CN1417878A - Lithium-containing hydrogen-storing alloy electrode material and its prepn - Google Patents

Lithium-containing hydrogen-storing alloy electrode material and its prepn Download PDF

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CN1417878A
CN1417878A CN02158001A CN02158001A CN1417878A CN 1417878 A CN1417878 A CN 1417878A CN 02158001 A CN02158001 A CN 02158001A CN 02158001 A CN02158001 A CN 02158001A CN 1417878 A CN1417878 A CN 1417878A
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lithium
hydrogen storage
storage alloy
alloy
electrode material
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CN1180495C (en
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吴锋
高学平
曲金秋
金季荪
李玉刚
牛广良
袁华堂
宋德瑛
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Nankai University
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Abstract

In the present invention, during the ball milling of AB5 type hydrogen-storing alloy is a special high-energy ball mill, LiH or Li is made to form alloy mechanically with AB5 type hydrogen-storing alloy to prepare composite hydrogne-storing alloy electrode material with Li content of 0.1-2.0 wt%. The present invention is also suitable for preparing composite lithium-containing hydrogen-storing alloy electrode material with AB, A2B and AB2 type hydrogen-storing alloy. The present invention utilizes the leaching of Li in alkali solution of make hydrogen-storing alloy form pores and to raise the electric catalytic activity of Ni/MH cell negative pole. In addition, Li dissolved in the alkali solutio to form LiOH can protect the positive pole of the cell, and raise the circulation life and discharge capacity of cell.

