WO2012000854A1 - Matériau d'électrode négative pour batteries au lithium-ion - Google Patents

Matériau d'électrode négative pour batteries au lithium-ion Download PDF

Info

Publication number
WO2012000854A1
WO2012000854A1 PCT/EP2011/060403 EP2011060403W WO2012000854A1 WO 2012000854 A1 WO2012000854 A1 WO 2012000854A1 EP 2011060403 W EP2011060403 W EP 2011060403W WO 2012000854 A1 WO2012000854 A1 WO 2012000854A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
gas stream
wires
particles
electrode material
Prior art date
Application number
PCT/EP2011/060403
Other languages
English (en)
Inventor
Jean Scoyer
Stijn Put
Daniël NELIS
Kris Driesen
Original Assignee
Umicore
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 Umicore filed Critical Umicore
Publication of WO2012000854A1 publication Critical patent/WO2012000854A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Definitions

  • This invention relates to a negative electrode material for lithium-ion batteries and the synthesis of this powder using a gas phase technology.
  • Li-ion batteries are the most widely used secondary systems for portable electronic devices. Compared to aqueous rechargeable cells, such as nickel-cadmium and nickel metal hydride, Li-ion cells have higher energy density, higher operating voltages, lower self discharge and low maintenance requirements. These properties have made Li-ion cells the highest performing available secondary battery.
  • the composite lithium-ion battery electrode needs to posses mixed conductivity with both ionic lithium and electrons.
  • a complex medium is generally obtained by mixing together the active material particles with different additives such as a very fine powder of carbon black and a polymeric binder.
  • the conductive additive can be a type of carbon black, but also graphites, graphenes, carbon fibres or carbon nanotubes and combinations thereof.
  • the binder additive has a complex role since it not only gives mechanical strength to the composite electrode but also allows for a good adhesion between the electrode layer and the current collector. The binder gives the composite electrode a sufficient liquid electrolyte uptake to provide internal ionic percolation.
  • Suitable binders include, but are not limited to, carboxymethyl cellulose (CMC), polysaccharides, polyvinylidene fluoride (PVDF) polyolefins, florinated polyolefins, polyimides, polyacrylates, natural or synthetic rubbers. Dispersants and additives known by those skilled in the art can be used to control the porosity or to optimize the distribution and contact of the active material within the 3D structure of the battery electrode. 'Calendering' is used to increase the density of the electrode or to increase contact between the different particles of the composite electrode. As described above Si-based negative electrode materials could significantly enhance the energy density of the commercial lithium ion batteries. Silicon has the largest theoretical gravimetric capacity (3579 mAh/g) corresponding to the following reaction:
  • a common approach to increase the electrochemical behaviour of Si based electrodes is to use (metal) wires/fibers, since in this way the current collectivity can be improved due to the formation of conductive paths among the anode active material particles.
  • the concept of using wires in battery applications is technologically introduced in several ways.
  • Carbon nanotubes can be incorporated as conductive material in the preparation of the silicon based electrode to prevent degradation of electron conductivity.
  • a Si-based anode containing a plurality of metal fibers is disclosed in US2009-0269677.
  • the metal fibers e.g. Ti, Ni, Fe, ...) form a three-dimensional network structure that provides conductive paths for the silicon particles.
  • Another approach to solve the problems associated with silicon powder particles is to use pure silicon submicron sized fibers or wires. In this way not only the conductive paths are formed as mentioned above. Additionally, submicron sized wire anodes are believed to sustain larger strains during charging and discharging of the electrode (see for example Chan et al. in Nature Nanotech. 3 (2008) 31 -35). The wires do not pulverize into smaller particles when cycled at high capacities. An important disadvantage of the use of such Si wires in battery electrodes is however that they are inherently fluffy and thus result in a low density in the deposited layer, due to the limited packing properties.
