CN101728527A - Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline - Google Patents

Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline Download PDF

Info

Publication number
CN101728527A
CN101728527A CN200910227963A CN200910227963A CN101728527A CN 101728527 A CN101728527 A CN 101728527A CN 200910227963 A CN200910227963 A CN 200910227963A CN 200910227963 A CN200910227963 A CN 200910227963A CN 101728527 A CN101728527 A CN 101728527A
Authority
CN
China
Prior art keywords
hydrogen
hydrogen storage
polyaniline
alloy powder
bearing alloy
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.)
Granted
Application number
CN200910227963A
Other languages
Chinese (zh)
Other versions
CN101728527B (en
Inventor
韩树民
沈文卓
蒿建生
刘治平
李媛
扈琳
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.)
ZHONGSHAN TIANJIAO RARE-EARTH MATERIAL Co Ltd
Yanshan University
Original Assignee
ZHONGSHAN TIANJIAO RARE-EARTH MATERIAL Co Ltd
Yanshan University
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 ZHONGSHAN TIANJIAO RARE-EARTH MATERIAL Co Ltd, Yanshan University filed Critical ZHONGSHAN TIANJIAO RARE-EARTH MATERIAL Co Ltd
Priority to CN2009102279634A priority Critical patent/CN101728527B/en
Publication of CN101728527A publication Critical patent/CN101728527A/en
Application granted granted Critical
Publication of CN101728527B publication Critical patent/CN101728527B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a method for improving the electrochemical properties of hydrogen storage alloy powder by using polyaniline, which comprises the following steps of: soaking the hydrogen storage alloy powder to be treated in mixed solution of a certain proportion of aniline and sulfuric acid, and stirring the mixture; and by using the air as an oxidant and under the autocatalysis action of the polyaniline, performing attached oxidation on the surface of the hydrogen storage alloy powder to form a conductive polyaniline membranous layer. The method is suitable for AB2 type, AB3 type and AB5 type hydrogen storage alloys, and can significantly improve the hydrogen storage capacity, the activation property and the high-magnification discharge performance of the hydrogen storage alloys. The invention provides an effective method capable of being practically applied to the surface treatment of the hydrogen storage alloys, and the method has the advantages of simple treatment process, low raw material cost and the like.

