CN101626078A - La-Mg-Ni negative hydrogen storage material for nickel-hydrogen batteries - Google Patents

La-Mg-Ni negative hydrogen storage material for nickel-hydrogen batteries Download PDF

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CN101626078A
CN101626078A CN200910163893A CN200910163893A CN101626078A CN 101626078 A CN101626078 A CN 101626078A CN 200910163893 A CN200910163893 A CN 200910163893A CN 200910163893 A CN200910163893 A CN 200910163893A CN 101626078 A CN101626078 A CN 101626078A
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hydrogen storage
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CN101626078B (en
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刘华福
李蓉
吴建民
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BEIJING HARMOFINERY TECHNOLOGY Co Ltd
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Abstract

The invention provides an La-Mg-Ni negative hydrogen storage material for nickel-hydrogen batteries with ultra-low self discharge and durable memory property. The La-Mg-Ni negative hydrogen storage material comprises constituents in an atomic ratio: La (0.65-x-y) Ndx, Dyy Ce0.1 Mg0.25, Ni3.27 and Al0.13, wherein x is larger than or equal to 0.1 and smaller than or equal to 0.3; and y is larger than or equal to 0.01 and smaller than or equal to 0.05. The La-Mg-Ni negative hydrogen storage material is a compound in a complex-phase structure, and the phase composition mainly comprises two different A5B19 type compounds in different structures with different space groups, wherein one compound is in a Pr6Co19 structure in a space group of P63/mmc, the other compound is in a Ce5Co19 structure in a space group of R-3m, and a ratio of the two compounds is about 6:4. In addition, the La-Mg-Ni negative hydrogen storage material also comprises a small amount of Ce2Ni7 type and PuNi3 type structural compounds and can be used as a negative electrode material for preparing the nickel-hydrogen batteries with ultra-low self discharge and durable memory property.

