CN1044175C - Magnesium base hydrogen-storing alloy electrode - Google Patents

Magnesium base hydrogen-storing alloy electrode Download PDF

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Publication number
CN1044175C
CN1044175C CN94113952A CN94113952A CN1044175C CN 1044175 C CN1044175 C CN 1044175C CN 94113952 A CN94113952 A CN 94113952A CN 94113952 A CN94113952 A CN 94113952A CN 1044175 C CN1044175 C CN 1044175C
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China
Prior art keywords
alloy
powder
magnesium
hydrogen
magnesium base
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CN94113952A
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CN1102014A (en
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雷永泉
吴京
王启东
孙大林
吴煜明
刘卫红
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National Hi Tech New Energy Storage Material Engineering Development Center
Zhejiang University ZJU
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National Hi Tech New Energy Storage Material Engineering Development Center
Zhejiang University ZJU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a magnesium-based hydrogen-storing alloy electrode which is characterized in that amorphous magnesium-based alloy of which the chemical formula is Mg <x> Ni<100-x> is used as an active substance. The amorphous magnesium-based alloy directly uses a mechanical alloying method to make magnesium-based alloy powder of which the granularity is from 300 to 400 meshes. The magnesium-based alloy powder and copper powder or nickel powder are mixed to be cold pressed into a required electrode. Compared with the prior art, the magnesium-based hydrogen-storing alloy electrode has good electrochemical activity, can enhance electrochemical capacity in multiples, and is especially suitable for manufacturing a special hydride-nickel battery with high weight, energy and density requirements.