Description

A kind of method of improving electrochemical properties of hydrogen storage alloy powder by using polyaniline
Technical field
The present invention relates to a kind of aniline that utilizes and form the method that macromolecule membranous layer improves its chemical property at the direct polymerization reaction take place in hydrogen-bearing alloy powder surface, this method is relevant with the polyaniline rete of the improved hydrogen storage alloy electrochemical performance that forms on the hydrogen-bearing alloy powder surface, belongs to the hydrogen bearing alloy technical field of surface.
Background technology
Advantages such as nickel metal hydride battery (MH-Ni battery) is novel high-performance, free of contamination secondary cell, has the energy density height, has extended cycle life, and environment compatibility is good.The MH-Ni battery comprises in electric motor car (EV) that mainly fields such as hybrid electric vehicle (HEV), various portable Military Electronic Equipment are used widely.Searching can improve the method for MH-Ni battery performance, becomes the key point that improves MH-Ni Battery Market competitiveness and widen its range of application.Polyaniline (PANI) is fragrant heterocycle conducting polymer, but it is except having the character that is had with other fragrant heterocycle conducting polymers, because of it has the doping phenomenon of special construction, structure variation, uniqueness, and have resistance to oxidation and characteristics such as good heat resistance and excellent physical chemistry, enjoy polymer researcher's concern, be considered to the conducting polymer composite that is hopeful to be applied in practice most.
At present, do not see that relevant polyaniline improves the patent report of hydrogen bearing alloy performance, add research paper in the hydrogen bearing alloy to as additive machinery but have on a small quantity about polyaniline.2006, India scientist Reddy[A.Leela Mohana Reddy, et al.Journal of Alloys and Compounds, 373 (2004) 237-245] study and point out, can accelerate AB by direct interpolation polyaniline 2The hydrogen diffusion rate of type hydrogen storage alloy.The Qi[Y.N.Qi of the Chinese Academy of Sciences in 2007, H.L.Chu, F.Xu, et al.Effect of polyaniline onhydrogen absorption-desorption properties and discharge capacity of AB3 alloy.International Journal ofHydrogen Energy, 2007,32 (15): 3395-3401] by research AB 3The hydrogen kinetics of diffusion performance of alloy has also obtained same conclusion.Because the strong rigidity and the strong interaction between key of the molecular link that polyaniline combines with the alloy body are poor, the simple interpolation is difficult to reach the effect that it improves alloy property.Simultaneously, polyaniline is dissolved in any common organic solvent hardly, and not fusion under decomposition temperature is difficult to melt-processed.In order to address the above problem, the present invention proposes a kind of direct polymerization reaction take place on the hydrogen-bearing alloy powder surface that passes through, make polyaniline be attached to the method that the hydrogen bearing alloy surface forms one deck coating film, improved the chemical property of hydrogen bearing alloy significantly.
Summary of the invention
The object of the present invention is to provide a kind of by improve the method for hydrogen storage alloy electrochemical performance at the direct plating polymer polyanilinc rete in hydrogen-bearing alloy powder surface.This method is to utilize the nothing electricity auto polymerization of aniline to be reflected at the hydrogen-bearing alloy powder particle surface to form hydrogen storage capability, activity function and the high-rate discharge ability that the polyaniline coating film with conductivity and corrosion resistance has improved the hydrogen alloy.This method has material and is easy to get, the easy and tangible advantage of action effect of processing method, and this invention is significant to the practical application performance that improves hydrogen bearing alloy.
Method of the present invention comprises following concrete steps:
1, preparation contains aniline 0.25～0.5mol/l and sulfuric acid 2～4 * 10 -3The mixed solution of mol/l;
2, be that 100～400 purpose hydrogen-bearing alloy powders are soaked in the mixed solution with granularity, low whipping speed is to stir 5～60 minutes under 120～300 rev/mins of conditions.Wherein, the mass ratio of hydrogen storing alloy powder and mixed solution is 20～200/100.
3, will mix alloyed powder after molten through washing, suction filtration, and place vacuum drying chamber stand-by after 60 ℃ of following vacuumize.
The present invention is suitable for AB 2Type, AB 3Type, AB 5Type hydrogen storage alloy.Its operating process and technology are simple, and polyaniline is synthetic to need not to add oxidant and organic solvent, and production cost is low.A spot of oligomer of phenylamine is only arranged in the waste liquid, can be by simple mechanical filter recycling.
Description of drawings
Fig. 1 is AB among the embodiment 1 5Type (MlNi 4.19Mn 0.31Co 0.42Al 0.23) the Fourier transform infrared spectroscopy curve of hydrogen-bearing alloy powder.(a)-untreated hydrogen storing alloy powder, (b)-hydrogen storing alloy powder after handling.
Fig. 2 is AB among the embodiment 1 5Type (MlNi 4.19Mn 0.31Co 0.42Al 0.23) the field emission scanning electron microscope figure of hydrogen-bearing alloy powder.
Fig. 3 is AB among the embodiment 1 5Type (MlNi 4.19Mn 0.31Co 0.42Al 0.23) the activity function curve of hydrogen storing alloy powder.(a)-untreated hydrogen storing alloy powder, (b)-hydrogen storing alloy powder after handling.
Fig. 4 is AB among the embodiment 1 5Type (MlNi 4.19Mn 0.31Co 0.42Al 0.23) the multiplying power discharging property curve of hydrogen storing alloy powder.(a)-untreated hydrogen storing alloy powder, (b)-hydrogen storing alloy powder after handling.
Embodiment
Below by specific embodiment technical solution of the present invention is described further.
Embodiment 1
1) preparation 100g contains aniline 0.5mol/l, sulfuric acid 2 * 10 -3The mixed solution of mol/l;
2) in aforementioned mixed solution, add 20g AB 5Type (MlNi 4.19Mn 0.31Co 0.42Al 0.23) hydrogen-bearing alloy powder;
3) be to stir 8 minutes under 120 rev/mins of conditions at the air medium velocity;