Description

La-Mg-Ni negative hydrogen storage material for nickel-hydrogen batteries
Technical field
The present invention relates to a kind of nickel-hydrogen battery negative electrode hydrogen storage material, relate in particular to a kind of La-Mg-Ni type nickel-hydrogen battery negative electrode hydrogen storage material.
Technical background
Metal hydride-nickel cell is since last century, put goods on the market the nineties, because that it has a capacity height, life-span is long, characteristics such as memory-less effect, non-environmental-pollution extensively receive an acclaim, and occupation rate of market is more and more higher.Cell types is also developed to other polytypes by AA, AAA common batteries, and product is widely used in electric tool, household electrical appliance, computer, space flight, communication and vehicle using motor etc., develops very rapid.Along with the increase of metal hydride-nickel cell application, also more and more higher to the requirement of battery performance.Particularly people recognize that progressively the memory property of battery and self-discharge characteristics have very big influence to the performance of battery in recent years, the memory property of battery is bad will directly to cause scrapping of battery, and the self discharge of battery too senior general be unfavorable for the use of battery, also will cause waste of electric energy simultaneously.Therefore the battery of research and development with long-term storage characteristic and low self-discharge characteristic becomes focus in recent years.
The self discharge of battery mainly be since battery under non operating state, anodal oxygen is separated out to combine with the hydrogen of negative pole and is produced.And the self-discharge characteristics main method of improving battery is exactly to improve the anodal oxygen and the stability of hydrogen in electrode of negative pole.People have done many work for this reason, as positive powder is coated cobalt, improve barrier film and electrolyte, in both positive and negative polarity, add some stability additives etc., these work have played some improvement effects really to the self-discharge characteristics of Ni-MH battery, but still do not tackle the problem at its root.
In recent years, add the AB of Mg 3～35Type La-Mg-Ni hydrogen storage material is because theoretical capacity surpasses 400mAh/g, and has good activation characteristic, becomes new research focus.The applicant is with La 1-xMg xNi 3.5Be research object, by adding different element kinds therein, thereby proposed a kind of cathode hydrogen storage material that uses for nickel-hydrogen battery of multiphase structure compound, this multiphase structure compound is P6 by space group mainly 3The Pr of/mmc 5Co 19The compound of structure and space group are the Ce of R-3m 5Co 19The compound of structure is formed, and two kinds of shared ratios of compound are about 6: 4, also have a spot of Ce in addition 2Ni 7And PuNi 3The type structural compounds.Battery studies show that the Ni-MH battery that utilizes this kind hydrogen storage material to make has extraordinary long-term storage characteristic and low self-discharge characteristic.
Summary of the invention
The objective of the invention is to obtain the cathode hydrogen storage material that the present commercially available prod of a kind of ratio has better long-term storage characteristic and low self-discharge characteristic, with the demand of satisfied storage characteristic for a long time and low self-discharge Ni-MH battery product by the composition improvement.
Specifically, the invention provides a kind of La-Mg-Ni type cathode hydrogen storage material that is applicable to Ni-MH battery with multiphase structure, it has extraordinary long-term storage characteristic and low self-discharge characteristic, and the atomic ratio composition of this La-Mg-Ni type cathode hydrogen storage material consists of La 0.65-x-yNd xDy yCe 0.1Mg 0.25Ni 3.27Al 0.13, wherein 0.1≤x≤0.3,0.01≤y≤0.05.
Preferably, cathode hydrogen storage material of the present invention is La 0.65-x-yNd xDy yCe 0.1Mg 0.25Ni 3.27Al 0.13, 0.1≤x≤0.2,0.01≤y0.03 wherein.
More preferably, cathode hydrogen storage material of the present invention is La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13
La-Mg-Ni type cathode hydrogen storage material of the present invention can be Pr 5Co 19Type and Ce 5Co 19The complex phase cathode hydrogen storage material that the type structure is mixed.
Preferably, Pr of the present invention 5Co 19Type and Ce 5Co 19Type complex phase cathode hydrogen storage material is La 0.65-x-yNd xDy yCe 0.1Mg 0.25Ni 3.27Al 0.13, 0.1≤x≤0.2,0.01≤y≤0.03 wherein.
More preferably, Pr of the present invention 5Co 19Type and Ce 5Co 19Type complex phase cathode hydrogen storage material is La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13
La-Mg-Ni type Pr 5Co 19And Ce 5Co 19Structure cathode hydrogen storage material and AB 5The intermetallic compound that hydrogen storage material equally is made up of elements A (as La, Nd, Mg etc.) and other element B (as Ni, Al, Mn, Co etc.) of easy generation stable hydride, its charge discharge capacity mainly comes to inhale to be put the hydrogen ion in the electrolyte in the hydrogen process electron transfer in the oxidation-reduction process takes place on hydrogen-bearing alloy electrode, and it is as follows that the charge discharge of ni-MH battery reacts ordinary representation:
The charging reaction:
At negative pole, when applying an electrode potential to negative electrode, the water in the electrolyte is broken down into hydrogen ion and hydroxide ion, and hydrogen ion becomes hydrogen atom at cathode hydrogen storage material surface electron gain, is inhaled in the alloy, and hydroxide ion is left in the electrolyte:
Alloy+H 2O+e -→Alloy[H]+OH -????????????????(1)
Alloy represents hydrogen bearing alloy in the formula.
