into the molten salt, supplying power to electrolyze so as to decompose lithium chloride in the molten salt, and enabling the metal lithium in the molten salt to enter gaps of Ti55V10Ni35, thereby forming the hydrogen storage alloy Ti55V10Ni35+Li.
Description
Technical field
The present invention relates to hydrogen storage material technical field, and in particular to a kind of Ti based Quasi-crystals hydrogen bearing alloy containing the high Entropy Changes of lithium and
Its preparation method.
Background technology
Ni-MH battery has many excellent specific properties such as pollution-free, high specific energy, high-power, fast charging and discharging, ruggedness and standby
Attract attention, the Ti base regular dodecahedron quasi-crystalline substances with high capacity hydrogen storage characteristic are the electrode materials as clear energy sources of new generation,
It is the candidate material of energy stores of new generation and conversion simultaneously.
The hydrogen-absorbing ability of metal or alloy chemical affinity mainly between hydrogen and metallic atom, metal hollow gap
Type, the actual size and total quantity in crystal space are relevant.Generally there can be two types with the lattice voids of hydrogen storage：It is octahedra and
Tetrahedron space.In most of transition metal, hydrogen tends in tetrahedron and octahedral interstices.Hydrogen molecule is first in table
Face and near surface are adsorbed, after decomposition, from surface to alloy diffusion inside, into crystal clearance position, when local hydrogen concentration
More than certain limit, hydride can be generated.In hydrogen discharge reaction, identical step can occur in reverse order, and hydrogen is from alloy
Inside diffuses to the surface, the hydrogen atom of alloy surface absorption generates molecule, is released in the form of molecule.And regular dodecahedron quasi-crystalline substance
It is made up of the rotationally symmetrical point group of regular dodecahedron, includes substantial amounts of tetrahedron space, therefore theoretically this kind of quasi-crystalline substance
Possesses good hydrogen storage ability.Research later shows that regular dodecahedron quasi-crystalline substance (Ti-Zr-Ni) is with very strong hydrogen storage energy
Power, each metallic atom can reach the level for absorbing two hydrogen atoms；So far TiZrNi systems with Ti, Zr and Ni as constitution element
Alloy is widely used, but hydrogen balance governs the hydrogen storage property of TiZrNi alloys always the characteristics of pressing through low, and which is in electrochemistry
Performance on hydrogen storage property is unsatisfactory.
Entitled " a kind of regular dodecahedron titanio with hydrogen-storage function disclosed on December 21st, 2005 Patent Office of the People's Republic of China
The CN1709564 A patents of quasicrystal material and preparation method thereof ", the invention provides the single positive icosahedro with hydrogen-storage function
Body quasicrystal material, the alloy quasi-crystalline substance Forming ability are strong, and Thermodynamically stable is put with excellent hydrogen sucking function and excellent electrochemistry
Capacitance, can be applicable to gaseous state hydrogen storage material and cell negative electrode material, but single regular dodecahedron Icosahedral phases prepares difficulty,
In the long-time ma process of 100-200h, the Icosahedral phases of generation are easy to be partially converted to solid solution phase, its storage hydrogen
Stability is not high, to bringing obstacle in practical application.
It is entitled disclosed in No. 1 Patent Office of the People's Republic of China of in September, 2010 " the icosahedral quasicrystal hydrogen storage material containing amorphous and its
Quenching production method " CN101816915 A patents, the advantage of the invention is：The storage of the icosahedral quasicrystal containing amorphous is prepared
Hydrogen material, meets hydrogen storage material in chemical hydrogen-storaging, gaseous state storage demand of the hydrogen to hydrogen storage material diversification of varieties, and which is store in gaseous state
Under hydrogen 250, reversible hydrogen adsorption and desorption amount is close to 2.3mass%, but the potential showed in gaseous state hydrogen storage by TiZrNi Icosahedral phases
Do not completely extend on electrochemical hydrogen storage, and the Metal Palladium in alloy system, higher cost makes which in actual production
May be limited using in.
