CN1248338C - Negative pole material for high-temperature NiH battery and its prepn process - Google Patents

Abstract

The present invention relates to a negative electrode material especially suitable for preparing a high temperature nickel-hydrogen battery, which belongs to the fields of a function material and preparation of the function material. The negative electrode material comprises the following component (atom%): A1B5 which is characterized in that the A in the component of the negative electrode material comprises La, Ce, Pr, Nd and Y, and the B comprises Ni, Co, Mn and Al; the negative electrode material comprises the following ingredients (weight %): 14.7 to 23.1% of the La, 4.0 to 12.1% of the Ce, 1.0 to 1.8% of the Pr, 2.0 to 3.8% of the Nd, 0.5 to 5% of the Y, 4.5 to 6.5% of the Co, 6.5 to 8.5% of the Mn and 0.6 to 1.8% of the Al, and the rest is the Ni. A preparing method of the material is characterized in that an alloy flake is prepared in a single roller quick quenching method, and the linear speed of a cooling roller is controlled to be from 15 to 30 m/s. Compared with the prior art, the negative material of the present invention has the characteristics of wide temperature range, high charge and discharge efficiency, good use effect, simple and economical preparing process, no heat treatment for products, etc.

Description

Be used for negative material of high-temperature Ni/H 2 battery and preparation method thereof

Affiliated field

The invention belongs to the preparation field of functional material and this material.Be particularly useful for making the negative material of high-temperature Ni/H 2 battery.

Background technology

An important use of Ni-MH battery is to be used in the field of power tools at present, because wireless chargeable electric tool fast development in recent years, bring great convenience to people's work, so people are to the also increase greatly of battery requirements amount of rechargeable.In numerous secondary cells, Ni-MH battery has become the first-selected battery of many electronic products with its high power capacity, long-life, excellent specific property such as pollution-free.The rechargeable battery that uses in electric tool at present mainly is a nickel-cadmium cell, but the nickel-cadmium cell capacity is lower, has serious environmental again and pollutes, and Ni-MH battery can exchange with the voltage of nickel-cadmium cell, and higher capacitance is arranged, thereby will become best substitute.Ni-MH battery product of the prior art, subject matter in actual applications is that the capacity of battery has decline along with the rising of temperature, different with general electronic products, electric tool in use requires heavy-current discharge, also require Ni-MH battery should have energy large current charge function in order to shorten the charging interval in addition, and fill at big electric current, the energy that consumes on the internal resistance of cell in the discharge process will increase, thereby the rising (will be elevated to about 40～55 ℃ usually) that inevitably will produce battery temperature, therefore also just require this negative material when temperature raises, filling of material itself, discharge capacity does not descend or few decline, and promptly this material should have high filling at wide temperature range, discharge capacity and big electric current fill, the ability of discharge.Current people are making great efforts to develop the rechargeable nickel-hydrogen battery of used for electric vehicle, the used for electric vehicle rechargeable nickel-hydrogen battery requires hydrogen storage material should have better big electric current charge and discharge characteristic and high temperature serviceability equally, and than electric tool battery performance demands more harsh (the charge and discharge electric current is bigger, temperature rise is higher), so in the wide temperature range of high power capacity, use the Ni-MH battery of big electric current charge and discharge, the composition design of its cathode hydrogen storage material and the more apparent key of preparation.Ni-MH battery mainly is made up of nickel hydroxide positive plate, hydrogen storage alloy negative, barrier film, potassium hydroxide electrolyte.The performance of entire cell and the performance of each parts are all closely bound up.When Ni-MH battery is in hot environment, the overpotential of its anodal oxygen reaction of formation reduces, cause anodal charge efficiency to reduce, the equalizing pressure owing to hydrogen bearing alloy increases in the negative pole simultaneously, and the hydrogen of hydrogen bearing alloy also reduces, so the hydrogen dividing potential drop in the battery increases, this hydrogen passes barrier film and enters positive pole, quickened anodal capacity and reduced, so the high temperature serviceability of hydrogen bearing alloy not only affects the negative pole of Ni-MH battery, and have influence on anodal capacity.For improving the high temperature serviceability of entire cell, can improve the high temperature serviceability of nickel hydroxide positive plate (Chinese patent application 99116113.0), hydrogen storage alloy negative and alkaline electrolyte (Chinese patent application 00108386.4) and barrier film respectively.Chinese patent application 99116113.0 is passed through at Ni (OH) ₂Add with respect to Ni (OH) in the positive pole ₂Weight is the high-temperature charging efficient that the titanium elements additive of 0.1-15wt% improves Ni-MH battery, but its employed temperature does not have higher temperature data introduction only about 50 ℃.Chinese patent application 00108386.4 adds wolframic acid ion and sodium ion in electrolyte, the W element that exists with the wolframic acid ion is absorbed by positive pole, forms film electrochemical stability, that cover positive electrode active material powder.Sodium ion is in the battery charging and discharging circulation, and the lattice of penetrable positive active material makes lattice generation strain, and these can both improve the charge efficiency of battery under hot environment, and the characteristics such as self-discharge performance that improve this battery are arranged.China authorizes patent of invention ZL 97120151.X to adopt single-roller method rapid solidification spray alloy sheet in addition, and its chill roll linear resonance surface velocity is 31-45m/s, and this cooling rate is very fast, intensity of cooling is bigger, to the equipment requirements height, and also needs two phase heat treatment, operation is many, technology cost height.This patent only for solving hydrogen bearing alloy capacity and the cycle life under the normal temperature, is not considered the operating position of hydrogen bearing alloy under higher temperature.