At positive pole, two valency nickel in the hickelous nydroxide lose an electronics and are oxidized to nickelic and combine with hydroxide ion in the electrolyte and become nickel hydroxide:
Ni(OH) 2+OH -→NiOOH+H 2O+e -????????????????????(2)
Exoelectrical reaction:
At negative pole, be absorbed in that hydrogen in the hydrogen bearing alloy is released and be combined into water with hydroxide ion in the electrolyte, contribute an electronics simultaneously and form electric current.
Alloy[H]+OH -→Alloy+H 2O+e -???????????????????(3)
At positive pole, nickel hydroxide obtains an electronics and is reduced into the lower valency hickelous nydroxide and discharges hydroxide ion and enter in the electrolyte.
NiOOH+H 2O+e -→Ni(OH) 2+OH -????????????????????(4)
As Pr of the present invention 5Co 19Type and Ce 5Co 19The example of type complex phase cathode hydrogen storage material, atomic ratio one-tenth is grouped into and can be:
La 0.54Nd 0.1Dy 0.01Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.53Nd 0.1Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.52Nd 0.1Dy 0.03Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.51Nd 0.1Dy 0.04Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.50Nd 0.1Dy 0.05Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.44Nd 0.2Dy 0.01Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.42Nd 0.2Dy 0.03Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.41Nd 0.2Dy 0.04Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.40Nd 0.2Dy 0.05Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.34Nd 0.3Dy 0.01Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.33Nd 0.3Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.32Nd 0.3Dy 0.03Ce 0.1Mg 0.25Ni 3.27Al 0.13；
La 0.31Nd 0.3Dy 0.04Ce 0.1Mg 0.25Ni 3.27Al 0.13Or
La 0.30Nd 0.3Dy 0.05Ce 0.1Mg 0.25Ni 3.27Al 0.13Deng.
Pr of the present invention 5Co 19Type and Ce 5Co 19Type complex phase cathode hydrogen storage material can adopt conventional smelting method for preparing.
For example; can be La: Nd: Dy: Ce: Mg: Ni: Al=0.65-x-y: x: y with mol ratio: 0.1: 0.25: 3.27: 0.13 (0.1≤x≤0.3; carry out melting and be cast into ingot casting 0.01 raw material≤y≤0.05) is inserted the vaccum sensitive stove that vacuumizes the back and feed argon shield; then; ingot casting is carried out homogenizing in the heat-treatment furnace that vacuumizes afterwards and feed argon shield handle; treatment temperature is 1020 ℃, and temperature retention time is 8 hours, treats to take out ingot casting again behind the stove cool to room temperature.
Pr of the present invention 5Co 19Type and Ce 5Co 19Type complex phase cathode hydrogen storage material can be used for preparing the negative pole of Ni-MH battery.Adopt Pr of the present invention 5Co 19Type and Ce 5Co 19Type complex phase cathode hydrogen storage material has excellent long-term storage characteristic and ultralow self-discharge characteristics as the Ni-MH battery of negative pole.
With the AB that sells in the market 5The type hydrogen storage material is (as the traditional cathode hydrogen storage material MmNi for preparing with identical smelting technology 3.55Co 0.75Mn 0.4Al 0.3, wherein Mm is the lucium that contains La, Ce, Pr and Nd, its each composition percentage composition is 65wt%La, 24wt%Ce, 3wt%Pr and 8wt%Nd) compare Pr of the present invention 5Co 19Type and Ce 5Co 19Type cathode hydrogen storage material La 0.65-x-yNd xDy yCe 0.1Mg 0.25Ni 3.27Al 0.13The charge/discharge capacity of (0.1≤x≤0.3,0.01≤y≤0.05) significantly improves, and good cycle life is arranged.Correspondingly, adopt Pr of the present invention 5Co 19Type and Ce 5Co 19The long-term storage characteristic and the ultralow self-discharge characteristics of the excellence that the Ni-MH battery that type complex phase cathode hydrogen storage material prepares has than commercially available Ni-MH battery.
Description of drawings
Fig. 1 is La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13The X-ray Rietveld of sample composes fitting result entirely.
Fig. 2 a La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13Sample has been produced battery its capacity of insulation under 60 ℃ and has been reached over time and AB 5The contrast of the made battery of type hydrogen storage material.
Fig. 2 b La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13Sample has been produced battery its voltage of insulation under 60 ℃ and has been reached over time and AB 5The contrast of the made battery of type hydrogen storage material.
Fig. 2 c La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13Sample has been produced its capacity restoration characteristic of battery and time relation and and AB 5The contrast of the made battery of type hydrogen storage material.
Embodiment
Below in conjunction with embodiment the present invention is launched further description.But should be appreciated that following execution mode only is used for the present invention is illustrated and is not in order to limit scope of the present invention.
Percentage by weight according to each element of alloy in the table 1 is prepared burden; the alloy raw material for preparing is carried out the melting casting vacuumizing the back and feed in the induction furnace that argon shield is arranged; then ingot casting is fed after vacuumizing and carry out the homogenizing processing in the heat-treatment furnace that argon shield is arranged; treatment temperature is 1020 ℃; temperature retention time is 8 hours, treats to take out ingot casting again behind the stove cool to room temperature.
The composition of table 1 embodiment of the invention and prior art is (wt%) relatively
Figure G2009101638930D00051