The content of the invention
Embodiments of the invention provide a kind of Ti based Quasi-crystals hydrogen bearing alloys containing the high Entropy Changes of lithium and preparation method thereof, and this contains lithium
Electrochemical hydrogenation and dehydrogenation cyclical stability and excellent multiplying power discharging that quasi-crystalline substance hydrogen bearing alloy with high Entropy Changes characteristic has had
Energy.
To reach above-mentioned purpose, embodiments of the invention are adopted the following technical scheme that：
A kind of Ti based Quasi-crystals hydrogen bearing alloys containing the high Entropy Changes of lithium, the expression formula of the hydrogen bearing alloy is Ti55V10Ni35+ Li,
Wherein, metal Li enters Ti based Quasi-crystals Ti55V10Ni35Space in.
A kind of preparation method of above-mentioned hydrogen bearing alloy, including：
Step one：By metal Ti, V and Ni according to non-stoichiometric Ti55V10Ni35Ratio weigh, be then placed in it is non-from
In consumption vacuum arc furnace ignition, melt back 4 times is smelted into alloy pig, the alloy pig is put into vacuum chilling then casting integrated
In machine, the Ti containing I phases is prepared55V10Ni35Quasi-crystalline substance composite diphase material strip；
Step 2：Potassium chloride and lithium chloride that mass ratio is 4: 6 are weighed respectively, are put in graphite crucible, at 400-480 DEG C
Under the conditions of melt, formed melting fused salt；Then the Ti for step one being obtained55V10Ni35Quasi-crystalline substance composite diphase material strip is put into
In the fused salt of melting, be powered electrolysis, the lithium chloride in the fused salt is decomposed, and lithium metal is entered in making the fused salt
Ti55V10Ni35Space in, formed hydrogen bearing alloy Ti55V10Ni35+Li。
Optionally, it is described that the alloy pig is put in the casting integrated machine of vacuum chilling, prepare containing I phases
Ti55V10Ni35Quasi-crystalline substance composite diphase material strip, specifically includes：
The alloy pig is put into bottom to be provided with the quartz ampoule of diameter 0.3-0.5mm apertures, the quartz ampoule is placed in
In the casting integrated machine of the vacuum chilling, 1 × 10 is evacuated to-3MPa-5×10-3MPa, is filled with high-purity argon gas to 0.5 ± 0.1
Alloy pig in quartz ampoule is melted under the conditions of 2000 ± 100 DEG C, injection pressure 0.1- by individual atmospheric pressure using sensing heating
0.2MPa, copper roller linear velocity are 20-40m/s, obtain the Ti containing I phases55V10Ni35Quasi-crystalline substance composite diphase material strip,
Wherein, the Ti55V10Ni35The thickness of quasi-crystalline substance composite diphase material strip is 50～70 μm, and width is 2～3mm.
Optionally, the step 2 is specifically included：
By the Ti55V10Ni35Quasi-crystalline substance composite diphase material strip puts into the quartz ampoule that bottom is provided with diameter 0.5-1mm osculums
In, the quartz ampoule is immersed in the graphite crucible of the fused salt for being formed with melting by fixing device copper sheet；
A copper wire coil and the Ti are inserted in the quartz ampoule55V10Ni35Quasi-crystalline substance composite diphase material strip is contacted, and
The copper wire coil is not immersed in the fused salt of the melting；
Fixing device copper sheet is connected with iontophoresis device so that the Ti55V10Ni35Quasi-crystalline substance composite diphase material strip one is terminated
Negative pole, be connected a termination positive pole with the graphite crucible, is regulated and controled electric current, is electrolysed；30min is electrolysed under stabling current, is stopped
Only it is electrolysed；
At 380 DEG C hang salt protectiveness come out of the stove, negative pole is extracted rapidly and is put in rustless steel pannikin, and close the lid treat its from
Preserve during vacuum bag is put into after being so cooled to room temperature；
By the hydrogen bearing alloy Ti from the nearest formation of the quartzy bottom of the tube55V10Ni35+ Li takes out, and deionized water is repeatedly
Rinse 5-7 time, then the salt of removal surface solidification carry out drying preservation in baking oven.
