CN1299819C - Regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and its preparing method - Google Patents

Regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and its preparing method Download PDF

Info

Publication number
CN1299819C
CN1299819C CNB2005100167176A CN200510016717A CN1299819C CN 1299819 C CN1299819 C CN 1299819C CN B2005100167176 A CNB2005100167176 A CN B2005100167176A CN 200510016717 A CN200510016717 A CN 200510016717A CN 1299819 C CN1299819 C CN 1299819C
Authority
CN
China
Prior art keywords
quasi
crystal material
hydrogen
ball
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2005100167176A
Other languages
Chinese (zh)
Other versions
CN1709564A (en
Inventor
王立民
刘宝忠
吴耀明
彭秋明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CNB2005100167176A priority Critical patent/CN1299819C/en
Publication of CN1709564A publication Critical patent/CN1709564A/en
Application granted granted Critical
Publication of CN1299819C publication Critical patent/CN1299819C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The present invention provides a single regular icosahedron quasi-crystal material with the function of hydrogen storage, which comprises Ti100-x-y-zZrxNiyCuz (10<x<45, 5<y<20, 1<z<10). The forming capability of alloy quasi-crystals is strong, the formed quasi-crystal material is in a single regular icosahedron structure, and the thermodynamics is stable. The quasi-crystal material has good hydrogen storage properties and can be applied to gas hydrogen storage materials and battery negative electrode materials. The present invention simultaneously provides a preparing method for the material. In the preparing method of the present invention, according to the metering required by the general formula for the composition of the quasi-crystal material, powders of Ti, Zr, Ni, and Cu of 100 meshes per cm<2> of chemical purity are used to be filled in a ball milling tank of a high-energy ball mill with the ratio of grinding media to materials is 20: 1, the powders are ball-milled for 100 to 200 hours under the protection of argon, the ball-milled alloy powders are enclosed in a quartz tube and are thermally treated under 1*10<-3>Pa for 0.5 to 6 hours at the heat treatment temperature of between 480 and 650 DEG C. The present invention has the advantages of simple processes, strong operability and easy industrialization.