Description

Lithium-containing composite hydrogen storage alloy electrode material and preparation method thereof
Technical Field
The invention relates to a lithium-containing composite hydrogen storage alloy electrode material and a preparation method thereof, belonging to hydrogen storage alloy electrode materials and preparation technologies.
Background
Nickel-metal hydride batteries (Ni/MH batteries) have been rapidly developed because of their advantages of high energy density, long cycle life, no memory effect and no environmental pollution. The small cylindrical nickel-metal hydride battery is industrialized and commercialized; the high-capacity power Ni/MH battery is selected as the power battery of the electric vehicle due to the environmental pollution caused by the exhaust gas of fuel motorcycles and automobiles, and research and development are being accelerated. At present, the Ni/MH battery negative electrode hydrogen storage material is basically multielement AB5Hydrogen occluding alloy, wherein Mm (Ni-Co-Mn-Al)5(J62020-25-A, CA 107: 99728f) was widely used. Hydrogen storage alloy electrode material MmNi5-x-y-z-uAxByCzDuOne of the groups-Mm (Ni-Mn-Co-Al-Li) in (A ═ Mn, Sn or V; B ═ Cr, Co, Ti, Nb, Zr or Si; C ═ Al, Mg or Ca; D ═ Li, Na or K; ZL 92100029.4; US 5, 242656; EP 0554617B1)5The electrochemical capacity is more than or equal to 320mAh/g, the Ni/MH battery is assembled by the prepared electrode, and inthe activation and use process of the battery, Li in the alloy is dissolved out in alkali liquor (electrolyte of the battery), so that the hydrogen storage alloy forms micropores, and the cathode electrocatalytic activity of the Ni/MH battery is improved. Meanwhile, Li is dissolved in alkali liquor to form LiOH, so that the effect of protecting the positive electrode of the battery is achieved, and the cycle life and the discharge capacity of the battery are improved. However, Mm (Ni-Co-Mn-Al-Li)5During smelting of the hydrogen storage alloy in a vacuum induction furnace, because the melting point and the boiling point of Li are much lower than those of other metals (the melting point of Li is 180 ℃, the boiling point is 1330 ℃, the boiling point of other metals is the lowest Mn 2150 ℃ and the boiling point of other metals is the highest La 3470 ℃), the Li is extremely volatile, cannot be operated and is difficult to smelt, and meanwhile, the content of Li in the alloy is difficult to control in advance. To solve this problem, LiH is added to the master alloy powder Mm (Ni-Co-Mn-Al)5-x(x is the atomic ratio of Li in the alloy) diffusion method for preparing Mm (Ni-Co-Mn-Al-Li)5The hydrogen-absorbing alloy (journal of chemistry 1999, 57: 1338; J. alloys Comp., 2000, 302: 65) has the same properties as the hydrogen-absorbing alloy produced by the smelting process. The diffusion process comprises the following steps: LiH and Mm (Ni-Co-Mn-Al)5-xMixing the master alloy powders, tabletting, diffusing at 850 ℃ for 3 hours under the protection of inert atmosphere, and crushing to prepare powder. The diffusion method solves the problem that Li is very easy to volatilize in the smelting methodThe diffusion method has the defects of difficult operation, increased process and equipment, more energy consumption, product cost increase (about 20 percent) and difficult realization of industrialization.
Disclosure of Invention
The invention aims to provide a lithium-containing composite hydrogen storage alloy electrode material and a preparation method thereof. The phase of the lithium-containing composite hydrogen storage alloy electrode material is the same as that of the original hydrogen storage alloy, and the cycle service life is long; the preparation method has low energy consumption, simple adopted equipment and easy industrialization.
The lithium content in the composite hydrogen storage alloy is 0.1-2.0%, the phase of the material is the same as that of the original hydrogen storage alloy, and the electrochemical hydrogen storage is more than or equal to 320 mAh/g.
The invention is realized by the following technical scheme. And (2) adopting a special high-energy ball mill, and spraying lithium hydride powder decomposed into lithium mist particles by the high-energy ball mill or spraying molten lithium mist particles into the hydrogen storage alloy fragments in the crushing process. The specific technology is that argon is filled in a cylinder of the ball mill, the diameter of a steel ball is 4-15nm, and the mass ratio of the steel ball to alloy is (60-10) to 1; under the ball milling condition that the ball milling stirring speed is 100 plus 1000 r/min, molten metal lithium mist particles (180 plus 200 ℃) with the mass of 0.1-2.0% of the alloy are sprayed into the hydrogen storage alloy in the process of crushing and ball milling the hydrogen storage alloy, or lithium hydride powder with the mass of 0.1-2.3% of the alloy and more than 200 meshes is sprayed into the hydrogen storage alloy.
The hydrogen storage alloy of the present invention includes rare earth nickel-based Alloy (AB)5) Zirconium-based Laves phase Alloy (AB)2) Titanium-nickel-based Alloy (AB) and magnesium-based alloy (A)2B)。