Optionally, the electric current of the electrolysis that is powered is 0.3A, 0.6A or 0.9A.
In above-mentioned technical proposal, elemental lithium enters Ti based Quasi-crystals Ti55V10Ni35Space process be entropy increase process,
The lithium on alloyed powder surface and alkaline reaction and enter electrolyte, this process is the process that entropy is reduced, with Ti55V10Ni35Hydrogen storage is closed
Metallographic ratio, the addition of lithium make multiphase alloy Ti55V10Ni35+ Li Entropy Changes during discharge and recharge increases, and improves battery cathode
Catalysis activity, so that its discharge capacity is significantly improved.The dissolving of surface lithium simultaneously also leaves many for the diffusion of hydrogen
Passage, improves the multiplying power discharging property of battery.Test result indicate that：After oozing lithium, the discharge capacity of the quasi-crystalline substance is improved, and
Activate number of times completely to significantly reduce needed for initially, multiplying power discharging property is also improved.
Ooze lithium titanium vanadium nickel quasi-crystalline substance complex phase hydrogen bearing alloy Ti55V10Ni35The structure that lithium atom volume inside+Li enters I phases is empty
In gap, there is reversible reaction in charge and discharge process, with titanium vanadium nickel hydrogen bearing alloy Ti55V10Ni35Compare, the addition of lithium makes complex phase
Alloy Ti55V10Ni35+ Li Entropy Changes during discharge and recharge increases, additionally, lithium to generate Lithium hydrate in the alkaline electrolyte blunt
Change corrosion and efflorescence that film can prevent alloy electrode, therefore, the electrochemical hydrogen storage performance of the complex phase hydrogen storage material of quasi-crystalline substance containing lithium is more
Plus it is excellent, this cooperative effect makes that alloy system discharge capacity is higher and cyclical stability is more preferable.
The present invention's oozes lithium titanium vanadium nickel quasi-crystalline substance complex phase hydrogen bearing alloy Ti55V10Ni35+ Li is with titanium vanadium nickel complex phase hydrogen bearing alloy
For base, lithium is added by the method for fused salt electric osmose, preparation process is simple, safe, workable, can be by adjusting electric osmose
Electric current, the time control electric osmose process, ensure Ti55V10Ni35Lithium is successfully penetrated on the premise of not being destroyed by middle I phases
Ti55V10Ni35In quasicrystal structure space, increase proton diffusibility, improve battery cathode catalysis activity, and then improve hydrogen storage
The multiplying power discharging property of material system.
Description of the drawings
Fig. 1 is a kind of preparation method flow process of Ti based Quasi-crystals hydrogen bearing alloys containing the high Entropy Changes of lithium provided in an embodiment of the present invention
Schematic diagram；
Fig. 2 is a kind of structural representation of electrolysis unit provided in an embodiment of the present invention；
Fig. 3 is Ti provided in an embodiment of the present invention55V10Ni35The quasi-crystalline substance complex phase hydrogen storage material obtained with embodiment 1～3
Ti55V10Ni35The XRD figure of+Li；
Fig. 4 is with Ti55V10Ni35The quasi-crystalline substance complex phase hydrogen storage material Ti that quasicrystalline alloy and embodiment 1～3 are obtained55V10Ni35+
Simulated battery cycle-index and discharge capacity graph of relation of the Li for negative electrode active material；
Fig. 5 is with Ti55V10Ni35The quasi-crystalline substance complex phase hydrogen storage material Ti that quasicrystalline alloy and embodiment 1～3 are obtained55V10Ni35+
Multiplying power discharging property and discharge capacity graph of relation of the Li for negative electrode active material.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiments provide a kind of Ti based Quasi-crystals hydrogen bearing alloys containing the high Entropy Changes of lithium, the expression of the hydrogen bearing alloy
Formula is Ti55V10Ni35+ Li, wherein, metal Li enters Ti based Quasi-crystals Ti55V10Ni35Space in.