Description

A kind of regular icosahedron titanium-base quasi-crystal material and preparation method thereof with hydrogen-storage function
Technical field:
The invention belongs to quasicrystal material with hydrogen-storage function, particularly a kind of Thermodynamically stable and single regular dodecahedron quasicrystal material of Ti-Zr-Ni-Cu of being easy to produce and preparation method thereof.
Background technology:
Quasicrystalline alloy has special symmetrical structure, and easily with the symmetrical crystal face of H-H reaction with help the crystal structure of hydrogen in the structure cell diffusion inside, one of hydrogen-storage alloy that the quasicrystalline alloy conduct has development potentiality is paid attention to by people; United States Patent (USP) discloses and has been entitled as the patent of " hydrogen-storage alloy and be used for alkaline secondary cell " for No. 006030724, quasicrystalline alloy such as the Mg-Ca-Zn of this patent employing regular dodecahedron and Mg-Al-Zn system, fill-put hydrogen circulation 500 times, its quasicrystal structure does not still have destroyed, and having kept percentage by weight is 3.5% hydrogen storage amount, and this hydrogen-storage alloy can be used as the negative material of Ni-MH battery.0.5C circulate 820 times, the electrochemistry capacitance of this hydrogen-storage alloy still keeps 320mAh/g, surpasses the LaNi that present Ni-MH battery generally uses 5Hydrogen-storage alloy powder; But; this invention weak point is the selection of formation element basic 1,2,3,4 main groups and 1,2,3,8 subgroups at the periodic table of elements of quasicrystal material; although that protects in the claim is very wide; it is the active element of Mg, Ca, Zn, these easy oxidations of Al basically that the main body of selecting in fact constitutes element, for actual production and application bring difficulty.
Summary of the invention:
One of purpose of the present invention is to provide a kind of Ti-Zr-Ni-Cu single regular dodecahedron quasicrystal material, and this Material Thermodynamics is stable, is easy to produce, and has good hydrogen-storage function simultaneously.
The invention provides a kind of single regular dodecahedron quasicrystal material of Ti-Zr-Ni-Cu with hydrogen-storage function, it is characterized in that: this alloy material is made up of the accurate crystalline phase of single regular dodecahedron, and the alloying component general formula is Ti 100-x-y-zZr xNi yCu z, 10＜x＜45,5＜y＜20,1＜z＜10 wherein.
Another purpose of the present invention also provides above-mentioned Ti-Zr-Ni-Cu the preparation method of single regular dodecahedron quasicrystal material; it is characterized in that: by the metering of described alloying component general formula requirement; select the chemical pure Ti of 100 orders, Zr, Ni, Cu powder for use; pack into the ball grinder of high energy ball mill; ratio of grinding media to material is 20: 1; ball milling is 100～200 hours under argon shield, with behind the ball milling alloyed powder enclose in the quartz ampoule, 1 * 10 -3Heat-treat under the Pa, heat treatment temperature is 480～650 ℃, and the time is 0.5～6 hour.
The invention has the advantages that: the accurate brilliant formation ability of this material is strong, and the quasicrystal material of formation is single regular dodecahedron structure, and Thermodynamically stable, has good hydrogen sucking function and high electrochemical discharge capacity.Quasicrystal material with storage hydrogen function of the present invention can be used as hydrogen storage material and cell negative electrode material; Method technology of the present invention is simple, workable, is easy to industrialization.
Description of drawings:
Fig. 1 is X-ray diffraction (XRD) result of embodiment 1, and Fig. 1 also is the specification digest accompanying drawing;
Fig. 2 is 5 symmetrical electron diffraction patterns of embodiment 1;
Fig. 3 is the suction hydrogen kinetic curve of embodiment 1;
Fig. 4 is the electrochemical discharge curve of embodiment 1;
Fig. 5 is the XRD result of embodiment 2;
Fig. 6 is the XRD result of embodiment 4.
The specific embodiment:
Embodiment 1:
Press composition Ti 45Zr 35Ni 17Cu 3, select the chemical pure Ti of 100 orders, Zr, Ni, Cu powder for use, the ball grinder of the high energy ball mill of packing into, ratio of grinding media to material is 20: 1, under argon shield, ball milling 200 hours is enclosed the alloyed powder behind the ball milling in the quartz ampoule, 1 * 10 -3Heat-treat under the Pa, temperature is 580 ℃, and the time is 0.5 hour, and with the alloyed powder XRD and the electron diffraction analysis that obtain, result such as Fig. 1 and Fig. 2 show that alloy is single regular dodecahedron quasicrystal structure.Measure physics hydrogen storage amount and hydrogen sucking function then, in the time of 250 ℃, the mass percent of inhaling hydrogen in 20 minutes reaches 1.6mass%, inhales hydrogen kinetic curve such as Fig. 3; Measure its electrochemistry suction-hydrogen discharging performance at the MH-Ni Experimental cell of negative restriction simultaneously, once circulating in the time of 70 ℃ reaches maximum discharge capacity 702mAh/g, and discharge curve as shown in Figure 4.Charged experiment is carried out under 70 ℃ ± 1 ℃, charged conservation rate QH calculates according to formula QH=Cb/0.5 (Ca+Cc), wherein Ca is charged preceding last discharge capacity, Cb is the discharge capacity first of starting shooting after charged, discharge capacity when Cc is for the second time normal charge and discharge of charged back start, the charged time is 72 hours, and QH is 95%.
Embodiment 2:
Composition is Ti 65Ni 30Zr 10Cu 5, ball milling 150 hours was 580 ℃ of following heat treatments 1 hour.All the other are with embodiment 1.The XRD result of alloy such as Fig. 5 are indicated as single regular dodecahedron quasicrystal structure.In the time of 250 ℃, the mass percent of inhaling hydrogen in 20 minutes reaches 1.8mass%.Once circulating in the time of 50 ℃ reaches maximum discharge capacity 512mAh/g, and charged experiment is carried out under 50 ℃ ± 1 ℃, and QH is 93%.
Embodiment 3:
Composition is Ti 50Ni 30Zr 10Cu 10, ball milling 100 hours was 530 ℃ of following heat treatments 3 hours.All the other are with embodiment 1.Alloy is single regular dodecahedron quasicrystal structure.In the time of 250 ℃, the mass percent of inhaling hydrogen in 20 minutes reaches 1.4mass%.Once circulate in the time of 30 ℃ and reach maximum discharge capacity 376mAh/g.Charged experiment is carried out under 30 ℃ ± 1 ℃, and QH is 98%.
Embodiment 4:
Composition is Ti 55Ni 30Zr 20Cu 5, ball milling 150 hours was 605 ℃ of following heat treatments 4.5 hours.All the other are with embodiment 1.The XRD result of alloy such as Fig. 5 are indicated as single regular dodecahedron quasicrystal structure.In the time of 250 ℃, the mass percent of inhaling hydrogen in 20 minutes reaches 1.7mass%.Once circulating in the time of 50 ℃ reaches maximum discharge capacity 498mAh/g, and charged experiment is carried out under 50 ℃ ± 1 ℃, and QH is 92%.
Embodiment 5:
Composition is Ti 40Zr 40Ni 15Cu 5, ball milling 130 hours was 480 ℃ of following heat treatments 5 hours.All the other are with embodiment 1.Alloy is single regular dodecahedron quasicrystal structure.In the time of 250 ℃, the mass percent of inhaling hydrogen in 20 minutes reaches 1.9mass%.Once circulate in the time of 70 ℃ and reach maximum discharge capacity 654mAh/g.Charged experiment is carried out under 70 ℃ ± 1 ℃, and QH is 91%.