4) alloyed powder after will handling carries out Fourier transform infrared spectroscopy and field emission scanning electron microscope characterizes, the results are shown in accompanying drawing 1 and Fig. 2, among the figure as can be known: handling benzoquinones (N=Q=N), carbon-carbon double bond (C=C) characteristic peak that polyaniline in eigenstate appears in the back alloy in the fourier-transform infrared collection of illustrative plates is 1168cm -1, 3200cm -1, can find among the field emission scanning electron microscope figure that alloy surface generates the coralliform polyaniline.To handle the back alloyed powder and make the hydrogen-storage electrode negative pole, use Ni (OH) 2(capacity is more than 4 times of negative material capacity to/NiOOH electrode as positive pole, to guarantee accurately to test the performance of negative material), form the half-cell test macro with the KOH aqueous solution of 6M as electrolyte, use the chemical property of DC-5 cell tester test negative pole.Test condition is under 25 ℃, and the charging and discharging currents of discharge capacity test is 9mAh/g, 8 weeks of repeated charge-discharge cycles; Multiplying power discharging test charging current is 45mAh/g, and discharging current is respectively 9mAh/g, 45mAh/g, 90mAh/g, 135mAh/g, 180mAh/g and 225mAh/g.The charge and discharge cycles test result shows: the activation number of turns of hydrogen-bearing alloy electrode reduced to for 2 weeks from 5 weeks, and discharge capacity is increased to 325mAh/g from 294mAh/g, high-rate discharge ability HRD ( HRD = C i C max × 100 % ; C iBe discharge capacity under the different discharge current densities, C MaxBe big discharge capacity.Down together.) bring up to 50% from 8%.Correlated results is seen accompanying drawing 3 and Fig. 4.
Embodiment 2
1) preparation 100g contains aniline 0.3mol/l, sulfuric acid 3 * 10 -3The mixed solution of mol/l;
2) in aforementioned mixed solution, add 30g AB 5Type (MlNi 3.67Mn 0.25Co 0.50Al 0.28) hydrogen-bearing alloy powder;
3) be to stir 10 minutes under 150 rev/mins of conditions at the air medium velocity;
4) alloyed powder after will handling carries out Fourier transform infrared spectroscopy and field emission scanning electron microscope characterizes, and experimental result shows: handling benzoquinones (N=Q=N), carbon-carbon double bond (C=C) characteristic peak that polyaniline in eigenstate appears in the back alloy in the fourier-transform infrared collection of illustrative plates is 1163cm -1, 3195cm -1, can find among the field emission scanning electron microscope figure that alloy surface generates the coralliform polyaniline.To handle the back alloyed powder and make electrode and carry out electro-chemical test, experiment condition is with embodiment 1.Experimental result shows: the hydrogen-bearing alloy electrode activation number of turns reduced to for 3 weeks from 7 weeks, and discharge capacity is increased to 334mAh/g from 304mAh/g, and high-rate discharge ability HRD brings up to 60% from 10.2%.
Embodiment 3
1) preparation 100g contains aniline 0.5mol/l, sulfuric acid 4 * 10 -3The mixed solution of mol/l;
2) in aforementioned mixed solution, add 50gAB 3Type (La 0.88Mg 0.12Ni 2.95Mn 0.10Co 0.55Al 0.10) hydrogen-bearing alloy powder;
3) be to stir 15 minutes under 200 rev/mins of conditions at the air medium velocity;
4) alloyed powder after will handling carries out Fourier transform infrared spectroscopy and field emission scanning electron microscope characterizes, and experimental result shows: handling benzoquinones (N=Q=N), carbon-carbon double bond (C=C) characteristic peak that polyaniline in eigenstate appears in the back alloy in the fourier-transform infrared collection of illustrative plates is 1170cm -1, 3206cm -1, can find among the field emission scanning electron microscope figure that alloy surface generates the coralliform polyaniline.To handle the back alloyed powder and make electrode and carry out electro-chemical test, experiment condition is with embodiment 1.Experimental result shows: the hydrogen-bearing alloy electrode activation number of turns reduced to for 3 weeks from 6 weeks, and discharge capacity is increased to 362mAh/g from 329mAh/g, and high-rate discharge ability HRD brings up to 56% from 9.5%.
Embodiment 4
1) preparation 100g contains aniline 0.4mol/l, sulfuric acid 3 * 10 -3The mixed solution of mol/l;
2) in aforementioned mixed solution, add 100gAB 2Type (Zr 0.9Ti 0.1Ni 1.1Mn 0.7V 0.2) hydrogen-bearing alloy powder;
3) be to stir 30 minutes under 250 rev/mins of conditions at the air medium velocity;
4) alloyed powder after will handling carries out Fourier transform infrared spectroscopy and field emission scanning electron microscope characterizes, and experimental result shows: handling benzoquinones (N=Q=N), carbon-carbon double bond (C=C) characteristic peak that polyaniline in eigenstate appears in the back alloy in the fourier-transform infrared collection of illustrative plates is 1163cm -1, 3190cm -1, can find among the field emission scanning electron microscope figure that alloy surface generates the coralliform polyaniline.To handle the back alloyed powder and make electrode and carry out electro-chemical test, experiment condition is with embodiment 1.Experimental result shows: the hydrogen-bearing alloy electrode activation number of turns brought up to for 2 weeks from 5 weeks, and discharge capacity is increased to 321mAh/g from 298mAh/g, and high-rate discharge ability HRD brings up to 58.7% from 10.1%.
Embodiment 5
1) preparation 100g contains aniline 0.25mol/l, sulfuric acid 3 * 10 -3The mixed solution of mol/l;
2) in aforementioned mixed solution, add 200g AB 5Type (LaNi 3.50Co 0.13Mn 0.35Al 0.16Fe 0.93) hydrogen-bearing alloy powder;
3) be to stir 60 minutes under 300 rev/mins of conditions at the air medium velocity;
4) alloyed powder after will handling carries out Fourier transform infrared spectroscopy and field emission scanning electron microscope characterizes, and experimental result shows: handling benzoquinones (N=Q=N), carbon-carbon double bond (C=C) characteristic peak that polyaniline in eigenstate appears in the back alloy in the fourier-transform infrared collection of illustrative plates is 1175cm -1, 3221cm -1, can find among the field emission scanning electron microscope figure that alloy surface generates the coralliform polyaniline.To handle the back alloyed powder and make electrode and carry out electro-chemical test, experiment condition is with embodiment 1.Experimental result shows: the hydrogen-bearing alloy electrode activation number of turns reduced to for 2 weeks from 4 weeks, and discharge capacity is increased to 343mAh/g from 321mAh/g, and high-rate discharge ability HRD brings up to 48.6% from 9.8%.