X-ray diffraction is the result show, this compound is mainly by Pr 5Co 19Type and Ce 5Co 19The compound of two kinds of structures of type is formed, and also contains a spot of Ce in addition 2Ni 7And PuNi 3The type structural compounds.It is La that Fig. 1 has provided composition 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13The X-ray Rietveld of sample composes fitting result entirely, and its phase structure, space group are as shown in table 2 with each percentage composition mutually:
Table 2:La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13In contained phase and each mutually shared ratio
Phase structure ??Pr 5Co 19 ??Ce 5Co 19 ??Ce 2Ni 7 ??PuNi 3
Space group ??P6 3/mmc ??R-3m ??P6 3/mmc ??R-3m
Percentage composition ??46.52％ ??31.15％ ??12.16％ ??10.17％
The method of testing of electrochemistry capacitance is as follows: the hydrogen bearing alloy steel ingot after at first homogenizing being handled becomes less than 200 purpose alloyed powders in grinding at room temperature, then will be less than 200 purpose negative alloy powder 0.25g and nickel powder 1: 4 mixed by weight, and add an amount of poly-vinyl alcohol solution as binding agent, the cake that is cold-pressed into diameter and is 15mm uses the [Ni (OH) that used positive electricity is very identical with Ni-MH battery as negative electrode 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 storage hydrogen negative material is fully activated 30 ℃ of current densities with 60mA/g, the activation system is as follows: adopt the current density of 60mA/g to charge 450 minutes, paused 15 minutes in the charging back, then with the current density of 60mA/g discharge into the negative electrode current potential with respect to the electrode potential of reference electrode for till-0.5 volt, carry out the next round charge and discharge cycle again.Increase along with the activation number of times, capacity of negative plates will progressively increase and be relatively stable following after reaching a maximum, this moment, activation finished, and this maximum is decided to be the hydrogen storage capability of material under 30 ℃, will obtain the needed charge and discharge cycles number of times of this maximum and be called the activation number of times.
The compound hydrogen storage material of each execution mode of the present invention that said method is recorded under 30 ℃, 60mA/g charging and discharging currents density maximum electrochemistry capacitance test result and traditional AB of activation number of times and prior art 5Electrochemistry capacitance and the activation number of times of type hydrogen storage material under 30 ℃, 60mA/g charging and discharging currents density listed in the table 3.
Test for cycle life, charging and discharging currents density is chosen as 300mA/g, method of testing is as follows: at first adopt the current density of 60mA/g to activate by the method for above-mentioned test capacity with the activation number of times at 30 ℃ specimen, after activation is good, adopt the current density of 300mA/g that storage hydrogen negative material was charged 85 minutes at 30 ℃, paused 15 minutes in the charging back, then with the current density of 300mA/g discharge into the negative electrode current potential with respect to the electrode potential of reference electrode for till-0.5 volt, carrying out next round again fills, discharge cycles, in order to contrast conveniently, the cycle life of sample is defined as cycle-index when its capacity under this experiment condition drops to 160mAh/g, and its test result all is given in the table 3.
Activity function and electrochemistry capacitance (mAh/g) and under 30 ℃, 300mA/g charging and discharging currents density the cycle life relatively (by capacity is 160mAh/g) of table 3 hydrogen bearing alloy under 30 ℃, 60mA/g charging and discharging currents density
Figure G2009101638930D00071
By the data of table 3 as can be known: keeping a spot of Ce content, substituting La, when substituting amount more after a little while with Nd and Dy, can improve the electrochemistry capacitance and the cycle life of alloy, but along with the increase that substitutes amount, the electrochemistry capacitance and the cycle life of alloy reduce on the contrary, but with conventional AB 5Type alloy phase ratio, though the life-span is poor slightly, capacity has very big increase, its high electrochemistry capacitance has reached 370mAh/g, far above the AB that sells in the market 5The electrochemistry capacitance value of type hydrogen storage material.
The present invention's composition is La in addition 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13Sample has been produced battery and has been investigated its self-discharge performance, its result as shown in Figure 2, as seen from the figure, with AB 5Type hydrogen storage alloy is compared, no matter the battery of producing with this alloy be capability retention, voltage retention, or the capacity restoration rate is all keeping higher level, the advantage that highly significant is arranged, so this alloy is very suitable for producing the Ni-MH battery with ultralow self discharge and long-time storage performance.
In sum, at La-Mg-Ni is in the hydrogen storage material, suitable selection atom proportioning, and substitute La with Ce, Nd and Dy, when substituting amount more after a little while, available can be excellent is suitable for compound high power capacity, long-life that Ni-MH battery the uses cathode hydrogen storage material that uses for nickel-hydrogen battery.Its electrochemistry charge and discharge capacity reaches as high as 370mAh/g, far above present commercially available AB 5The electrochemistry charge and discharge capacity of type hydrogen storage alloy.With AB 5Type hydrogen storage alloy is compared, no matter the battery of producing with this alloy be capability retention, voltage retention, or the capacity restoration rate is all keeping higher level, the advantage that highly significant is arranged, so this alloy is very suitable for producing the Ni-MH battery with ultralow self discharge and long-time storage performance.