Claims (2)

1, a kind of single regular dodecahedron quasicrystal material of Ti-Zr-Ni-Cu with hydrogen-storage function, it is characterized in that: this alloy is single regular dodecahedron quasicrystal material, and the general formula of its composition is expressed as Ti 100-x-y-zZr xNi yCu z, 10＜x＜45,5＜y＜20,1＜z＜10 wherein.
2, the preparation method of the single regular dodecahedron quasicrystal material of the described Ti-Zr-Ni-Cu of a kind of claim 1; metering by the requirement of described quasicrystal material composition general formula; select the chemical pure Ti of 100 orders, Zr, Ni, Cu powder for use; pack into the ball grinder of high energy ball mill; ratio of grinding media to material is 20: 1; ball milling is 100～200 hours under argon shield, and the alloyed powder behind the ball milling is enclosed in the quartz ampoule, 1 * 10 -3Heat-treat under the Pa, heat treatment temperature is 480～630 ℃, and the time is 0.5～6 hour.
CNB2005100167176A 2005-04-18 2005-04-18 Regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and its preparing method Expired - Fee Related CN1299819C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100167176A CN1299819C (en) 2005-04-18 2005-04-18 Regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and its preparing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100167176A CN1299819C (en) 2005-04-18 2005-04-18 Regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and its preparing method

Publications (2)

Publication Number Publication Date
CN1709564A CN1709564A (en) 2005-12-21
CN1299819C true CN1299819C (en) 2007-02-14

Family

ID=35705895

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100167176A Expired - Fee Related CN1299819C (en) 2005-04-18 2005-04-18 Regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and its preparing method

Country Status (1)

Country Link
CN (1) CN1299819C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104911513A (en) * 2015-04-24 2015-09-16 燕山大学 Large size ZrTi quasicrystal material and preparation method thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101816915B (en) * 2009-12-11 2013-01-02 河南理工大学 Amorphous-containing icosahedral quasicrystal hydrogen storage alloy and quenching production method thereof
CN104726745B (en) * 2013-12-20 2017-07-11 北京有色金属研究总院 A kind of Ti Zr bases lightweight high power capacity hydrogen-absorbing material and its preparation and application
US11634793B2 (en) * 2019-04-30 2023-04-25 Samsung Electronics Co., Ltd. Quasicrystalline material and semiconductor device applying the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859413A (en) * 1987-12-04 1989-08-22 The Standard Oil Company Compositionally graded amorphous metal alloys and process for the synthesis of same
CN1043060C (en) * 1995-07-21 1999-04-21 洪国治 Hydrogen storage method and chemical composition of hydride electrode material
US6332908B1 (en) * 1999-11-19 2001-12-25 Korea Advanced Institute Of Science And Technology Method for modifying surface of hydrogen storage alloy for NI/MH secondary battery using flake type metal
US6689193B1 (en) * 1999-06-24 2004-02-10 Honda Giken Kogyo Kabushiki Kaisha Hydrogen storage alloy powder and method for producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859413A (en) * 1987-12-04 1989-08-22 The Standard Oil Company Compositionally graded amorphous metal alloys and process for the synthesis of same
CN1043060C (en) * 1995-07-21 1999-04-21 洪国治 Hydrogen storage method and chemical composition of hydride electrode material
US6689193B1 (en) * 1999-06-24 2004-02-10 Honda Giken Kogyo Kabushiki Kaisha Hydrogen storage alloy powder and method for producing the same
US6332908B1 (en) * 1999-11-19 2001-12-25 Korea Advanced Institute Of Science And Technology Method for modifying surface of hydrogen storage alloy for NI/MH secondary battery using flake type metal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104911513A (en) * 2015-04-24 2015-09-16 燕山大学 Large size ZrTi quasicrystal material and preparation method thereof