Goal of the invention and content

The objective of the invention is to propose a kind of being applicable under (30-80 ℃) high temperature, have charge and discharge efficient height, result of use is good, and simple, the economic high-temperature Ni/H 2 battery of preparation technology is with negative material and this preparation methods.

According to purpose of the present invention, we have carried out rational adjustment to high-temperature Ni/H 2 battery with the composition of negative material, and obtain the negative electrode battery material of charge and discharge excellent in efficiency under (30-80 ℃) high temperature, i.e. hydrogen bearing alloy in conjunction with the preparation method of single roller rapid quenching.For Ni-MH battery, used negative material mainly is mishmetal MmNi at present ₅-type hydrogen storage alloy, alloy capacity are generally about 300mAh, and in order to improve the capacity of negative pole hydrogen bearing alloy, that is developing at present has a Zr-base AB ₂Type Laves' phases alloy, Ti-Zr base AB type alloy and A ₂Type B Mg ₂The Ni magnesium base alloy, but remove small part AB owing to activating reasons such as slow or cycle life difference ₂Outside the type alloy, other alloys all do not reach practical application.

AB ₅Hydrogen bearing alloy be by the elements A of easy generation stable hydride (as Mm, Ca, Zr) intermetallic compound of forming with other element B (as Ni, Al, Mn, Si, Zn, Cr, Fe, Cu, Co etc.) belongs to CaCu ₅Type hexagonal structure, such material are after inhaling hydrogen, and hydrogen is to be present on the octahedron and position, tetrahedral interstice in the alloy lattice with atomic state, and accompanying drawing 1 is its crystal structure schematic diagram, and accompanying drawing 2 is that hydrogen atom is at typical AB ₅Hydrogen bearing alloy LaNi ₅Octahedron in the atom and position, tetrahedral interstice.When such material when inhaling hydrogen, initial atomic hydrogen dissolves in the metal lattice in the gap mode, forms the lower α phase solid solution of hydrogen content, this moment equilibrium hydrogen pressure P _H2With square being directly proportional of solid solution H/M value.Along with the increase of hydrogen, α changes the high β phase of hydrogen content mutually into.

The hydrogen pressure of phase transition process is a certain value.When α all change into mutually β mutually after, equilibrium hydrogen pressure continues to raise.Hydrogen bearing alloy is inhaled and is put the process that the hydrogen process is a phase transformation, and meets Gibbs phase rule, and this process is all represented (seeing accompanying drawing 3) by pressure-concentration-thermoisopleth (P-C-T curve) usually, and accompanying drawing 3 is the desirable P-C thermoisopleth (T of hydrogen bearing alloy ₁＜T ₂＜T ₃).By accompanying drawing 3 as seen, raise with temperature rising P-C-T curve platform, the hydrogen partial pressure value increases, and platform shortens, and this raises with temperature with regard to the reversible hydrogen adsorption and desorption capacity that means alloy and reduces.Actual hydrogen bearing alloy absorption of using and the P-C thermoisopleth of emitting show some hysteresis, and platform has some inclinations simultaneously.The hydrogen dividing potential drop of hydrogen bearing alloy and the relation of temperature meet Van ' t-Hoff equation, $\ln P=\frac{\mathrm{\ΔH}}{\mathrm{RT}}-\frac{\mathrm{\ΔS}}{R},$ And heat release when inhaling hydrogen, absorb heat when putting hydrogen.According to Van ' tHoff equation as can be known, capacity hydrogen bearing alloy preferably at high temperature, the hydrogen dividing potential drop under its high temperature is inevitable relatively low, and the stability that generates hydride then can improve.