Claims (7)

1 one kinds of La-Mg-Ni type cathode hydrogen storage materials, its atomic ratio one-tenth is grouped into and is expressed from the next:
La 0.65-x-yNd xDy yCe 0.1Mg 0.25Ni 3.27Al 0.13, wherein 0.1≤x≤0.3,0.01≤y≤0.05.
2 cathode hydrogen storage materials as claimed in claim 1 is characterized in that, 0.1≤x in the above-mentioned formula≤0.2,0.01≤y≤0.03.
3 cathode hydrogen storage materials as claimed in claim 1 is characterized in that, described cathode hydrogen storage material is expressed from the next:
La 0.54Nd 0.1Dy 0.01Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.53Nd 0.1Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.52Nd 0.1Dy 0.03Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.51Nd 0.1Dy 0.04Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.50Nd 0.1Dy 0.05Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.44Nd 0.2Dy 0.01Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.42Nd 0.2Dy 0.03Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.41Nd 0.2Dy 0.04Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.40Nd 0.2Dy 0.05Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.34Nd 0.3Dy 0.01Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.33Nd 0.3Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.32Nd 0.3Dy 0.03Ce 0.1Mg 0.25Ni 3.27Al 0.13
La 0.31Nd 0.3Dy 0.04Ce 0.1Mg 0.25Ni 3.27Al 0.13Or
La 0.30Nd 0.2Dy 0.05Ce 0.1Mg 0.25Ni 3.27Al 0.13。
4 cathode hydrogen storage materials as claimed in claim 3 is characterized in that described cathode hydrogen storage material is expressed from the next: La 0.43Nd 0.2Dy 0.02Ce 0.1Mg 0.25Ni 3.27Al 0.13
5 as any described cathode hydrogen storage material in the claim 1～4, it is characterized in that described cathode hydrogen storage material is Pr 5Co 19Type and Ce 5Co 19The complex phase cathode hydrogen storage material that the type structure is mixed.
The application of any described cathode hydrogen storage material in the preparation nickel-hydrogen battery negative pole in 6 claims 1～5.
7 application as claimed in claim 6 is characterized in that, described Ni-MH battery is the Ni-MH battery with low self-discharge and good memory property.
CN2009101638930A 2009-08-14 2009-08-14 La-Mg-Ni negative hydrogen storage material for nickel-hydrogen batteries Expired - Fee Related CN101626078B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102054982A (en) * 2010-10-27 2011-05-11 北京宏福源科技有限公司 La-Mg-Ni type negative-pole hydrogen storage material for low-temperature nickel-hydrogen battery
CN103094531A (en) * 2011-11-01 2013-05-08 北京宏福源科技有限公司 La-Mg-Ni negative electrode hydrogen storage material used in power-type nickel-metal hydride battery
CN106086569A (en) * 2016-08-22 2016-11-09 河南理工大学 Multiphase Mg-RE-Ni hydrogen storage alloy and application thereof
CN112708801A (en) * 2020-12-03 2021-04-27 包头稀土研究院 Single-phase PuNi3Superlattice La-Y-Ni hydrogen storage alloy and preparation method thereof
CN114946051A (en) * 2020-04-10 2022-08-26 日本重化学工业株式会社 Hydrogen-absorbing alloy for alkaline storage battery

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102054982A (en) * 2010-10-27 2011-05-11 北京宏福源科技有限公司 La-Mg-Ni type negative-pole hydrogen storage material for low-temperature nickel-hydrogen battery
CN103094531A (en) * 2011-11-01 2013-05-08 北京宏福源科技有限公司 La-Mg-Ni negative electrode hydrogen storage material used in power-type nickel-metal hydride battery
CN103094531B (en) * 2011-11-01 2015-11-11 北京宏福源科技有限公司 A kind of power-type La-Mg-Ni negative hydrogen storage material for nickel-hydrogen batteries
CN106086569A (en) * 2016-08-22 2016-11-09 河南理工大学 Multiphase Mg-RE-Ni hydrogen storage alloy and application thereof
CN106086569B (en) * 2016-08-22 2017-11-14 河南理工大学 Multiphase Mg-RE-Ni hydrogen storage alloy and its application
CN114946051A (en) * 2020-04-10 2022-08-26 日本重化学工业株式会社 Hydrogen-absorbing alloy for alkaline storage battery
CN114946051B (en) * 2020-04-10 2024-06-11 日本重化学工业株式会社 Hydrogen storage alloy for alkaline storage battery
CN112708801A (en) * 2020-12-03 2021-04-27 包头稀土研究院 Single-phase PuNi3Superlattice La-Y-Ni hydrogen storage alloy and preparation method thereof

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