Also Published As

Publication number Publication date
CN1709564A (en) 2005-12-21

Similar Documents

Publication Publication Date Title
CN101849305B (en) Nickel-metal hydride battery and method for producing hydrogen storage alloy
Rongeat et al. Evaluation of different approaches for improving the cycle life of MgNi-based electrodes for Ni-MH batteries
JPS6145563A (en) Active substance for hydrogen storage electrode, method of forming same and electrochemical application
Huang et al. Structural characterization and electrochemical hydrogen storage properties of Mg2Ni1− xMnx (x= 0, 0.125, 0.25, 0.375) alloys prepared by mechanical alloying
CN1299819C (en) Regular icosahedron titanium-base quasi-crystal material with hydrogen-storage function and its preparing method
CN105063457A (en) Nano-graphite compounded high-capacity RE-Mg-Ni-based hydrogen storage material and preparation method thereof
Huang et al. Effects of annealing treatment and partial substitution of Cu for Co on phase composition and hydrogen storage performance of La0. 7Mg0. 3Ni3. 2Co0. 35 alloy
EP2813588B1 (en) Hydrogen absorption alloy powder, negative electrode, and nickel-hydrogen secondary cell
Zhang et al. Effect of magnesium on the crystal transformation and electrochemical properties of A2B7-type metal hydride alloys
Casini et al. Effects of substituting Cu for Sn on the microstructure and hydrogen absorption properties of Co-free AB5 alloys
Shang et al. Investigations on hydrogen storage performances and mechanisms of as-cast TiFe0. 8-mNi0. 2Com (m= 0, 0.03, 0.05 and 0.1) alloys
Zhang et al. The phase transformation and electrochemical properties of TiNi alloys with Cu substitution: Experiments and first-principle calculations
CN108588521A (en) A kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys and preparation method thereof
JPH03191040A (en) Hydrogen storage alloy electrode
CN108097947A (en) A kind of high capacity Mg-Zn-Ni ternary hydrogen-storage alloys and preparation method thereof
WO2016029861A1 (en) Rare-earth based hydrogen storage alloy and application thereof
Jankowska et al. Electrochemical performance of sealed NiMH batteries using nanocrystalline TiNi-type hydride electrodes
Takasaki et al. Synthesis of Ti-Zr-Ni amorphous and quasicrystal powders by mechanical alloying, and their electrochemical properties
JP2004204309A (en) Hydrogen storage material, and production method therefor
CN1272461C (en) Non crystal state hydrogen storge composite material and its producing method
CN1027762C (en) Hydrogen storage alloy used in negative pole of secondary battery
CN106756355B (en) Fuel cell stores hydrogen intermediate alloy, hydrogen storage material and preparation method with Mg-Sn-Ni ternary
CN106941155B (en) Rare earth hydride-carbon nano composite material and preparation method and application thereof
CN1326265C (en) Amorphous magnesium-Nickel series hydron-storage electrode material and producing method thereof
Zhang et al. An electrochemical investigation of melt-spun nanocrystalline Mg20Ni10− xCux (x= 0–4) electrode alloys

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20070214

Termination date: 20100418