The main component that uses for nickel-hydrogen battery in the hydrogen bearing alloy mishmetal is La, Ce, Pr, Nd, because lanthanide series has the group of the lanthanides shrinkage phenomenon, successively decreased to the Nd atomic radius by La, and the atomic radius of class rare earth metal y and Ce, Pr, Nd is approaching.When increasing the element of little atomic radius, whole lattice volume is reduced, atom packing is tightr, makes alloy hydrogen dividing potential drop increase, and has reduced the hydride stability of hydrogen bearing alloy, the alloy high-temp capacity is reduced, especially Ce element, the stability influence maximum to the hydride of alloy makes to inhale and puts the descending Ce of being followed successively by of ability＞Nd＞Pr that the hydrogen pressure platform raises, therefore to improve the high-temperature behavior of hydrogen bearing alloy, be necessary to reduce the Ce content in the alloy.AB in addition ₅Hydrogen bearing alloy reduces with the Ni element in the B side element, and replacing element increases the especially increase of thick atom such as Mn, Al element, lattice enlarges, just can obtain the alloy that the hydrogen branch forces down, the stability of hydride then can increase in the alloy, and the high temperature charge and discharge efficient of hydrogen bearing alloy will improve.Therefore high-temperature Ni/H 2 battery proposed by the invention becomes to be grouped into (atom %) with negative material: A ₁B ₅, it is characterized in that forming high-temperature Ni/H 2 battery is La, Ce, Pr, Nd, Y element with the A in the negative material; B is Ni, Co, Mn, Al element; The concrete composition of this negative material is respectively (weight %) La 14.7-23.1%; Ce 4.0-12.1%; Pr 1.0-1.8%; , Nd 2.0-3.8%; Y 0.5-5%; Co 4.5-6.5%; Mn 6.5-8.5%; Al 0.6-1.8%; All the other are Ni.Also having A by high-temperature Ni/H 2 battery proposed by the invention with other features of negative material is lanthanide rare and class rare earth element, and B is a transiting group metal elements, and the atom % of A: B is: (A) ₁(B) ₅

According to the preparation method of high-temperature Ni/H 2 battery proposed by the invention with negative material; this method is by above-mentioned composition designing requirement; put into the induction furnace of argon shield after earlier raw material being prepared again; smelt and ingot casting; adopt the fast quenching equipment of prior art that alloy cast ingot is prepared into the hydrogen bearing alloy thin slice then; after it is characterized in that the alloy pig fusion in quick-quenching method; the winding-up temperature that forms alloy liquid is 1100-1300 ℃; the blowing pressure of winding-up alloy liquid is 0.01-0.05Mpa; the body of inflating is any one in nitrogen and the argon gas; spacing between nozzle and the chill roll is 0.2-0.45mm, and the linear velocity of chill roll rotation is 15-30m/s.The chill roll of the used fast quenching equipment of the present invention is a water-cooled copper system chill roll, and the prepared hydrogen bearing alloy product that goes out is the thin slice of ultra-fine brilliant storage hydrogen negative material.

Adopt high-temperature Ni/H 2 battery proposed by the invention compared with prior art with the preparation method of negative material and this negative material, have broad application temperature range, charge and discharge efficient height, result of use is good, preparation technology is simple and economical, and product such as does not need to heat-treat at characteristics again.Cast alloy of the present invention in addition also increases on the high temperature charge/discharge capacity to some extent, but increasing degree is not too obvious.And through the alloy of quick-quenching method of the present invention preparation, high temperature (30-80 ℃) charge and discharge capacity and have greatly improves, electrochemistry charge and discharge capacity in the time of its 50 ℃ is greater than 300mAh/g, the charge and discharge capacity reaches more than the 250mAh/g in the time of 70 ℃, and the highest charge and discharge capacity can reach 247mAh/g in the time of 80 ℃.Therefore will make this negative material use the stronger advantage that at high temperature has.