  • silicon submicron sized wires There are several production methods for silicon submicron sized wires. They can be prepared by etching a silicon-based substrate, where in a second step the pillars can be harvested. When the wires are grown on the current collector or attached to the current collector an efficient electron transport is maintained between current collector and the wires. Si fibers can also be bonded together, prepared by wet or dry etching of a substrate and detaching the resulting fibers from the surface. High capacities at high currents are possible as disclosed in US2009-0042101 , where submicron sized wires are growth-rooted from the substrate. The structures are produced using vapor-solid or vapor-liquid-solid growth.
  • the invention can provide a negative electrode material for use as in a rechargeable battery, comprising a Si based material comprising a mixture of submicron sized Si particles and submicron sized Si wires, wherein the average particle size of the Si particles is at least 5 times the average width of the Si wires, and preferably at least 10 times the average width of the Si wires.
  • the Si based material may be free-standing, that is, not grown on or attached to a substrate. In such an embodiment, the Si based material may be obtained in a plasma gas stream.
  • the Si based material may also have a tap density of at least 0.25 g/cm 3 .
  • the submicron sized Si particles may have an average primary particle size greater than 10 nm and less than 500 nm.
  • the silicon powder may have an average particle size of between 0.04 and 0.3 pm, where the average particle size (d av ) can be derived from SEM or TEM analysis.
  • the Si based material may also consist of pure Si.
  • the Si based material described above may have Si wires having a width between
  • the Si wires may also have an aspect ratio (length:width) of more than 5:1. In one embodiment the aspect ratio may be more than 10: 1 , and in another embodiment more than 20:1. In another embodiment each of the submicron sized Si wires may be in contact with at least two submicron sized Si particles. In yet another embodiment, the Si based material may further comprise oxygen, with an oxygen content of less than 20 wt%.
  • the invention can provide a process for manufacturing the Si based material described above, comprising the steps of:
  • the temperature of the gas stream may be above 3500 K when injecting the Si based precursor, whereafter the gas stream may be quenched at a temperature between 1600 and 2500 K.
  • the Si based precursor is a micron-sized Si powder having an average particle size of less than 100 pm.
  • the hot gas stream may be provided by means of either one of a gas burner, a hydrogen burner, an RF plasma, or a DC arc plasma.
  • the gas stream may also be provided by means of a radio frequency inductively coupled plasma, and the gas stream may comprise a mixture of argon and nitrogen.
  • the invention can provide an electrode composition for a rechargeable Li-ion battery comprising the Si based material described above and a carboxymethyl cellulose (CMC) binder material.
  • the electrode can further comprise styrene butadiene rubber as binder material.
  • the electrode can consist of 20-60 wt% of the Si based material, 20-40 wt% binder material, the remainder being a compound consisting of carbon.
  • the carbon compound can consist of acetylene black powder.
  • the electrode can consist of 50 wt% of the Si based material, 25 wt% binder material, and 25 wt% acetylene black powder.
  • the invention can provide a process for preparing an electrode assembly for a rechargeable Li-ion battery comprising an electrode composition described before, comprising the steps of:
  • the electrode assembly comprising the slurry at a temperature between 125 and 175°C.
  • the invention can provide a process for preparing an electrode assembly for a rechargeable Li-ion battery comprising an electrode composition described above, comprising the steps of: - providing an aqueous solution of the binder material,
  • the electrode assembly comprising the slurry at a temperature between 125 and 175°C.
  • the current collector is a copper foil.