The embodiment of the present invention additionally provides a kind of above-mentioned Ti based Quasi-crystals hydrogen bearing alloys containing the high Entropy Changes of lithium, preparation side
Method, as shown in figure 1, the method comprising the steps of：
S1, prepare the Ti containing I phases55V10Ni35Quasi-crystalline substance composite diphase material strip.
By metal Ti, V and Ni according to non-stoichiometric Ti55V10Ni35Ratio weigh, be then placed in non-consumable vacuum
Alloy pig is smelted in electric arc furnace, in order to ensure composition is uniform, melt back 4 times is smelted into alloy pig, then by the alloy
Ingot is put in the casting integrated machine of vacuum chilling, prepares the Ti containing I phases55V10Ni35Quasi-crystalline substance composite diphase material strip.
Specifically, the present invention is first according to quasi-crystalline substance complex phase hydrogen storage material composition expression formula Ti55V10Ni35Weigh Ti metals (pure
Spend for 99.7%), V metals (purity 99.9%) and Ni metals (purity 99.5%), be put in non-consumable arc furnace repeatedly
Melting, forms alloy pig；Then, the alloy pig is put into bottom to be provided with the quartz ampoule of diameter 0.3-0.5mm apertures, should
Quartz ampoule is placed in the casting integrated machine of vacuum chilling, it is evacuated to 1 ×10 -3MPa-5×10-3MPa, preferably 3.0 × 10-3MPa,
High-purity argon gas are filled with to 0.5 ± 0.1 atmospheric pressure, using sensing heating under the conditions of 2000 ± 100 DEG C by the conjunction in quartz ampoule
Ingot melts, injection pressure 0.1-0.2MPa, and copper roller linear velocity is 20-40m/s, preferably 34m/s, is obtained containing I phases
Ti55V10Ni35Quasi-crystalline substance composite diphase material strip.Wherein, the Ti55V10Ni35The thickness of quasi-crystalline substance composite diphase material strip is 50～70 μm,
Width is 2～3mm.
S2, hydrogen bearing alloy Ti is prepared by molten-salt electrolysis55V10Ni35+Li。
Potassium chloride and lithium chloride that mass ratio is 4: 6 are weighed respectively, are put in graphite crucible, under the conditions of 400-480 DEG C
Fusing, forms the fused salt of melting；Then the Ti for step one being obtained55V10Ni35Quasi-crystalline substance composite diphase material strip is put into melting
In fused salt, be powered electrolysis, the lithium chloride in the fused salt is decomposed, and lithium metal enters into Ti in making the fused salt55V10Ni35
Space in, formed hydrogen bearing alloy Ti55V10Ni35+Li。
Specifically, as shown in Fig. 2 by Ti obtained above55V10Ni35Quasi-crystalline substance composite diphase material strip is put into bottom and is provided with
It is in the quartz ampoule of osculum (diameter 0.5-1mm, it is ensured that fused salt can be infiltered, and quasi-crystalline substance band will not leak in crucible), excellent
The electric osmose fused salt mass ratio 40%LiCl-60%KCl of choosing, preferred crucible are graphite crucible, have melting in graphite crucible
LiCl-KCl fused salts, the temperature of electric osmose is：400-480 DEG C, preferred heating furnace (as shown in Fig. 2 heating furnace include adiabatic wall and
Heated wall) 450 DEG C of temperature, will be equipped with Ti after fused salt all melts55V10Ni35The quartzy Gutron of quasi-crystalline substance composite diphase material strip
Cross outside fixing device (copper sheet as shown in Figure 2) to be immersed in fused salt crucible.In order to form complete loop with outside, I
A copper wire coil and Ti are inserted in quartz ampoule55V10Ni35Quasi-crystalline substance composite diphase material strip is contacted, and pays special attention to be inserted into
Ti55V10Ni35The copper wire coil of quasi-crystalline substance composite diphase material strip can not be immersed in fused salt, prevent the short-circuit (inside of the iontophoresis device
Plane graph such as Fig. 2).Then the negative pole of the iontophoresis devices such as the copper sheet of fixing device and electric cabinet is connected, it is ensured that Ti55V10Ni35It is accurate
Brilliant composite diphase material strip one terminates negative pole, and be connected a termination positive pole with graphite crucible, after the inspection of line is errorless, power-on, and control