Description of drawings

See that in specification of the present invention accompanying drawing 1 is AB ₅The crystal structure schematic diagram of negative material; Accompanying drawing 2 is LaNi ₅Hydrogen in the negative material is present in octahedra and the locational structural representation of tetrahedral interstitial void with atomic state; Accompanying drawing 3 is the desirable P-C thermoisopleth (T of hydrogen bearing alloy ₁＜T ₂＜T ₃); Accompanying drawing 4 is the high temperature capacity of as cast condition hydrogen bearing alloy; Accompanying drawing 5 is a capacity restoration performance 30 ℃ time the behind the as cast condition hydrogen bearing alloy high temperature; Accompanying drawing 6 is a fast quenching hydrogen bearing alloy high-temperature behavior; Accompanying drawing 7 is a capacity restoration performance 30 ℃ time the behind the fast quenching hydrogen bearing alloy high temperature; Accompanying drawing 8 is that fast quenched alloy of the present invention typical case and Comparative Examples alloy high-temp performance compare; Accompanying drawing 9 is fast quenched alloy of the present invention typical case and Comparative Examples alloy high-temp volume percent.Zero be the A atom in the accompanying drawing 1 wherein, ● be the BI atom, о is the BII atom; Sequence number 7# selects comparative alloy for the present invention in the accompanying drawing 8,9; Sequence number 12# is the Comparative Examples alloy; Sequence number 13# is Comparative Examples alloy (commercially available).

Embodiment

Embodiment 1

According to alloy in the table 1 (A) ₁(B) ₅The percentage by weight of each element is prepared burden, and the alloy raw material for preparing is carried out melting and ingot casting in the arc furnace of argon shield, waits to obtain to become stand-by less than 200 purpose alloyed powders in grinding at room temperature behind the as cast condition hydrogen bearing alloy.Then will be less than 200 purpose negative alloy powders and nickel powder mixed by 1: 1, and add an amount of poly-vinyl alcohol solution as binding agent, be cold-pressed into diameter then and use [the Ni (0H) that used positive electricity is very identical with Ni-MH battery as negative electrode for the cake of (d=15mm) ₂-NiOOH] electrode, the Capacity design of positive electrode is the capacity far above negative electrode, so that negative electrode material reaches fully saturated when charging, [Hg/HgO/6M KOH] is reference electrode.In the electrode performance test process, at first adopt the electric current of 60mA/g that storage hydrogen negative material is fully changed at 30 ℃, the system that changes into is as follows: the current charges 400min that adopts 60mA/g, paused 15 minutes in the charging back, till being-0.5 volt to the negative electrode current potential with respect to the electrode potential of reference electrode with the current discharge of 60mA/g then, carry out the next round charge and discharge cycle again.Capacity of negative plates carries out capacity and will reach a maximum along with what change into, and relatively stablely gets off, and then changes into end.This maximum is the hydrogen storage capability of material under 30 ℃, and the system temperature that raises then adopts the identical hydrogen storage capability of charge and discharge system test negative material under different temperatures in 30-80 ℃ of scope.

As shown in Table 2, each cast alloy capacity is suitable substantially in the time of 30 ℃, but raises with temperature, and all alloy capacity all reduce gradually, and the amplitude of reduction is different with the difference of alloying component.

Experimental result shows that the Y content one in the 1#-4# composition regularly can adopt Ce, Pr, Nd to replace La, and high temperature charge and discharge efficient descends to some extent, and then capacity descends at most when Ce content increases.

Alloying component is by 5#, 1#, 6#, 7#, to 8#, and Y content is increased to 4.5wt% from 0.5wt% in the alloy, and corresponding C e content drops to 5.1 by 9.1, and the high temperature capacity of alloy increases afterwards earlier and reduces, and high-temperature behavior was best when Y content was 3.5wt%.These alloys that contain Y element and Y content are that 0 Comparative Examples 12#, 13# compare, and capacity improves, and temperature is high more, and the amplitude that capacity improves is big more, and particularly during higher temperature, capacity can be brought up to 192mAh/g (7#) by 152mAh/g (12#) during as 80 ℃.

Alloy 7# and 9#, 10#, 11# more as can be known, Mn, Al, Co content increase the hydrogen dividing potential drop that helps reducing alloy, improve the high temperature efficiency for charge-discharge of alloy.But Al content is unsuitable too high, because it generates dense oxidation film easily in the metal surface, stops entering of hydrogen, and the alloy capacity is descended.The metal Co price is more expensive, and present research and development direction is low cobalt hydrogen bearing alloy, and by the contrast of Comparative Examples alloy 12# and 13# as can be known, arrives 10.4wt% (13# Comparative Examples alloy) even increase the amount of Co, and the high temperature capacity of alloy also increases seldom.

