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Improved NiMH performance by a surface treatment that creates magnetic Ni-clusters
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK).
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK).
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK).
Antal upphovsmän: 42016 (Engelska)Ingår i: International journal of hydrogen energy, ISSN 0360-3199, E-ISSN 1879-3487, Vol. 41, nr 23, s. 9933-9938Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

A surface treatment method has been developed to activate the surface of an AB(5) type (La-20 Ce-7 Pr-1 Nd-4 Al-2 Mn-5 Co-6 Ni-55) alloy. In the process the surface is covered with a porous surface layer containing needle shaped rare earth hydroxides after etching by a potassium hydroxide solution. TEM studies show in addition the presence of a denser surface oxide layer with embedded Ni containing clusters covering the bulk alloy. The magnetic properties of the alloy powders change with the surface treatment. In addition to a paramagnetic component of the bulk alloy, surface treated alloy also displays superparamagnetic and ferromagnetic properties. In electrochemical half-cell tests, the alloy shows better high-rate dischargeability with increasing presence of magnetic clusters in the metal hydride particles surface.

Ort, förlag, år, upplaga, sidor
2016. Vol. 41, nr 23, s. 9933-9938
Nyckelord [en]
Metal hydrides, NiMH batteries, Surface treatment, Ni clusters, Discharge kinetics, Rare earths hydroxides
Nationell ämneskategori
Oorganisk kemi
Forskningsämne
oorganisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-132397DOI: 10.1016/j.ijhydene.2016.01.145ISI: 000378359400029OAI: oai:DiVA.org:su-132397DiVA, id: diva2:952570
Konferens
1st International Symposium on Materials for Energy Storage and Conversion (ESC-IS), Middle East Technical University, Ankara, Turkey, September 07-09, 2015
Tillgänglig från: 2016-08-15 Skapad: 2016-08-11 Senast uppdaterad: 2022-02-23Bibliografiskt granskad
Ingår i avhandling
1. Structure determination of beam sensitive crystals by rotation electron diffraction: the impact of sample cooling
Öppna denna publikation i ny flik eller fönster >>Structure determination of beam sensitive crystals by rotation electron diffraction: the impact of sample cooling
2017 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

Electron crystallography is complementary to X-ray crystallography. Single crystal X-ray diffraction requires the size of a crystal to be larger than about 5 × 5 × 5 μm3 while a TEM allows a million times smaller crystals being studied. This advantage of electron crystallography has been used to solve new structures of small crystals. One method which has been used to collect electron diffraction data is rotation electron diffraction (RED) developed at Stockholm University. The RED method combines the goniometer tilt and beam tilt in a TEM to achieve 3D electron diffraction data. Using a high angle tilt sample holder, RED data can be collected to cover a tilt range of up to 140o. 

Here the crystal structures of several different compounds have been determined using RED. The structure of needle-like crystals on the surface of NiMH particles was solved as La(OH)2. A structure model of metal-organic layers has been built based on RED data. A 3D MOF structure was solved from RED data. Two halide perovskite structures and two newly synthesized aluminophosphate structures were solved. For those beam sensitive crystals characterized here, sample cooling down to -170oC was used to reduce the beam damage. The low temperature not only reduces electron beam damage, but also keeps the structure more stable in the high vacuum in a TEM and improves the quality of the diffraction data. It is shown that cooling can improve the resolution of diffraction data for MOFs and zeolites, for samples undergoing phase changes at low temperature, the data quality could be worse by cooling. In summary, cooling can improve the ED data quality as long as the low temperature does not trigger structural changes. 

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University, 2017
Nyckelord
electron crystallography, rotation electron diffraction, structure determination, cooling
Nationell ämneskategori
Oorganisk kemi
Forskningsämne
oorganisk kemi
Identifikatorer
urn:nbn:se:su:diva-145636 (URN)978-91-7649-856-9 (ISBN)978-91-7649-857-6 (ISBN)
Disputation
2017-10-11, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (Engelska)
Opponent
Handledare
Anmärkning

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Manuscript. Paper 3: Submitted.

Tillgänglig från: 2017-09-18 Skapad: 2017-08-14 Senast uppdaterad: 2022-02-28Bibliografiskt granskad
2. Development of metal hydride surface structures for high power NiMH batteries: Also extended cycle-life and lead to more effective recycling methods
Öppna denna publikation i ny flik eller fönster >>Development of metal hydride surface structures for high power NiMH batteries: Also extended cycle-life and lead to more effective recycling methods
2018 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

By combining alkaline etching of hydrogen storage alloys or their hydrides with a controlled oxidation, it was possible to improve reaction kinetics and accelerate activation of MH-electrodes. Both AB5 and AB2 alloys were studied where A is mixtures of rare earth elements for AB5 alloys and titanium and/or vanadium, zirconium for AB2 alloys; nickel contributes the major part of B. With SEM and TEM studies the surface could be described as consisting of several phases where an interphase with active Ni-containing cluster protected the inner metallic hydrogen storage part of the powder particles. These catalytic Ni-clusters presumably lead to the fast activation and high discharge capacity of alloy.

This interphase was observed to be stable enough to allow us to develop a method, where we could add pure oxygen to a NiMH battery pack in order to regenerate the amount of electrolyte that was lost during long time cycling of the battery. Meanwhile, the method will rebalance the electrodes mitigating excessive pressures during over charge. Therefore, the internal resistance of cells can be reduced and cycle life will increase.

It was also shown that the stable interphase could survive a mild ball milling or sonication which enabled us to upcycle material from spent NiMH batteries into a better working MH-electrodes with improved kinetics and activation properties. Reuse of ball-milled or sonicated material could serve as a simple recycling alternative to energy-demanding metallurgical smelting methods and chemical consuming hydrometallurgical recycling processes, where the possibilities of up-scaling further favour the less complex mechanical treatments. The stable but catalytic interphase protecting the inner particles indicates that the MH-electrode material may perform better in its second life in a new NiMH battery.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University, 2018. s. 44
Nyckelord
Metal hydrides, NiMH batteries, Surface treatment, Ni clusters, Rare earths hydroxides, Oxygen, Hydrogen
Nationell ämneskategori
Oorganisk kemi Materialkemi
Forskningsämne
oorganisk kemi
Identifikatorer
urn:nbn:se:su:diva-154581 (URN)978-91-7797-218-1 (ISBN)978-91-7797-219-8 (ISBN)
Disputation
2018-12-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (Engelska)
Opponent
Handledare
Anmärkning

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.

Tillgänglig från: 2018-11-15 Skapad: 2018-04-03 Senast uppdaterad: 2022-02-26Bibliografiskt granskad

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Shen, YangPeng, FeiNoréus, Dag

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International journal of hydrogen energy
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