  • the aqueous solution of binder material has a concentration of 2-4 wt% of Na- CMC.
  • the aqueous solution of binder material is aged under stirring for at least 5 hours, before dispersing either one of the silicon powder and the carbon compound in the aqueous binder solution.
  • the pH of the aqueous solution of binder material is adjusted to a value between 3.5 and 6, preferably by addition of formic acid, before dispersing either one of the Si based material and the carbon compound in the aqueous binder solution.
  • Si nanoparticles are here preferred because of their higher reactivity and moreover they will not pulverize if cycled below the maximum capacity and expansion ( ⁇ 2000 mAh/g).
  • the Si particle size may be larger than 10 nm, because otherwise the specific surface are and therefore the reactivity can be too high.
  • the density of the mixture of Si particles and wires may not be too close to the density of the pure Si wires, because this may lead to the disadvantage described before. Therefore it is provided that the average particle size of the Si particles is at least 5 times the average width of the Si wires, and preferably at least 10 times the average width of the Si wires. Too large particles (> 500 nm) may however break up upon cycling.
  • a method for preparing an electrode material by reacting silicon or tin with a metal oxide, reacting a silicon oxide or a tin oxide with a metal, or reacting a silicon compound or a tin compound with a metal compound.
  • the reaction can take place in a plasma furnace.
  • Metal core particles e.g. silicon
  • This core-shell fibrous structure may be composed of a silicon core and an amorphous silicion oxide shell.
  • the diameter of the particles is nearly the same as the width of the core-shell fibers.
  • the invention here includes a powder consisting of Si nanowires and Si nanoparticles, obtained by the optimization of the scalable high temperature plasma process.
  • the developed powders combine the specific advantages of both submicron sized particles and wires.
  • Figure 1 SEM (A) and TEM image (B) illustrating Si nanoparticles, no Si nanowires can be observed.
  • Figure 2 SEM (A) and TEM image (B) illustrating Si nanoparticles and Si nanowires.
  • Figure 3 Density versus applied pressure for a powder with only spherical particles
  • Figure 4 SEM image illustrating Si nanowires, no Si nanoparticles can be observed.
  • the invention may be practiced, for example, by way of the different examples described below.
  • the starting material is a micron-sized Si powder (from ECKA - Austria, specified as being ⁇ 75 pm).
  • a 60 kW radio frequency (RF) inductively coupled plasma (ICP) is applied, using an argon plasma with 2.5 Nm 3 /h argon gas.
  • the solid silicon precursor is injected in the plasma at a rate of 800 g/h, resulting in a prevalent (i.e. in the reaction zone) temperature above 3500 K.
  • the Si precursor is totally vaporized followed by a nucleation into submicron sized Si powder.
  • An argon flow of 90 L/min (expressed as function of the power and the amount of injected precursor this corresponds to 112.5 L/kg.kW) is used as quench gas immediately downstream of the reaction zone in order to lower the
  • the average particle size can be calculated from the specific surface area as the average primary particle size, assuming spherical particles of equal size, according to the following formula:
  • p refers to the theoretical density of the powder (2.33 g/cc for pure Si) and BET refers to the specific surface area (m 2 /g) as determined by the N 2 adsorption method of Brunauer- Emmett-Teller.
  • the measured average particle size using the formula above corresponds to the observations with TEM and SEM.
  • the starting material is the micron-sized Si powder of CEx A.
  • a 60 kW radio frequency (RF) inductively coupled plasma (ICP) is applied, using an argon plasma with
  • the solid silicon precursor is injected in the plasma at a rate of 800 g/h, resulting in a prevalent (i.e. in the reaction zone) temperature above 3500 K.
  • the Si precursor is totally vaporized followed by a nucleation into nano-sized Si powder.
  • An argon flow of 40 L/min (expressed as function of the power and the amount of injected precursor this corresponds to 50 L/kg.kW) is used as quench gas immediately downstream of the reaction zone in order to lower the temperature of the gas below 2000 K. In this way the metal nuclei are formed.