In sum, the Ni-based hydrogen bearing alloy A of as cast condition mishmetal ₁B ₅The high temperature charge and discharge efficient of the content influence alloy of middle Y element, when particularly temperature was higher, charge and discharge efficient showed certain raising.In embodiments of the present invention, sequence number 1#-11# is embodiments of the invention, and sequence number 12#-13# is a Comparative Examples in embodiments of the present invention.

Embodiment 2

Get 5# in the table 1,1#, 6#, 7#, 8# and Comparative Examples 12#, 13# alloy part ingot casting respectively, the induction furnace of putting into fast quenching equipment carries out remelting, alloy liquid is at the copper chill roll surface cool flakiness of high speed rotating, the technological parameter of its cooling means sees Table 3, and the linear velocity of chill roll is set at 12,18,24,30 respectively, 36m/s.The fast quenching hydrogen bearing alloy thin slice that obtains is become less than 200 purpose alloyed powders at grinding at room temperature with as cast condition hydrogen bearing alloy ingot.The fast quenching sample difference label of gained as cast condition sample and different cooling is as shown in table 3.Again will be less than 200 purpose negative alloy powders and nickel powder mixed by 1: 1, and the poly-vinyl alcohol solution of adding convention amount is as binding agent, be cold-pressed into diameter then and use [the Ni (OH) that used positive electricity is very identical with Ni-MH battery as negative electrode for the cake of (d=15mm) ₂-NiOOH] electrode, the Capacity design of positive electrode is the capacity far above negative electrode, so that negative electrode material reaches fully saturated when charging, [Hg/HgO/6M KOH] is reference electrode.In the electrode performance test process, at first adopt the electric current of 60mA/g that hydrogen storage material is fully changed into down at 30 ℃, the system that changes into is as follows: the current charges 400min that adopts 60mA/g, paused 15 minutes in the charging back, till being-0.5 volt to the electrode potential of negative pole with respect to the electrode potential of reference electrode with the current discharge of 60mA/g then, carry out the next round charge and discharge cycles again.Capacity of negative plates carries out capacity and will reach a maximum along with what change into, and relatively stablely gets off, and then changes into end, and this maximum is the hydrogen storage capability C of material under 30 ℃ ₃₀, the system temperature that raises then adopts the identical hydrogen storage capability C of the system that discharges and recharges test negative material under different temperatures in 30-80 ℃ of scope _T, and the hydrogen storage capability C during with 30 ℃ ₃₀Be the basis, calculate the efficiency for charge-discharge R of negative material under the high temperature, R=(C _T/ C ₃₀) * 100%.Behind the high-temperature behavior EOT, the three-electrode system temperature is rolled back 30 ℃, still adopt the restorability after the same system that discharges and recharges is tested negative material high temperature.

Table 4 is 1# (Y content the is 1.5wt%) alloy under the different fast quenching speed and the high temperature capacity of 7# (Y content is 3.5wt%) alloy and cast alloy thereof.As can be seen, the alloy that composition is identical, fast quenching speed is different, along with the speed of quenching increases (by 12m/s to 24m/s), high-temperature behavior improves gradually, and the speed of quenching continues increase (by 24m/s to 36m/s), high temperature charge and discharge decrease in efficiency.Compare with cast alloy, the high temperature capacity of all fast quenched alloy all increases.But when fast quenching speed is low; as 12m/s, gained fast quenching thin strap average thickness is 105 μ m, and crystallization crystal grain is also bigger; it is few that lattice strain improves; fast quenching speed is too high, and as 36m/s, gained fast quenching thin strap average thickness only is 35 μ m; crystal grain is extremely tiny; occurred the structure of crystallite, nanocrystalline, amorphous coexistence in the alloy, amorphous is not inhale hydrogen, so the too high or too low capacity that all can make of fast quenching speed reduces.As seen alloying component and preparation process condition all are the factors that influences its high temperature charge and discharge performance, and it is big more to increase influence with temperature.In sum, the favor speed of alloy fast quenching of the present invention is 24m/s.