Description

The manufacture method of magnesium base hydrogen-storing alloy electrode material
The present invention relates to a kind of based on the electrode of magnesium-nickel alloy as active material, the manufacture method of particularly amorphous magnesium base hydrogen-storing alloy electrode material.
With the hydride-nickel secondary battery of hydrogen-storage alloy as negative electrode active material, owing to have advantages such as specific energy height, non-environmental-pollution and memory-less effect, now become a kind of novel high-capacity secondary cell and noticeable, the hydrogen-storing alloy electrode material of wherein progressively realizing industrialization mainly is AB 5Type mishmetal-nickel system alloy and AB 2The big series of type Laves phase alloy two, the former is as European patent EP 271043, Japan Patent JP63-264869, the latter such as U.S. Pat P4716088, European patent EP 0450590A etc.This two classes hydrogen-storage alloy all belongs to crystal alloy, and its weight energy density is 230～360mAh/g, because the weight of crystal alloy itself is bigger, has limited the further raising of its weight energy density; When simultaneously crystal alloy was inhaled hydrogen, its lattice cubical expansivity was bigger, reaches 15～25%, and alloy causes alloy inducing capacity fading and cycle life low with further efflorescence and suffer oxide etch in long-term charge and discharge process.
Along with the requirement of fields such as wireless telecommunications, household electrical appliance, electric automobile, artificial satellite to energy content of battery density improves day by day, the research and development high-energy-density and cheaply the high-performance hydrogen-storage alloy electrode material become the focus of people concern.
Characteristics such as magnesium base hydrogen-storing alloy has that hydrogen storage amount is big, in light weight, aboundresources, cost are low, but reason owing to the thermodynamics and kinetics aspect, the crystalline state magnesium base hydrogen-storing alloy must could be inhaled hydrogen in pressure is the high pressure hydrogen of 0.3～1MPa, just can put hydrogen under the hot conditions about 300 ℃, such hydrogen sucting discharging hydrogen condition is quite harsh.It is Mg that Chinese patent CN92100030.8 provides a kind of chemical formula 1.8Ni 0.8Sn 0.2Al 0.2Magnesium base alloy, prepare by vacuum melting method, wear into 300～400 purposes casting crystalline state magnesium base alloy powder with vibrating ball-mill again after pulverizer is pulverized, its activation processing is after alloy powder soaks through the hydro carbons organic substance, to use chemical plating method at its coating surface layer of Ni, Cr, P metallic compound.The magnesium base alloy powder that plating is crossed is put into vacuum furnace and was handled 10～20 hours down at 60～100 ℃, and technology is made magnesium base hydrogen-storing alloy electrode routinely at last.The kind electrode material can carry out the electrochemistry hydrogen sucting discharging hydrogen at normal temperatures and pressures, and under the discharging condition of 0.1C multiplying power, the heap(ed) capacity of alloy is 240mAh/g.Obviously, above-mentioned magnesium base alloy electrode material preparation process is than more complicated, and weight energy density also far can not satisfy the requirement of high power capacity hydride-nickel-based battery.
Studies show that the atom in the crystalline state hydrogen-storage alloy is regularly arranged by orderly lattice structure, the atom in the amorphous state hydrogen-storage alloy then is loose disordered structure, causes electrochemical hydrogenation and dehydrogenation mechanism to have significant difference thus.Hydrogen is only stored with the solid solution form in amorphous alloy, there is not the phase transition process that generates metal hydride, its P-C-T characteristic curve does not have land regions, because the generation and the volumetric expansion of metal hydride are the main causes that causes the absorption hydrogen efflorescence, the amorphous state hydrogen-storage alloy has superior anti-efflorescence characteristic.Simultaneously, the amorphous state hydrogen-storage alloy also has good antiacid caustic corrosion performance, is expected further to improve the cycle life of hydrogen-storing alloy electrode material, and therefore, the research and development of amorphous state hydrogen-storing alloy electrode material cause people's great interest.
U.S. Pat 4623597 announces that a kind of radio frequency sputtering method that adopts is deposited on Ni-Mg series non-crystalline state oxygen-storaged alloy film electrode on the nickel plate, its energy density is up to 566mAh/g, but the radio-frequency (RF) sputtering equipment costliness of preparation membrane electrode, the technology more complicated only is suitable for using for experimental study work.From hydride-nickel-based battery industrialization demand, the radio frequency sputtering method also can not mass-produce price can be the amorphous state hydrogen-storing alloy electrode material of market acceptance.
The object of the present invention is to provide a kind of manufacture method of amorphous magnesium base hydrogen-storing alloy electrode material, directly adopt the mechanical alloying method that the alloy raw material ball milling is become amorphous magnesium base alloy powder, this electrode material can successfully be realized the electrochemical hydrogenation and dehydrogenation process at normal temperatures and pressures, and its electrochemistry capacitance is up to 500mAh/g.
The objective of the invention is to adopt the method for mechanical alloying to realize.Raw material magnesium powder, nickel powder, perhaps Mg with component alloy 2The spherical tank of putting into ball mill after Ni, nickel powder mix carries out ball milling, and mechanical milling process makes that metal dust deforms repeatedly, superimposed, cold welding, pulverizing, finally reaches alloying and decrystallized purpose.For preventing alloy oxidation, whole process of preparation should be carried out in argon atmosphere.
A kind of manufacture method of magnesium base hydrogen-storing alloy electrode material is characterized in that its manufacturing process flow is:
---with purity is 99% magnesium powder, nickel powder, perhaps Mg 2Ni powder, nickel powder are raw material, weigh by the component proportioning that this electrode material is required, mix in being full of the glove box of argon gas;
---mixed powder places in the ball mill spherical tank; ball milling becomes the amorphous magnesium base hydrogen-storing alloy powder of 300～400 orders under argon atmosphere, and during ball milling, adopting the weight ratio of abrading-ball and alloy raw material is 15: 1; drum's speed of rotation is 220～230 rev/mins, and the ball milling time is 10～100 hours.The non-crystallization degree of magnesium base hydrogen-storing alloy can pass through X-ray diffraction analysis, differential thermal analysis or transmission electron microscope observing and determine.
With prior art relatively, the present invention program has following outstanding advantage:
1. adopt the method for mechanical alloying directly to prepare amorphous magnesium base hydrogen-storing alloy, this alloy has good electrochemical hydrogenation and dehydrogenation function at normal temperatures and pressures, and its electrochemistry capacitance is up to 500mAh/g;
2. this amorphous magnesium base hydrogen-storing alloy can be directly used in the manufacturing hydride electrode, without any need for activation processing, at the circulation time first time, can reach its high discharge capacity;
3. adopt the method for mechanical alloying to prepare amorphous magnesium base hydrogen-storing alloy, equipment is simple, and is easy to operate, is suitable for large-scale mass production;
4. small investment, cost is low, has the market competitiveness.
Embodiment:
A kind of manufacture method of amorphous magnesium base hydrogen-storing alloy electrode material is that 99% magnesium powder and nickel powder are raw material with purity, presses Mg 50Ni 50Stoichiometry, after in being full of the glove box of argon gas, mixing, place in the spherical tank that is full of argon gas of planetary ball mill, the weight ratio of abrading-ball and raw metal is 15: 1 in the control jar, drum's speed of rotation is 225 rev/mins, the ball milling time is 60 hours, obtains powdery Mg 50Ni 50Alloy is determined its non-crystallization degree through X-ray analysis, differential thermal analysis and transmission electron microscope observation, and the result is all decrystallized through 60 hours alloys of ball milling.
Test Mg 50Ni 50The electrochemistry capacitance of amorphous alloy electrode material, charging current is the 40mA/g alloy during test, overcharges 150%; Discharging current is respectively 20mA/g alloy and 100mA/g alloy, and the discharge stopping potential is-600mV.
Table 1 is amorphous Mg 50Ni 50The test data of the electrochemistry capacitance of alloy and ball milling time relationship.Test data shows that electrochemistry capacitance improves with alloy amorphousization degree and increases, and the final value of tending towards stability.Properties of Amorphous Mg Based Alloys hydrogen-storing alloy electrode material by this method manufacturing has good electrochemical properties, need not any activation processing during hydride electrode in preparation, in first time during charging cycle, can reach its high discharge capacity.
As a comparison, to Mg by the vacuum melting gained 50Ni 50The hydride electrode material of magnesium base alloy preparation because alloy is difficult to activation, is under the condition of 20mA/g alloy at discharging current, and its maximum discharge capacity only is 18～50mAh/g alloy.
Table 1
The ball milling time (hour) 10 30 50 70 100
Electrochemistry capacitance (mAh/g) C (20mA/g alloy) 15 365 460 497 500
C (100mA/g alloy) 7.5 255 298 380 419