The high-energy ball milling enables metal powder to bear the action of impact, shearing, friction and compression under the repeated collision of a ball milling medium, and the metal powder is subjected to repeated extrusion, cold welding and crushing processes to become dispersed ultrafine particles, and alloying is realized in a solid state to form an alloy (Met. trans., 1970, 1: 2943; scientific. Amer., 1976, 234: 40). High energy ball milling also increases the energy stored in the system, causing a temperature rise at the interface at the moment the ball collides with the Powder particle, which not only promotes diffusion at the interface, but also induces heterogeneous chemical reactions therein (New Material by Mechanical Alloying, Eimformations Geselschaft, 1988; J Japan Soc Powder and Powder Metallurgy, 1991, 38: 83; J Mater Sci letter, 1990, 97: 1014).
LiH or Li and Mm (Ni-Co-Mn-Al)5-xThe process of forming the Li-containing composite hydrogen storage alloy electrode material in the high-energy ball milling process comprises the following steps: in master alloy Mm (Ni-Co-Mn-Al)5-xThe medium misch metal Mm has the greatest chemical affinity, so Li first and mainly alloys or chemically reacts with Mm. La represents the mixed rare earth element Mm and-La represents La in the alloy. The LiH is alloyed by the following ways:
， (1)
(2)
(3) under the high-energy ball milling, the reactions (1), (2) and (3) can be carried out, but the ball milling is carried out in a dry inert atmosphere, the surface of the newly pulverized alloy powderdoes not have-La2O3The existence of the surface of the bulk alloy is possible only before the pulverization, so that (3) rarely occurs in the formation of the composite hydrogen occluding alloy. Metal Li only passing through And (4) realizing alloying. During the ball milling mechanical alloying process, Li-containing hydrogen storage alloy is formed on the surfaces of the master alloy particles. Since there is a possibility that the inside of the master alloy particle is not alloyed with Li, or LiH or Li is locally non-uniform in the master alloy particle, and thus a small portion of the surface of the master alloy particle is not alloyed with Li, the Li-containing composite hydrogen storage alloy electrode material is formed integrally. Other AB, A2B、AB2Ti, Mg, Zr and AB in various hydrogen storage alloys5And the La is similar to the Li-containing composite hydrogen storage alloy electrode material.
The invention has the advantages that the alloy crushing and the mechanical alloying are synchronously carried out, so the preparation method has simple process and equipment, low energy consumption and low preparation cost, and is easy for industrialization and popularization. The material phase of the prepared lithium-containing composite hydrogen storage alloy electrode material is the same as that of the original hydrogen storage alloy, and belongs to CaCu5And (5) structure. The electrochemical test results show that the electrode has the advantages of fast activation, high specific capacity, good high-rate discharge performance, reduced impedance value of electrochemical reaction and long cycle service life.
Drawings
FIG. 1 is an X-ray diffraction pattern of a lithium-freemaster alloy in example 1 of the present invention.
FIG. 2 is an X-ray diffraction chart of a lithium-containing (0.04 atomic ratio) composite hydrogen storage alloy in example 1 of the present invention.
FIG. 3 is an X-ray diffraction chart of a lithium-containing (0.10 atomic ratio) composite hydrogen storage alloy in example 2 of the present invention.
Detailed Description
Example 1
5000 g of master alloy (MLNi) was taken3.8Co0.5Mn0.4Al0.27) The fragments (calculated by the sphere, the diameter is 5-10mm) are put into a fragment storage tank, and 4 g of lithium hydride (LiH) powder (sieved by a 200-mesh sieve) is weighed in a drying box and put into a powder storage tank. The two material storage tanks are hermetically connected with the upper chamber of the special high-energy ball mill. 4/5 high grinding balls (diameter is 5mm) are placed in the lower cavity of the ball mill, and the vortex type oscillating screen and the finished product packaging can are hermetically connected with the lower cavity. And opening a cooling water throttle, starting a vacuum pump to vacuumize, and inputting inert gas. Starting a motor stirring shaft to rotate, opening a valve of the fragment material tank, enabling the hydrogen storage alloy fragments to fall into the upper cavity, opening a valve of the powder storage tank, driving the lithium hydride powder to be sprayed on the moving fragments by inert gas, and enabling the lithium hydride powder to be uniformly dispersed in the hydrogen storage alloy fragments through stirring. And opening the upper and lower chamber openers, and allowing the mixed material in the upper chamber to fall into the upper part of the lower chamber filled with the hard alloy balls. The rotating speed of the stirring shaft is adjusted to be 600 rpm. The material moves to the bottom of the lower chamber along with the rotation of the stirring rod, and the stirring rod, the hard alloy ball and the material are repeatedly impacted, sheared, rubbed, cold welded and compressed to synchronously crush and alloy the mixed material, so as to prepare the lithium-containing composite hydrogen storage alloy electrode material. And feeding the material powder into a vibration sieve, and feeding the finished product powder into a finished product packaging tank through vortex vibration separation. Sampling for test analysis. For comparison, the master alloy was sampled and analyzed simultaneously (for convenience of the table, M-master alloy, L-Li-containing composite hydrogen storage alloy). The composition analysis is shown in Table 1 (measured by ICP method, Ni is EDTA capacity method, Li is atomic absorption method):