Voltage processed, regulates and controls electric current, carries out electric osmose.Due to being limited by termination and external environment condition, the more difficult control of experimentation voltage,
The embodiment of the present invention is tested using electric current as variable, has stable bubble to produce (Cl by observing in crucible2), illustrate electric osmose
Start.The electric osmose half an hour under stabling current (0.3A, 0.6A, 0.9A), stop electric osmose, closing switch.And salt guarantor is hung at 380 DEG C
Shield property is come out of the stove, and negative pole is extracted rapidly and is put in rustless steel pannikin, and to close the lid and vacuum is put into after which naturally cools to room temperature
Preserve in bag.The Ti after lithium will be oozed55V10Ni35That is Ti55V10Ni35+ Li quasi-crystalline substance bands, take out from quartz ampoule, preferably connect
The Ti of nearly quartz bottom of the tube55V10Ni35+ Li quasi-crystalline substance bands, and deionized water wash away quasi-crystalline substance belt surface solidification salt (rinse repeatedly
5-7 time), drying preservation is then carried out in baking oven.
Optionally, the lithium titanium vanadium nickel quasi-crystalline substance i.e. Ti of composite diphase material can be oozed by obtained above55V10Ni35+ Li quasi-crystalline substance bands grind
Mill, is preferably ground with porcelain alms bowl, forms Ti55V10Ni35+ Li quasi-crystalline substance composite diphase material powder, then will ooze lithium with sifter device
Ti55V10Ni35+ Li quasi-crystalline substance composite diphase material powder is allocated as different size, preferred Ti55V10Ni35Quasi-crystalline substance composite diphase material size of powder particles exists
Between 200-300 mesh.
Ti provided in an embodiment of the present invention55V10Ni35The phase structure of+Li quasi-crystalline substance composite diphase materials uses X-ray diffraction method
(XRD) characterize, during test adopt Cu-K α targets, continuous scanning speed be 4 °/min, 20 ° -80 ° of sweep limitss.Its electrochemical hydrogen storage
Performance test adopts DC-5 type cell testers, test process to carry out in simulation ni-mh experimental cell, battery production method tool
Body is：Using the vanadium nickel quasi-crystalline substance complex phase hydrogen bearing alloy of titanium containing lithium of the present invention as the active substance in ni-mh experimental cell negative pole, will
Carbonyl nickel powder of the active substance with 5 times of weight as collector is mixed homogeneously, and is cooled down using tablet machine molded for diameter
Negative pole of the disk of 10mm as battery, the lug of the negative pole using diameter 1mm nickel wire and by impulsed spot welding mode with it is negative
Pole piece connects, and the positive pole of experimental cell adopts the nickel hydroxide (Ni (OH) of commodity sintering2/ NiOOH), the barrier film between both positive and negative polarity
The polypropylene type barrier film of wettability and good air permeability, KOH aqueous solution of the electrolyte for concentration 6M are selected then.
Below, illustrate the present invention with the following Examples in further detail, the present invention is not only defined in these certainly
Embodiment.
Embodiment 1：When electroosmotic current is 0.3A, hydrogen bearing alloy Ti55V10Ni35The preparation method of+Li is as follows：
(1) vacuum arc melting furnace is evacuated to after 10-3Pa and is filled with the 0.5 of purity 99.999% (percentage by volume)
Individual atmospheric pressure high-purity argon gas as protective gas, by 11g Ti metals (purity is 99.7%), 2.125g V metal (purity
99.9%) melting is carried out and during 8.560g Ni metals (purity 99.5%) are put into vacuum arc furnace ignition, arc current is 300A, is melted
Refining 4 times, each melting 2min, natural cooling come out of the stove, and obtain alloy pig；It is put in the quartz ampoule of 0.5mm apertures is driven in bottom
Alloy pig is stated, is placed in the casting integrated machine of vacuum chilling, is evacuated to 3.0 × 10-3During MPa, high-purity argon gas are filled with big to 0.5
Alloy nail in quartz ampoule is melted at 2000 DEG C, injection pressure 0.1MPa by air pressure using sensing heating, and copper roller linear velocity is
34m/s, obtains strip thickness for 35 μm, and width is the Ti containing I phases of 2.5mm55V10Ni35Quasi-crystalline substance composite diphase material strip.