  • a nano-sized Si powder is obtained, composed of a mixture of wires and particles, and characterized by a cubic crystalline phase.
  • SEM and TEM characterization shows the presence of Si nanowires and Si nanoparticles (see Figure 2). From the TEM it can be derived that the nanoparticles have a diameter between
  • the apparatus according to Example B is operated in similar conditions using the same precursor. However, the conditions are modified in such a way that the quench is decreased to 10 L/min (equal to 12.5 L/kg.kW), and a quench temperature above 2500 K is obtained.
  • a nano-sized Si powder is obtained, characterized by a cubic crystalline phase and a specific surface area of 40 ⁇ 2 m 2 /g (BET).
  • SEM characterization shows the presence of only Si nanowires (see Figure 4).
  • the tap density is 0.024 g/cm 3 and the pressed density is around 0.8 g/cm 3 (see Figure 3: triangles) and thus much lower compared to the powders containing spherical nanoparticles.
  • An electrode with a composition of 50.0 wt% of Silicon-particles/Silicon-wires powder (obtained in Synthesis Example B), 25 wt% conductive additive acetylene black and 25 wt% sodium-CMC is prepared as described in WO 2011 -035876.
  • Formic acid is added to an aqueous solution of 2.0 wt% CMC (Alfa Aesar) to obtain pH 5.
  • an alumina vessel with 5 (1 cm) alumina balls 12.3 g of the binder solution is added to 0.5 g of acetylene black.
  • the vessel is mixed for 5 minutes in a planetary mill (Fritch Pulversisette 6, Fritsch Germany) at a speed set at 4.
  • a second mixing step 0.5 g of the Silicon-particles + Silicon-wires powder is added and further mixing was done for 10 minutes in the planetary mill at the speed setting 4.
  • An electrode with a composition of 50.0 wt% of Silicon powder (containing no nanowires, obtained in Comparative Synthesis Example A), 25 wt% conductive additive acetylene black and 25 wt% sodium-CMC is prepared as a comparative example following the same procedure as the Electrode Example B.
  • Coin cells are prepared from the Electrode Example A and Comparative Electrode Example B.
  • Half -cell batteries (versus lithium metal) are prepared in a glove box.
  • the electrolyte contains 1 M LiPF 6 in a solution of ethylene carbonate/dimethylene carbonate (1 :1 volume/volume) and 2 wt% vinylene carbonate.
  • the cells are cycled in an ARBIN 2000 by limiting the capacity at 1200 mAh/g silicon, this equals to 600 mAh/g for the electrode.
  • Electrode Example A (357.2 mA/g).
  • the number of lithiation cycles at 1200 mAh/g is measured and presented in Table 1.
  • the lithiation and delithiation cycle life (the number of cycles where it was possible to obtain 1200 mAh/g in de-lithiation) of Electrode Example A is much longer due to the presence of silicon wires. Silicon wires improve the long range connectivity between particles that are surrounded and electrically insulated by decomposed electrolyte.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Cette invention concerne un matériau d'électrode négative conçu pour être utilisé dans une batterie rechargeable. Ledit matériau comprend un matériau à base de Si comprenant un mélange de particules de Si submicroniques et de fils de Si submicroniques, la dimension moyenne des particules de Si étant au moins deux fois supérieure à la largeur moyenne des fils de Si, de préférence au moins cinq fois supérieure et idéalement au moins dix fois supérieure à la largeur moyenne des fils de Si. Le procédé de fabrication de ces matériaux à base de Si comprend les étapes consistant à : utiliser un précurseur à base de Si, utiliser un flux gazeux à une température supérieure au point d'atomisation du précurseur de Si, injecter le précurseur de Si dans le flux gazeux, refroidir le flux gazeux transportant le précurseur de Si vaporisé pour obtenir un mélange de particules de Si submicroniques et de fils de Si submicroniques, et séparer le mélange du flux gazeux.
PCT/EP2011/060403 2010-06-29 2011-06-22 Matériau d'électrode négative pour batteries au lithium-ion WO2012000854A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US35948010P 2010-06-29 2010-06-29
US61/359,480 2010-06-29
EP10015818.7 2010-12-20
EP10015818 2010-12-20