element(s) La Ce Pr Nd Ml Ni Co Mn Al Li
M(wt％) 17.8 9.48 1.25 4.81 33.34 52.8 6.98 5.20 1.72
L(wt％) 17.8 9.49 1.24 4.80 33.33 52.7 6.97 5.20 1.72 0.07
Note that the phase analysis of the misch metal with Ml of La, Ce, Pr and Nd (X-ray diffractometer Nippon science Dmax-2500 type, irradiation CuK α, graphite monochromator, working voltage 40Kv, current 100mA) shows that the phases of the master alloy and the Li-containing composite hydrogen storage alloy are basically the same and belong to the same CaCu5Structure (see figures 1 and 2). Electrochemical capacity test: a three-electrode system is adopted, the research electrode is a hydrogen storage alloy electrode, the auxiliary electrode is a nickel hydroxide electrode, and the reference electrode is an HgO/Hg electrode. After electrode conversion, the discharge capacity of the electrode was 0.7V after 5 hours discharge, the L electrode was 330.0mAh/g, and the M electrode was 325.2 mAh/g. 0.2C discharge capacity (table 2):
period of discharge 1 2 3 4 5 6 7 8 9 10
L(mAh/g) 286.9 300.3 310.5 320.1 329.4 329.8 329.7 330.1 329.9 330.0
M(mAh/g) 265.0 274.9 282.0 290.2 297.3 305.7 312.8 318.9 322.6 325.1
1C discharging: the 11 th cycle was discharged with 1C. L is 320.3mAh/g, and 0.2C/1C percent is 97.1 percent; m is 309.1mAh/g，0.2C/1C％＝95.1％。
Example 2
The lithium hydride (LiH) powder storage tank in the special high-energy ball mill in the embodiment 1 is changed into the lithium metal with electric heatingAnd (5) storing the lithium metal into a storage tank, and weighing 8 g of lithium metal in a drying box to be placed into the storage tank. The process is basically the same as that of example 1, except that the inert gas drives the lithium hydride powder to be sprayed on the moving fragments, and the inert gas drives the molten liquid metal lithium (180-. Finally sampling for test analysis. Composition analysis (see table 3) (ICP method measurement, but Ni is EDTA volumetric method and Li is atomic absorption method):
element(s) La Ce Pr Nd Ml Ni Co Mn Al Li
M(wt％) 17.8 9.48 1.25 4.81 33.34 52.8 6.98 5.20 1.72
L(wt％) 17.8 9.47 1.23 4.80 33.30 52.7 6.96 5.19 1.72 0.16
Note: mixed rare earth metal phase analysis with Ml of La, Ce, Pr and Nd (conditions same as example 1): compared with mother alloy, the X-ray diffraction pattern of lithium-containing composite hydrogen storage alloy has basically the same phase and belongs to CaCu5Structure (see figure 3). Electrochemical capacity test (see table 4) (conditions as in example 1), 0.2C discharge capacity is:
period of discharge 1 2 3 4 5 6 7 8 9 10
L(mAh/g) 284.8 296.4 315.5 321.5 323.8 325.3 3282 330.3 330.2 330.4
M(mAh/g) 265.0 274.9 282.0 290.2 297.3 305.7 312.8 318.9 322.6 325.1
1C discharging: the 11 th cycle was discharged with 1C. L is 321.9mAh/g, and 0.2C/1C percent is 97.4 percent; m is 309.1mAh/g, and 0.2C/1C% ═ 95.1%.
Example 3
Negative electrodes were prepared from the lithium-containing composite hydrogen absorbing alloy powder and master alloy powder prepared in example 1, respectively, and AA type pseudo Ni/MH batteries (L battery and L battery, respectively) were assembledM cells), a life test was performed. The discharge system is as follows: after the cell is converted into a telephone cell, the discharge capacity of the cell is 1V after 5 hours of discharge, the L cell is 1560mAh, and the M cell is 1515 mAh. According to 1C5In the full charge-discharge life standard, when the L battery is charged with 1560mA (M battery 1515mA) until- Δ V appears at 10mV, the L battery is stopped, and the L battery is left for 15 minutes, discharged to 1.0V with the same current, and then left for 15 minutes, and the L battery is transferred to the next cycle test. The internal resistance of the battery is measured once every 50 weeks after the end of the cycle discharge, and the battery discharge median voltage is 1C5Cell voltage at 30 minutes of discharge. The life test data is shown in table 5:
period of time 1 50 100 150 200 250 300
L Battery with a battery cell Discharge capacity mAh 1513 1518 1520 1517 1518 1520 1518
Median voltage mV 1241 1240 1239 1240 1238 1236 1233
M Battery with a battery cell Discharge capacity mAh 1439 1442 1445 1462 1460 1458 1455
Median voltage mV 1237 1239 1240 1239 1237 1236 1233
Period of time 350 400 450 500 550 600 650
L Battery with a battery cell Discharge capacity mAh 1488 1422 1386 1322 1279 1248 1170
Median voltage mV 1230 1222 1210 1186 1157 1132 1110
M Battery with a battery cell Discharge capacity mAh 1396 1328 1275 1212 1112 1065 1007
Median voltage mV 1229 1220 1206 1150 1103 1088 1057