Table 5 is the comparison of alloy (Y content is 0.5-4.5wt%) with the high temperature capacity of Comparative Examples alloy 12# and 13# of the different Y content with quenched state of as cast condition.As seen, behind the different Y content alloy fast quenchings (24m/s), except that 7# (Y content is 3.5wt%) capacity is constant substantially, all the other alloy capacity reduce during all than as cast condition in the time of 30 ℃ from table 5.Though each fast quenched alloy reduces with temperature rising capacity is also the same with as cast condition, in 40～80 ℃ of scopes, each alloy capacity increases during all than as cast condition, and when particularly temperature was higher, capacity improved greatly.What show that rapid quenching technique generates tiny and uniformly organizes the high temperature charge and discharge that more help alloy.Similar with cast alloy, except that 13# Comparative Examples commercial alloys, all the other alloys are increased to 3.5wt% with Y content by 0wt% in the fast quenched alloy, and the alloy capacity is tending towards increasing, and when Y content was 4.5wt%, capacity reduced.Therefore Y content is that the fast quenched alloy (24m/s) of 3.5wt% has best high temperature volumetric properties, and capacity still can reach 247mAh/g in the time of 80 ℃.

Table 6 is the capacity restoration performances of different Y content hydrogen bearing alloys in the time of 30 ℃.Data show that after the high temperature volume test, system temperature returns to 30 ℃, increase with cycle-index, and the alloy capacity all recovers to some extent.In the as cast condition hydrogen bearing alloy, Comparative Examples 13# commercial alloys capacity restoration the highest.But behind the employing rapid quenching technique, the capacity restoration performance of all alloys all is higher than its cast alloy respectively, and wherein Y content is fast quenched alloy capacity restoration the highest of 3.5wt% and 4.5wt%, and is higher than Comparative Examples 13# commercial alloys.

Accompanying drawing 4 and accompanying drawing 5 are that cast alloy 1# of the present invention, 7# and Comparative Examples cast alloy 12#, 13# return to the capacity restoration performance under 30 ℃ behind capacity under the 30-80 ℃ of condition and high temperature, during as seen less than 70 ℃, 2# of the present invention and 4# alloy capacity are more or less the same, a little more than Comparative Examples cast alloy 6#, 7.Temperature is elevated to 80 ℃, and 4# alloy capacity of the present invention reduces minimum and capacity is the highest, and all the other alloy capacity are suitable, but all dropped to below the 200mAh/g.But Comparative Examples 7# commercial alloys capacity restoration is the highest, and the capacity that all the other alloys recover is relatively low.

Accompanying drawing 6 and accompanying drawing 7 are that the fast quenched alloy 1# of the present invention, 7# and the fast quenched alloy 12# of Comparative Examples, 13# return to the capacity restoration performance under 30 ℃ behind capacity under the 30-80 ℃ of condition and high temperature, and its fast quenching speed is 24m/s.As seen, the capacity volume variance of these alloys strengthens behind the fast quenching, and it is with the obvious advantage that the adding of Y makes the high-temperature behavior of alloy in the alloy, and 7# alloy high-temp volumetric properties is best in the present invention.Rapid quenching technique also makes capacity restoration the highest of 7# alloy, and all the other alloy capacity restorations are more or less the same, but the capacity restoration performance of these alloys all is higher than its cast alloy respectively.

The fast quenched alloy that accompanying drawing 8 and accompanying drawing 9 are selected for the present invention relatively reaches the comparison of high temperature volume percent with the high-temperature behavior of Comparative Examples alloy, and fast quenching speed is 24m/s, wherein the high temperature volume percent $p=\frac{{\mathrm{<figure-callout\; id="30"\; label="C\; H\; C"\; filenames="C0315395700202.png,C0315395700221.png"\; state="\{\{state\}\}">C</figure-callout>}}_H}{C_{}}\&times;100\%,$ H is different probe temperature in the formula, and value is 30～80 ℃ respectively, C _HBe the capacity under the different temperatures, C ₃₀Be the capacity under 30 ℃.Clearly, the high temperature capacity of fast quenched alloy all substantially exceeds cast alloy, so rapid quenching technique helps improving the high temperature charge-discharge performance of alloy, and this is relevant with the small grains institutional framework with the even component distributing that rapid quenching technique is obtained.Among negative material composition of the present invention and the preparation method, the high-temperature behavior of preferred fast quenched alloy 7# (Y content is 3.5wt%) is best.By accompanying drawing 9 as can be known, raise with temperature, especially after temperature surpassed 60 ℃, as cast condition Comparative Examples 12# and 13# alloy capacity descended at most, secondly are that as cast condition 7# contains y alloy.The high temperature capacity decline ratio of fast quenched alloy is less, in the time of 80 ℃, the high temperature volume percent of Comparative Examples 12# 48.5% during by as cast condition is elevated to 68.4% of fast quenched alloy, Comparative Examples 13# 53.3% during by as cast condition is elevated to 67.2%, and preferred alloy 7# of the present invention 57.8% during by as cast condition 74.2% when being elevated to quenched state.