Claims (4)

1. the method for an improving electrochemical properties of hydrogen storage alloy powder by using polyaniline, it is characterized in that hydrogen-bearing alloy powder is placed a certain proportion of mixed solution that contains aniline and sulfuric acid, utilize air as oxidant, in mixing time is that 5～20 minutes and mixing speed are under 120～300 rev/mins the condition, make the hydrogen-bearing alloy powder surface form the polyaniline rete, significantly improve the chemical property of hydrogen bearing alloy with this.
2. according to the described method of improving the hydrogen bearing alloy performance of claim 1, it is characterized in that described mixed solution contains aniline 0.25～0.5mol/1, sulfuric acid 2～4 * 10 -3Mol/1.
3. according to the described method of improving the hydrogen bearing alloy performance of claim 1, it is characterized in that described hydrogen bearing alloy is AB 2, AB 3Or AB 5Type alloy a kind of, particle size is 100～400 orders.
4. according to the described method of improving the hydrogen bearing alloy performance of claim 1, the mass ratio of hydrogen-bearing alloy powder and mixed solution is 20/100～200/100 when it is characterized in that described the processing.
CN2009102279634A 2009-12-01 2009-12-01 Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline Expired - Fee Related CN101728527B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009102279634A CN101728527B (en) 2009-12-01 2009-12-01 Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009102279634A CN101728527B (en) 2009-12-01 2009-12-01 Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline

Publications (2)

Publication Number Publication Date
CN101728527A true CN101728527A (en) 2010-06-09
CN101728527B CN101728527B (en) 2013-04-17

Family

ID=42449068

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009102279634A Expired - Fee Related CN101728527B (en) 2009-12-01 2009-12-01 Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline

Country Status (1)

Country Link
CN (1) CN101728527B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102274965A (en) * 2011-06-02 2011-12-14 内蒙古稀奥科贮氢合金有限公司 Method for improving electrochemical performance of hydrogen storage alloy powder by utilizing electropolymerization polyaniline
CN102810665A (en) * 2012-07-30 2012-12-05 燕山大学 Method for improving electrochemical performance of hydrogen storing alloy by using polypyrrole
CN103078093A (en) * 2012-12-20 2013-05-01 燕山大学 Method for modifying electrochemical performance of hydrogen storing alloy by applying nickel/polyaniline
CN103618079A (en) * 2013-12-05 2014-03-05 燕山大学 Method for improving electrochemical performance of perovskite-type oxide lanthanum ferrite
CN103894602A (en) * 2012-12-27 2014-07-02 北京有色金属研究总院 Surface treatment method for improving cycle life of rare earth magnesium based hydrogen storage alloy
CN104923776A (en) * 2015-05-17 2015-09-23 桂林理工大学 Method for surface modification of AB3 hydrogen storage alloy by using aniline
CN104942279A (en) * 2015-05-17 2015-09-30 桂林理工大学 Method for using polyaniline surface modification AB3 type hydrogen storage alloy
CN105540538A (en) * 2015-12-18 2016-05-04 燕山大学 LiBH4-RPANI hydrogen storage composite material and preparation method thereof
CN107293752A (en) * 2017-06-20 2017-10-24 燕山大学 A kind of plating polyaniline that evaporates improves the method for negative plate of nickel-hydrogen battery chemical property
CN112680611A (en) * 2020-12-09 2021-04-20 浙江大学 Preparation method of polyaniline and Grignard reagent in-situ modified rare earth magnesium-based hydrogen storage material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289576B (en) * 2007-04-20 2010-08-25 中国科学院大连化学物理研究所 Composite material of conducting high polymers/alloy for nickel-hydrogen battery and preparation thereof
CN101245187B (en) * 2008-01-08 2010-06-30 上海大学 Process for preparing molybdenum trioxide/polyaniline laminated composite material

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102274965A (en) * 2011-06-02 2011-12-14 内蒙古稀奥科贮氢合金有限公司 Method for improving electrochemical performance of hydrogen storage alloy powder by utilizing electropolymerization polyaniline
CN102274965B (en) * 2011-06-02 2013-04-24 内蒙古稀奥科贮氢合金有限公司 Method for improving electrochemical performance of hydrogen storage alloy powder by utilizing electropolymerization polyaniline
CN102810665A (en) * 2012-07-30 2012-12-05 燕山大学 Method for improving electrochemical performance of hydrogen storing alloy by using polypyrrole
CN103078093B (en) * 2012-12-20 2015-09-16 燕山大学 A kind of application of nickel/polyaniline improves the method for Electrochemical Performance of Hydrogen Storage Alloy
CN103078093A (en) * 2012-12-20 2013-05-01 燕山大学 Method for modifying electrochemical performance of hydrogen storing alloy by applying nickel/polyaniline
CN103894602A (en) * 2012-12-27 2014-07-02 北京有色金属研究总院 Surface treatment method for improving cycle life of rare earth magnesium based hydrogen storage alloy
CN103894602B (en) * 2012-12-27 2017-02-08 北京有色金属研究总院 Surface treatment method for improving cycle life of rare earth magnesium based hydrogen storage alloy
CN103618079A (en) * 2013-12-05 2014-03-05 燕山大学 Method for improving electrochemical performance of perovskite-type oxide lanthanum ferrite
CN104923776A (en) * 2015-05-17 2015-09-23 桂林理工大学 Method for surface modification of AB3 hydrogen storage alloy by using aniline
CN104942279A (en) * 2015-05-17 2015-09-30 桂林理工大学 Method for using polyaniline surface modification AB3 type hydrogen storage alloy
CN105540538A (en) * 2015-12-18 2016-05-04 燕山大学 LiBH4-RPANI hydrogen storage composite material and preparation method thereof
CN105540538B (en) * 2015-12-18 2017-10-20 燕山大学 A kind of polyaniline thermal decomposition product LiBH4 composite for hydrogen storage and preparation method thereof
CN107293752A (en) * 2017-06-20 2017-10-24 燕山大学 A kind of plating polyaniline that evaporates improves the method for negative plate of nickel-hydrogen battery chemical property
CN112680611A (en) * 2020-12-09 2021-04-20 浙江大学 Preparation method of polyaniline and Grignard reagent in-situ modified rare earth magnesium-based hydrogen storage material
CN112680611B (en) * 2020-12-09 2021-10-12 浙江大学 Preparation method of polyaniline and Grignard reagent in-situ modified rare earth magnesium-based hydrogen storage material