Claims (4)

1. The lithium-containing composite hydrogen storage alloy electrode material is characterized by that the mass content of lithium in the composite hydrogen storage alloy is 0.1-2.0%, its phase is identical to original hydrogen storage alloy, and its electrochemical hydrogen storage is greater than or equal to 320 mAh/g.
2. The lithium-containing composite hydrogen storage alloy electrode material according to claim 1, characterized in that: the hydrogen storage alloy can include various types of hydrogen storage alloys AB5、AB2AB and A2B。
3. A method for preparing the lithium-containing composite hydrogen storage alloy electrode material according to claim 1, which is prepared by ball milling with a special high-energy ball mill, and is characterized in that lithium particles are sprayed into the lithium-containing composite hydrogen storage alloy during the crushing process of ball milling and crushing the hydrogen storage alloy, and the lithium particles can be provided by decomposing lithium hydride (LiH) powder through high-energy ball milling or spraying molten metal lithium mist particles.
4. The method for preparing the lithium-containing composite hydrogen storage alloy electrode material as claimed in claim 3, wherein argon gas is introduced into the ball mill cylinder, the diameter of the steel ball is 4-15mm, the mass ratio of the steel ball to the alloy is (60-10): 1, and the ball milling stirring speed is 100-.
CNB021580014A 2002-12-20 2002-12-20 Lithium-containing hydrogen-storing alloy electrode material and its prepn Expired - Fee Related CN1180495C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102437317A (en) * 2011-04-29 2012-05-02 中国科学院长春应用化学研究所 Super-entropy change method of AB 4.7 non-stoichiometric ratio hydrogen storage alloy
CN103107349A (en) * 2011-11-10 2013-05-15 通用汽车环球科技运作有限责任公司 Electrochemical process and device for hydrogen generation and storage
CN106865497A (en) * 2017-03-17 2017-06-20 南开大学 A kind of preparation method of the growth in situ nanometer magnesium-supported high-ratio surface material of hydrogenation
CN110405219A (en) * 2019-07-29 2019-11-05 四川大学 The preparation method and high power hydrogen-bearing alloy powder of high power hydrogen-bearing alloy powder

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102437317A (en) * 2011-04-29 2012-05-02 中国科学院长春应用化学研究所 Super-entropy change method of AB 4.7 non-stoichiometric ratio hydrogen storage alloy
CN102437317B (en) * 2011-04-29 2013-10-16 中国科学院长春应用化学研究所 Super-entropy change method of AB 4.7 non-stoichiometric ratio hydrogen storage alloy
CN103107349A (en) * 2011-11-10 2013-05-15 通用汽车环球科技运作有限责任公司 Electrochemical process and device for hydrogen generation and storage
CN103107349B (en) * 2011-11-10 2016-02-24 通用汽车环球科技运作有限责任公司 For generating and the electrochemical method of hydrogen storage and device
US9540738B2 (en) 2011-11-10 2017-01-10 GM Global Technology Operations LLC Electrochemical process and device for hydrogen generation and storage
CN106865497A (en) * 2017-03-17 2017-06-20 南开大学 A kind of preparation method of the growth in situ nanometer magnesium-supported high-ratio surface material of hydrogenation
CN106865497B (en) * 2017-03-17 2018-12-18 南开大学 A kind of growth in situ nanometer hydrogenates the preparation method of magnesium-supported high-ratio surface material
CN110405219A (en) * 2019-07-29 2019-11-05 四川大学 The preparation method and high power hydrogen-bearing alloy powder of high power hydrogen-bearing alloy powder

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