Publications (1)

Publication Number Publication Date
WO2012000854A1 true WO2012000854A1 (fr) 2012-01-05

Family

ID=43756749

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/060403 WO2012000854A1 (fr) 2010-06-29 2011-06-22 Matériau d'électrode négative pour batteries au lithium-ion

Country Status (2)

Country Link
TW (1) TW201203673A (fr)
WO (1) WO2012000854A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013087780A1 (fr) 2011-12-14 2013-06-20 Umicore Silicium positivement chargé pour batteries au lithium-ion
WO2013156888A1 (fr) * 2012-04-17 2013-10-24 Umicore Electrodes négative à faible coût à base de silicium ayant des performances de cycle améliorées
CN105308776A (zh) * 2013-05-07 2016-02-03 株式会社Lg化学 锂二次电池用负极活性材料、其制备方法和包含其的锂二次电池
WO2016075798A1 (fr) * 2014-11-14 2016-05-19 株式会社日立製作所 Matériau actif d'électrode négative pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion
US9559355B2 (en) 2011-09-19 2017-01-31 HYDRO-QUéBEC Particulate anode materials and methods for their preparation
CN109686952A (zh) * 2018-12-27 2019-04-26 国联汽车动力电池研究院有限责任公司 一种硅碳负极材料及包覆制备方法
US10476101B2 (en) 2014-01-24 2019-11-12 Nissan Motor Co., Ltd. Electrical device
US10535870B2 (en) 2014-01-24 2020-01-14 Nissan Motor Co., Ltd. Electrical device
US11749798B2 (en) 2017-03-03 2023-09-05 Hydro-Quebec Nanoparticles comprising a core covered with a passivation layer, process for manufacture and uses thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5776888B2 (ja) * 2011-05-25 2015-09-09 日産自動車株式会社 電気デバイス用負極活物質

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040126659A1 (en) 2002-09-10 2004-07-01 Graetz Jason A. High-capacity nanostructured silicon and lithium alloys thereof
JP2005011696A (ja) * 2003-06-19 2005-01-13 Matsushita Electric Ind Co Ltd 非水電解質二次電池用負極材料
US20080261112A1 (en) 2007-04-17 2008-10-23 Kaoru Nagata Electrode material for electrochemcial device, method for producing the same, electrode using the electrode material, and electrochemical device using the electrode material
US20090042101A1 (en) 2007-08-09 2009-02-12 Mcgervey Donald L High-Power Battery
EP2086671A1 (fr) 2006-12-01 2009-08-12 Umicore Procédé de fabrication de nano-poudres
JP2009199761A (ja) * 2008-02-19 2009-09-03 Nissan Motor Co Ltd リチウムイオン電池
US20090269677A1 (en) 2008-04-23 2009-10-29 Sony Corporation Anode and secondary battery
EP2204867A1 (fr) 2007-09-06 2010-07-07 Canon Kabushiki Kaisha Procede de production de materiau de stockage/liberation d'ions de lithium, materiau de stockage/liberation d'ions de lithium, structure d'electrode mettant en uvre ledit materiau et dispositif de stockage d'electricite associes
WO2011035876A1 (fr) 2009-09-23 2011-03-31 Umicore Nouvelles formulations pour électrodes à base de silicium destinées à être utilisées dans des batteries lithium-ion et procédé d'obtention associé

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040126659A1 (en) 2002-09-10 2004-07-01 Graetz Jason A. High-capacity nanostructured silicon and lithium alloys thereof
JP2005011696A (ja) * 2003-06-19 2005-01-13 Matsushita Electric Ind Co Ltd 非水電解質二次電池用負極材料
EP2086671A1 (fr) 2006-12-01 2009-08-12 Umicore Procédé de fabrication de nano-poudres
US20080261112A1 (en) 2007-04-17 2008-10-23 Kaoru Nagata Electrode material for electrochemcial device, method for producing the same, electrode using the electrode material, and electrochemical device using the electrode material
US20090042101A1 (en) 2007-08-09 2009-02-12 Mcgervey Donald L High-Power Battery
EP2204867A1 (fr) 2007-09-06 2010-07-07 Canon Kabushiki Kaisha Procede de production de materiau de stockage/liberation d'ions de lithium, materiau de stockage/liberation d'ions de lithium, structure d'electrode mettant en uvre ledit materiau et dispositif de stockage d'electricite associes
JP2009199761A (ja) * 2008-02-19 2009-09-03 Nissan Motor Co Ltd リチウムイオン電池
US20090269677A1 (en) 2008-04-23 2009-10-29 Sony Corporation Anode and secondary battery
WO2011035876A1 (fr) 2009-09-23 2011-03-31 Umicore Nouvelles formulations pour électrodes à base de silicium destinées à être utilisées dans des batteries lithium-ion et procédé d'obtention associé