(2) Ti that above-mentioned steps (1) are obtained55V10Ni35Quasi-crystalline substance composite diphase material strip puts into the stone that bottom is provided with osculum
Ying Guanzhong (diameter 0.5-1mm, it is ensured that fused salt can be infiltered, and quasi-crystalline substance band will not leak in crucible).At 450 DEG C,
After the electric osmose fused salt in graphite crucible all melts, the quartz ampoule of quasi-crystalline substance band is will be equipped with by outside fixing device (copper sheet)
It is immersed in fused salt crucible.In order to form complete loop with outside, we insert a copper wire coil in quartz ampoule with standard
Crystal zone contacts, and the copper wire coil for paying special attention to be inserted in quasi-crystalline substance band can not be immersed in fused salt, prevent short circuit.Then will be fixed
The iontophoresis devices such as device and electric cabinet are connected, it is ensured that Ti55V10Ni35Quasi-crystalline substance composite diphase material strip one terminates negative pole, is connected with crucible
One termination positive pole, after the inspection of line is errorless, power-on, control voltage so that loop current is 0.5A.By observing in crucible
There is stable bubble to produce (Cl2), illustrate that electric osmose starts, the electric osmose half an hour under the electric current, stop electric osmose, closing switch.And
Hang salt protectiveness to come out of the stove at a temperature of 380 DEG C, negative pole is extracted rapidly and is put in rustless steel pannikin, and is closed the lid and treated which naturally cools to
Preserve during vacuum bag is put into after room temperature.
(3) Ti after lithium will be oozed55V10Ni35+ Li quasi-crystalline substance bands, take out from quartz ampoule, are preferably close to quartz ampoule bottom
The Ti in portion55V10Ni35+ Li quasi-crystalline substance bands, and deionized water washes away the salt of quasi-crystalline substance belt surface solidification, is then dried in baking oven
It is dry to preserve.
The hydrogen storage material Ti that embodiment 1 is obtained55V10Ni35The XRD figure of+Li as shown in figure 3, adopt Cu-K α targets during test,
Continuous scanning speed is 4 °/min, 20 ° -80 ° of sweep limitss.
Embodiment 2：When electroosmotic current is 0.6A, hydrogen bearing alloy Ti55V10Ni35The preparation method of+Li is as follows：Step (1)
With step (3) with embodiment 1；Step (2) controls electric osmose loop current in 0.6A.
The hydrogen storage material Ti that embodiment 2 is obtained55V10Ni35The XRD figure of+Li as shown in figure 3, adopt Cu-K α targets during test,
Continuous scanning speed is 4 °/min, scans and encloses 20 ° -80 °.
Embodiment 3：Hydrogen bearing alloy Ti55V10Ni35The preparation method of+Li is as follows：Step (1) and step (3) are with embodiment 1；
Step (2) controls electric osmose loop current in 0.9A.
The hydrogen storage material Ti that embodiment 3 is obtained55V10Ni35The XRD figure of+Li as shown in figure 3, adopt Cu-K α targets during test,
Continuous scanning speed is 4 °/min, scans and encloses 20 ° -80 °.