In sum, adopt fast quenching preparation technology preparation to contain the hydrogen bearing alloy of class rare earth metal y, can obtain the negative material that the good suitable high-temperature Ni/H 2 battery of high-temperature behavior uses.This material possesses higher charge and discharge capacity in 30～80 ℃ of scopes, be much higher than commercially available hydrogen bearing alloy, electrochemistry charge and discharge capacity in the time of its 50 ℃ is greater than 300mAh/g, capacity reaches more than the 250mAh/g in the time of 70 ℃, and simple and reliable process does not need heat treatment.

The composition of table 1 embodiment of the invention and prior art is (wt%) relatively

Composition		La	Ce	Pr	Nd	Y	Ni	Co	Mn	Al
											The present invention	1#	20.0	8.1	1.1	2.2	1.5	52.5	5.5	7.8	1.3
2#	19.5	8.6	1.1	2.2	1.5	52.5	5.5	7.8	1.3
										3#		19.5	8.1	1.6	2.2	1.5	52.5	5.5	7.8	1.3
4#	19.5	8.1	1.1	2.7	1.5	52.5	5.5	7.8	1.3
										5#		20.0	9.1	1.1	2.2	0.5	52.5	5.5	7.8	1.3
6#	20.0	7.1	1.1	2.2	2.5	52.5	5.5	7.8	1.3
										7#		20.0	6.1	1.1	2.2	3.5	52.5	5.5	7.8	1.3
8#	20.0	5.1	1.1	2.2	4.5	52.5	5.5	7.8	1.3
										9#		20.0	6.1	1.1	2.2	3.5	53.2	5.5	7.1	1.3
10#	20.0	6.1	1.1	2.2	3.5	53.0	5.5	7.8	0.8
										11#		20.0	6.1	1.1	2.2	3.5	53.2	4.8	7.8	1.3
Comparative Examples	12#	20.0	9.6	1.1	2.2	0	52.5	5.5	7.8												1.3
										13# is commercially available	19.7	9.4	1.2	2.5	0	50.3	10.4	5.2	1.3

The discharge capacity (mAh/g) of table 2 as cast condition hydrogen bearing alloy under different temperatures

Temperature (℃) composition		30	40	50	60	70	80
								The present invention	1#	328	304	294	272	234	173
2#	328	300	279	258	215	157
							3#		328	303	290	269	230	170
4#	328	301	287	266	226	166
							5#		328	302	286	260	220	161
6#	328	315	299	272	236	177
							7#		332	312	300	277	240	192
8#	334	304	294	270	228	186
							9#		332	310	296	274	235	189
10#	332	310	298	276	238	191
							11#		332	310	297	274	237	190
Comparative Examples	12#	328	295	277	258	211									152
							13# is commercially available	315	299	285	259	212	168

The alloy sample of table 3 different technology conditions number

Process conditions and composition		The present invention's (single roller rapid quenching)			Comparative Examples
								As cast condition	Single roller rapid quenching
					Process conditions	The winding-up temperature (℃)	1125				1210	1280	/	1050	1330
Jetting pressure (Mpa)	0.04	0.03	0.02	/				0.06	0.01
						Mouth roll spacing (mm)	0.26			0.32	0.38	/	0.18	0.43
Roller speed (m/s)	18	24	30	/				12	36
						Composition	5#			/	kc5-24	/	5-zhu	/	/
1#	kc1-18	kc1-24	kc1-30	1-zhu	kc1-12			Kc1-36
							6#		/	kc6-24	/	6-zhu	/	/
7#	kc7-18	kc7-24	kc7-30	7-zhu	kc7-12			kc7-36
							8#		/	kc8-24	/	8-zhu	/	/
12#	/	kc12-24	/	12-zhu	/			/
							13#		/	kc13-24	/	13-zhu	/	/

The high temperature capacity (mAh/g) of alloy under table 4 Different Cooling Conditions

Temperature (℃) composition			30	40	50	60	70	80
									The present invention	1#	kc1-18	320	307	300	281	253	215
kc1-24	322	309	301	284	263	223
							kc1-30	320			307	298	279	251	208
7#	kc7-18	332	327	312	295	272										237
							kc7-24	333		327	315	299	280	247
	kc7-30	330	323	310	292	271									236
							Comparative Examples	1#		1-zhu	328	304	294	272		234	173
kc1-12	315	306	298	278	248	203
									kc1-36	316	305	296	275	243	190
7#	7-zhu	332	312	300	277	240										192
								kc7-12	330	325	310	290	260	222
	kc7-36	325	320	307	285	254									217