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHAN ET AL., IN NATURE NANOTECH, vol. 3, 2008, pages 31 - 35
HU, L., WU, H., HONG, S.S., CUI, L., MCDONOUGH, J.R., BOHY, S., CUI, Y.: "Si nanoparticle-decorated Si nanowire networks for Li-ion battery anodes", CHEMICAL COMMUNICATIONS, vol. 47, no. 1, 10 September 2010 (2010-09-10), pages 367 - 369, XP002631246, DOI: 10.1039/c0cc02078h *
HU, L.: "Si nanoparticle-decorated Si nanowire networks for Li-ion batery anodes", CHEMICAL COMMUNICATIONS, vol. 47, no. 1, pages 367 - 369, XP002631246, DOI: doi:10.1039/C0CC02078H
LV R ET AL: "Electrochemical behavior of nanoporous/nanofibrous Si anode materials prepared by mechanochemical reduction", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 490, no. 1-2, 4 February 2010 (2010-02-04), pages 84 - 87, XP026858991, ISSN: 0925-8388, [retrieved on 20091013] *
WEN Z ET AL: "Composite silicon film with connected silicon nanowires for lithium ion batteries", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 56, no. 1, 15 December 2010 (2010-12-15), pages 372 - 375, XP027484755, ISSN: 0013-4686, [retrieved on 20101109], DOI: DOI:10.1016/J.ELECTACTA.2010.08.066 *
YAN X Q ET AL: "H2-assisted control growth of Si nanowires", JOURNAL OF CRYSTAL GROWTH, ELSEVIER, AMSTERDAM, NL, vol. 257, no. 1-2, 1 September 2003 (2003-09-01), pages 69 - 74, XP004450883, ISSN: 0022-0248, DOI: DOI:10.1016/S0022-0248(03)01412-X *
YAN X. Q. ET AL.: "H2-assisted control growth of Si nanowires", JOURNAL OF CRYSTAL GROWTH, vol. 257, no. 1-2, pages 69 - 74, XP004450883, DOI: doi:10.1016/S0022-0248(03)01412-X

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9559355B2 (en) 2011-09-19 2017-01-31 HYDRO-QUéBEC Particulate anode materials and methods for their preparation
EP3546093A1 (fr) 2011-09-19 2019-10-02 Hydro-Québec Matériaux d'anode particulaires et procédé de préparation associés
US9837662B2 (en) 2011-09-19 2017-12-05 Hydro-Quebec Particulate anode materials and methods for their preparation
US10340516B2 (en) 2011-12-14 2019-07-02 Umicore Positively charged silicon for lithium-ion batteries
WO2013087780A1 (fr) 2011-12-14 2013-06-20 Umicore Silicium positivement chargé pour batteries au lithium-ion
US9692044B2 (en) 2012-04-17 2017-06-27 Umicore Low cost Si-based negative electrodes with enhanced cycling performance
WO2013156888A1 (fr) * 2012-04-17 2013-10-24 Umicore Electrodes négative à faible coût à base de silicium ayant des performances de cycle améliorées
TWI483447B (zh) * 2012-04-19 2015-05-01 Umicore Nv 用於鋰離子電池之帶正電荷矽
CN105308776A (zh) * 2013-05-07 2016-02-03 株式会社Lg化学 锂二次电池用负极活性材料、其制备方法和包含其的锂二次电池
US9780367B2 (en) 2013-05-07 2017-10-03 Lg Chem, Ltd. Anode active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including the same
EP2996180A4 (fr) * 2013-05-07 2016-06-08 Lg Chemical Ltd Matière active de cathode pour batterie rechargeable au lithium, son procédé de fabrication et batterie rechargeable au lithium comprenant celle-ci
JP2016514898A (ja) * 2013-05-07 2016-05-23 エルジー・ケム・リミテッド リチウム二次電池用負極活物質、この製造方法、及びこれを含むリチウム二次電池
US10476101B2 (en) 2014-01-24 2019-11-12 Nissan Motor Co., Ltd. Electrical device
US10535870B2 (en) 2014-01-24 2020-01-14 Nissan Motor Co., Ltd. Electrical device
JPWO2016075798A1 (ja) * 2014-11-14 2017-08-31 株式会社日立製作所 リチウムイオン二次電池用負極活物質、およびリチウムイオン二次電池
US20170309913A1 (en) * 2014-11-14 2017-10-26 Hitachi, Ltd. Negative Electrode Active Material for Lithium Ion Secondary Battery and Lithium Ion Secondary Battery
WO2016075798A1 (fr) * 2014-11-14 2016-05-19 株式会社日立製作所 Matériau actif d'électrode négative pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion
US11749798B2 (en) 2017-03-03 2023-09-05 Hydro-Quebec Nanoparticles comprising a core covered with a passivation layer, process for manufacture and uses thereof
CN109686952A (zh) * 2018-12-27 2019-04-26 国联汽车动力电池研究院有限责任公司 一种硅碳负极材料及包覆制备方法