Fig. 1 is Ti55V10Ni35The quasi-crystalline substance complex phase hydrogen storage material Ti obtained with embodiment 1～355V10Ni35The XRD figure of+Li；
It will be seen from figure 1 that Ti55V10Ni35Mainly by the Icosahedral phases with icosahedral structure of virus (I phases), the face-centered cubic of Ti2Ni- bases
V- based solid solution phases (spatial group Im3m) compositions of phase (spatial group R-3m), body-centered cubic structure.Ooze the titanium vanadium nickel quasi-crystalline substance after lithium
Material Ti55V10Ni35+ Li (0.3A), Ti55V10Ni35+ Li (0.6A), Ti55V10Ni35The XRD analysis of+Li+Li (0.9A) show,
Outside the lithium phase for adding except for an additional, its main phase structure for including and Ti55V10Ni35Icosahedral phases structural difference less, but is respectively spread out
Penetrate the intensity slightly difference at peak.Illustrate that the lithium of extra addition does not mutually destroy Ti55V10Ni35Quasi-crystalline substance phase structure, while adopt
Different electroosmotic currents, content of the lithium in quasi-crystalline substance also have difference.
Embodiment 4：The quasi-crystalline substance complex phase hydrogen storage material Ti that respectively embodiment 1～3 is obtained55V10Ni35+ Li and carbonyl nickel powder
1: 5 mix homogeneously is compared with weight in end, applies the pressure of 15MPa to the mixture of powders of gained, wait it is calm be pressed into diameter 10mm and
The disk of thickness 1.5mm adopts the nickel wire of diameter 1mm and by impulsed spot welding mode and negative pole as negative pole, the lug of the negative pole
Piece connects, and the positive pole of ni-mh experimental cell adopts the nickel hydroxide (Ni (OH) of commodity sintering2/ NiOOH), between both positive and negative polarity every
Film then selects the polypropylene type barrier film of wettability and good air permeability, KOH aqueous solution of the electrolyte for concentration 6M.
Will be with Ti55V10Ni35The quasi-crystalline substance complex phase hydrogen storage material Ti that quasicrystalline alloy and embodiment 1～3 are obtained55V10Ni35+ Li is
The simulated battery of negative electrode active material carries out performance test, and the test of cyclical stability and computational methods are：By battery with electric current
Density charges for 60mA/g, is discharged with 30mA/g.Its formula is：Sn=(electric discharges of the same battery after n-th charge and discharge cycles
The maximum discharge capacity of capacity/same battery) × 100%.
The test of multiplying power discharging property (HRD) and computational methods are：Battery after activation is filled with 60mA/g electric current densities
Electricity, is then discharged with different electric current densities, and discharge current density is followed successively by 30mA/g, 60mA/g, 90mA/g, 120mA/
G, 180mA/g and 240mA/g.Its formula is：HRD=(battery capacities of the same battery under different discharge current densities/same
Battery capacity of one battery under 30mA/g discharge current densities) × 100%.
Fig. 4 is with Ti55V10Ni35The quasi-crystalline substance complex phase hydrogen storage material Ti that quasicrystalline alloy and embodiment 1～3 are obtained55V10Ni35+
Simulated battery cycle-index and discharge capacity graph of relation of the Li for negative electrode active material.Fig. 5 is with Ti55V10Ni35Quasi-crystalline substance is closed
The quasi-crystalline substance complex phase hydrogen storage material Ti that gold and embodiment 1～3 are obtained55V10Ni35Multiplying power discharging properties of+the Li for negative electrode active material
With discharge capacity graph of relation.
As shown in Figure 5, the high Entropy Changes titanium vanadium nickel quasi-crystalline substance composite diphase material of lithium is oozed because the addition of lithium makes Ti55V10Ni35Complex phase quasi-crystalline substance material
The discharge performance of material is significantly improved, and concrete situation of change is shown in Table 1：
Table 1
Table 1 is with Ti55V10Ni35The quasi-crystalline substance complex phase hydrogen storage material Ti that quasicrystalline alloy and embodiment 1～3 are obtained55V10Ni35+
Stable circulation performance data of the Li for the simulated battery of negative electrode active material, as it can be seen from table 1 with comprising Ti55V10Ni35It is accurate
The negative pole of peritectic alloy is compared, quasi-crystalline substance complex phase hydrogen storage material Ti of the present invention55V10Ni35+ Li has for the simulated battery of negative electrode active material
There is more excellent efficient discharge performance.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention described should be defined by scope of the claims.