Also Published As

Publication number Publication date
CN101728527B (en) 2013-04-17

Similar Documents

Publication Publication Date Title
CN101728527B (en) Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline
CN106450265B (en) A kind of situ Nitrogen Doping carbon coating lithium titanate combination electrode material and preparation method thereof
CN102274965B (en) Method for improving electrochemical performance of hydrogen storage alloy powder by utilizing electropolymerization polyaniline
CN104733708A (en) Preparation method of lithium nickel cobalt manganese oxide composite material with surface coated with lithium iron phosphate
CN100589217C (en) Super capacitor and electric vehicle utilizing the same
CN103117400B (en) Secondary lithium-air battery cathode catalyst
CN107845802A (en) A kind of conducting polymer for lithium battery coats cobalt acid lithium and preparation method thereof
CN106853968A (en) A kind of preparation method of multielement codope lead carbon battery activated carbon
CN101593825B (en) Negative pole made of nanometer antimony/graphite nanosheet composite material of lithium ion battery and preparation method thereof
CN102157271A (en) Super capacitor
CN103825030B (en) A kind of three-dimensional grapheme based combined electrode and its preparation method and application
CN101060172B (en) Nano-sized nickel hydroxide/carbon composite material and its manufacture method and purpose
Pei et al. Study on the high-temperature electrochemical performance of perovskite-type oxide LaFeO3 with carbon modification
Li et al. Design and synthesis of one-dimensional Co 3 O 4/Co 3 V 2 O 8 hybrid nanowires with improved Li-storage properties
Dong et al. Enhanced electrochemical properties of LaFeO 3 with Ni modification for MH–Ni batteries
CN105406032B (en) The preparation method and applications of hydrogen bearing alloy and nanoporous nickel composite material (HSAs/NPNi)
Wang et al. Uniform AlF3 thin layer to improve rate capability of LiNi1/3Co1/3 Mn1/3O2 material for Li-ion batteries
CN101894686A (en) Super capacitor battery
CN115939361B (en) Copper phosphide doped hard carbon composite material and preparation method thereof
CN108923033B (en) Preparation method of porous carbon cathode material of lithium-sulfur battery based on phase transfer method
CN102593425A (en) Method for assembling high-performance lithium ion battery based on hollow carbon nanocage cathode material
Zhang et al. Electrochemical performances of AB5-type hydrogen storage alloy modified with Co3O4
CN111490233A (en) Polyimide and graphene composite-based rechargeable magnesium battery positive electrode material and preparation method thereof
CN108326290A (en) Rare earth new power hydrogen-storage alloy and preparation method thereof
CN102810665A (en) Method for improving electrochemical performance of hydrogen storing alloy by using polypyrrole

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: 20130417

Termination date: 20131201