Also Published As

Publication number Publication date
TW201203673A (en) 2012-01-16

Similar Documents

Publication Publication Date Title
US8241793B2 (en) Secondary lithium ion battery containing a prelithiated anode
Lu et al. An “electronegative” bifunctional coating layer: simultaneous regulation of polysulfide and Li-ion adsorption sites for long-cycling and “dendrite-free” Li–S batteries
Rao et al. LiNi1/3Co1/3Mn1/3O2-graphene composite as a promising cathode for lithium-ion batteries
WO2012000854A1 (fr) Matériau d'électrode négative pour batteries au lithium-ion
KR101368474B1 (ko) 리튬 이차 전지용 음극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
Zhao et al. In-situ growth amorphous carbon nanotube on silicon particles as lithium-ion battery anode materials
Yan et al. A simple, low-cost and scale-up synthesis strategy of spherical-graphite/Fe2O3 composites as high-performance anode materials for half/full lithium ion batteries
Zhang et al. Carboxylated carbon nanotube anchored MnCO3 nanocomposites as anode materials for advanced lithium-ion batteries
Zhang et al. A compact silicon–carbon composite with an embedded structure for high cycling coulombic efficiency anode materials in lithium-ion batteries
Zhang et al. Rational design of NiFe 2 O 4–rGO by tuning the compositional chemistry and its enhanced performance for a Li-ion battery anode
AU2010200960A1 (en) Open porous electrically conductive nanocomposite material
WO2012117991A1 (fr) Matériau actif d'électrode négative pour batterie au lithium-ion rechargeable, électrode négative pour batterie au lithium-ion rechargeable, et batterie au lithium-ion rechargeable
CN111342030A (zh) 一种多元复合高首效锂电池负极材料及其制备方法
Luo et al. Carbon nanotube-modified LiFePO4 for high rate lithium ion batteries
Cheng et al. Core-shell structured Si@ Ni nanoparticles encapsulated in graphene nanosheet for lithium ion battery anodes with enhanced reversible capacity and cyclic performance
Qiao et al. A chain-like compound of Si@ CNT nanostructures and MOF-derived porous carbon as an anode for Li-ion batteries
Zhou et al. Spherical-graphite/nano-Mn2O3 composites as advanced anode materials for lithium half/full batteries
JP2018120845A (ja) 非水系電解質二次電池用正極合剤ペーストとその製造方法、非水系電解質二次電池用正極とその製造方法、及び、非水系電解質二次電池
CN111342031A (zh) 一种多元梯度复合高首效锂电池负极材料及其制备方法
Ding et al. Nanoscale MnO and natural graphite hybrid materials as high-performance anode for lithium ion batteries
TW202209731A (zh) 含石墨烯的金屬化氧化矽複合材料
Zeng et al. Preparation of dual-shell Si/TiO2/CFs composite and its lithium storage performance
Han et al. Rapid microwave synthesis of Zn3 (OH) 2V2O7· 2H2O nanosheets for enhanced lithium storage performances
Fan et al. Deposition of nanocrystal Co3O4 on graphene nanosheets as anode materials for lithium ion batteries
Lee et al. Synthesis of Cu 3.8 Ni/CoO and Cu 3.8 Ni/MnO nanoparticles for advanced lithium-ion battery anode materials

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11729096

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11729096

Country of ref document: EP

Kind code of ref document: A1