Claims (5)
1. a kind of Ti based Quasi-crystals hydrogen bearing alloys containing the high Entropy Changes of lithium, it is characterised in that the expression formula of the hydrogen bearing alloy is
Ti55V10Ni35+ Li, wherein, metal Li enters Ti based Quasi-crystals Ti55V10Ni35Space in.
2. the preparation method of the hydrogen bearing alloy described in a kind of claim 1, it is characterised in that include：
Step one：By metal Ti, V and Ni according to non-stoichiometric Ti55V10Ni35Ratio weigh, be then placed in non-consumable true
In empty electric arc furnace, melt back 4 times is smelted into alloy pig, and then the alloy pig is put in the casting integrated machine of vacuum chilling,
Prepare the Ti containing I phases55V10Ni35Quasi-crystalline substance composite diphase material strip；
Step 2：Potassium chloride and lithium chloride that mass ratio is 4: 6 are weighed respectively, are put in graphite crucible, in 400-480 DEG C of condition
Lower fusing forms the fused salt of melting；Then the Ti for step one being obtained55V10Ni35Quasi-crystalline substance composite diphase material strip is put into the molten of melting
In salt, be powered electrolysis, the lithium chloride in the fused salt is decomposed, and lithium metal enters into Ti in making the fused salt55V10Ni35's
In space, hydrogen bearing alloy Ti is formed55V10Ni35+Li。
3. preparation method according to claim 2, it is characterised in that described that the alloy pig is put into into the casting of vacuum chilling
In all-in-one, the Ti containing I phases is prepared55V10Ni35Quasi-crystalline substance composite diphase material strip, specifically includes：
The alloy pig is put into bottom to be provided with the quartz ampoule of diameter 0.3-0.5mm apertures, the quartz ampoule is placed in described
In the casting integrated machine of vacuum chilling, 1 × 10 is evacuated to-3MPa-5×10-3MPa, is filled with high-purity argon gas big to 0.5 ± 0.1
Alloy pig in quartz ampoule is melted under the conditions of 2000 ± 100 DEG C, injection pressure 0.1- by air pressure using sensing heating
0.2MPa, copper roller linear velocity are 20-40m/s, obtain the Ti containing I phases55V10Ni35Quasi-crystalline substance composite diphase material strip,
Wherein, the Ti55V10Ni35The thickness of quasi-crystalline substance composite diphase material strip is 50～70 μm, and width is 2～3mm.
4. preparation method according to claim 2, it is characterised in that the step 2 is specifically included：
By the Ti55V10Ni35Quasi-crystalline substance composite diphase material strip is put into bottom and is provided with the quartz ampoule of diameter 0.5-1mm osculums, will
The quartz ampoule is immersed in the graphite crucible of the fused salt for being formed with melting by fixing device copper sheet；
A copper wire coil and the Ti are inserted in the quartz ampoule55V10Ni35Quasi-crystalline substance composite diphase material strip is contacted, and described
Copper wire coil is not immersed in the fused salt of the melting；
Fixing device copper sheet is connected with iontophoresis device so that the Ti55V10Ni35Quasi-crystalline substance composite diphase material strip one terminates negative pole,
Be connected a termination positive pole with the graphite crucible, is regulated and controled electric current, is electrolysed；30min is electrolysed under stabling current, stops electricity
Solution；
Salt protectiveness is hung at 380 DEG C to come out of the stove, negative pole is extracted rapidly and is put in rustless steel pannikin, and is closed the lid and treated which is naturally cold
But it is put in vacuum bag to room temperature and preserves；
By the hydrogen bearing alloy Ti from the nearest formation of the quartzy bottom of the tube55V10Ni35+ Li takes out, and deionized water is rinsed repeatedly
5-7 time, the salt of surface solidification is removed, drying preservation is then carried out in baking oven.
5. preparation method according to claim 2, it is characterised in that the stabling current of the energization electrolysis is 0.3A,
0.6A or 0.9A.
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