The discharge capacity of the different Y content of table 5 hydrogen bearing alloy under different temperatures

Y content (wt%)		0.5	1.5	2.5	3.5	4.5	0	0
									Temperature ℃	Sample	5-zhu	1-zhu	6-zhu	7-zhu	8-zhu	The 12-zhu Comparative Examples	13-zhu (commercially available) Comparative Examples
30	Cast alloy	328	328	328	332	334	328	315
									40	302	304	315	312	304	295	299
50		286	294	299	300	294	277	285
									60	260	272	272	277	270	258	259
70		220	234	236	240	228	211	212
									80	161	173	177	192	186	159	168
Temperature ℃		Sample	kc5-24	kc1-24	kc6-24	kc7-24	kc8-24	kc12-24									kc13-24
	30								Fast quenched alloy	319	322	325	333	321	313	308
40		310	309	315	327	317	306	301
	50									301	301	303	315	305	296	290
60		285	284	285	299	290	275	262
	70									257	263	270	280	273	249	236
80		221	223	228	247	240	214	207

Capacity restoration performance behind the different Y content of the table 6 hydrogen bearing alloy high temperature 30 ℃ the time

Sample	Number of times	5-zhu	1-zhu	6-zhu	7-zhu	8-zhu	The 12-zhu Comparative Examples	13-zhu (commercially available) (Comparative Examples)
									Cast alloy	1	165	180	185	196	196	174	184
2	169	187	188	200	200	183	199
								3		173	193	192	203	203	191	209
4	177	195	198	207	207	196	217
								5		180	196	203	212	212	203	221
6	183	200	206	216	216	207	226
								7		186	201	210	218	218	211	231
8	188	203	213	221	221	214	232
								9		189	205	217	223	223	216	232
10	192	205	220	225	225	218	233
								11		194	207	222	226	226	221	235
Sample	Number of times	kc5-24	kc1-24	kc6-24	kc7-24	kc8-24	kc12-24										kc13-24
								Fast quenched alloy	1	228	235	239	244	248	224	219
2	231	237	240	248	253	232	226
									3	237	238	242	252	256	239	233
4	240	239	244	255	259	241	237
									5	241	240	245	259	262	243	240
6	242	242	249	262	266	246	243
									7	242	243	250	265	267	248	246
8	241	244	252	268	270	250	247
									9	242	245	253	269	272	251	248
10	241	246	254	271	272	252	250
									11	241	247	255	271	272	253	251

Claims (3)

1, a kind of high-temperature Ni/H 2 battery negative material, the composition composed atom % of this negative material is: A ₁B ₅, it is characterized in that forming high-temperature Ni/H 2 battery with in the negative material,

A is La, Ce, Pr, Nd, Y element;

B is Ni, Co, Mn, Al element;

The concrete composition weight % of this negative material is respectively: La 14.7-23.1%; Ce 4.0-12.1%; Pr1.0-1.8%; , Nd 2.0-3.8%; Y 0.5-5%; Co 4.5-6.5%; Mn 6.5-8.5%; Al0.6-1.8%; All the other are Ni.

2, a kind of high-temperature Ni/H 2 battery is with the preparation method of negative material, and this method is that the weight % by the negative material composition is: La 14.7-23.1%; Ce 4.0-12.1%; Pr 1.0-1.8%; , Nd 2.0-3.8%; Y 0.5-5%; Co 4.5-6.5%; Mn 6.5-8.5%; Al 0.6-1.8%; All the other are prepared burden for Ni; putting into the induction furnace of argon shield after raw material prepares again smelts and ingot casting; adopt the fast quenching equipment of prior art that alloy cast ingot is prepared into the hydrogen bearing alloy thin slice then; after it is characterized in that the alloy pig fusion in this quick-quenching method; the winding-up temperature that forms alloy liquid is 1100-1300 ℃; the blowing pressure of winding-up alloy liquid is 0.01-0.05Mpa; spacing between nozzle and the chill roll is 0.2-0.45mm, and the linear velocity of chill roll rotation is 15-30m/s.

3, according to the preparation method of the described negative material of claim 2, the body of inflating of the alloy liquid that it is characterized in that jetting is any one in nitrogen and the argon gas.

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