Claims (1)

1. the manufacture method of a magnesium base hydrogen-storing alloy electrode material, it is characterized in that: its manufacturing process flow is:
---with purity is 99% magnesium powder, nickel powder, perhaps Mg 2Ni powder, nickel powder are raw material, weigh by the component proportioning that this electrode material is required, mix in being full of the glove box of argon gas;
---mixed powder places in the ball mill spherical tank; ball milling becomes the amorphous magnesium base hydrogen-storing alloy powder of 300～400 orders under argon atmosphere, and during ball milling, adopting the weight ratio of abrading-ball and alloy raw material is 15: 1; drum's speed of rotation is 220～230 rev/mins, and the ball milling time is 10～100 hours.
CN94113952A 1994-10-20 1994-10-20 Magnesium base hydrogen-storing alloy electrode Expired - Fee Related CN1044175C (en)

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Application Number Priority Date Filing Date Title
CN94113952A CN1044175C (en) 1994-10-20 1994-10-20 Magnesium base hydrogen-storing alloy electrode

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CN1044175C true CN1044175C (en) 1999-07-14

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1057314C (en) * 1996-03-22 2000-10-11 溧阳市冶建防腐材料厂 Double-component antirot zinc silicate paint and its use
CN1326265C (en) * 2005-08-30 2007-07-11 包头稀土研究院 Amorphous magnesium-Nickel series hydron-storage electrode material and producing method thereof
CN105483571B (en) * 2016-01-28 2017-07-25 同济大学 A kind of method that ball-milling method prepares amorphous magnesium alloy
CN105895888B (en) * 2016-06-22 2018-04-06 微山钢研稀土材料有限公司 Ni MH batteries RE Mg Ni Ti Cu Al B system AB types electrode metals and preparation method
CN113199021B (en) * 2021-04-09 2022-12-13 宁波职业技术学院 High-performance magnesium alloy composite powder for building material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623597A (en) * 1982-04-28 1986-11-18 Energy Conversion Devices, Inc. Rechargeable battery and electrode used therein
JPH01134861A (en) * 1987-11-20 1989-05-26 Sanyo Electric Co Ltd Manufacture of hydrogen absorption alloy electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623597A (en) * 1982-04-28 1986-11-18 Energy Conversion Devices, Inc. Rechargeable battery and electrode used therein
JPH01134861A (en) * 1987-11-20 1989-05-26 Sanyo Electric Co Ltd Manufacture of hydrogen absorption alloy electrode

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