US20150010826A1 - Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof - Google Patents

Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof Download PDF

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Publication number
US20150010826A1
US20150010826A1 US14/371,922 US201314371922A US2015010826A1 US 20150010826 A1 US20150010826 A1 US 20150010826A1 US 201314371922 A US201314371922 A US 201314371922A US 2015010826 A1 US2015010826 A1 US 2015010826A1
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Prior art keywords
lithium metal
lithium
stabilized
stabilized particulate
particulate lithium
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Abandoned
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US14/371,922
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Inventor
Ulrich Wietelmann
Christoph Hartnig
Ute Emmel
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Albemarle Germany GmbH
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Rockwood Lithium GmbH
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Assigned to Rockwood Lithium GmbH reassignment Rockwood Lithium GmbH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HARTNIG, CHRISTOPH, EMMEL, UTE, WIETELMANN, ULRICH
Assigned to ALBEMARLE GERMANY GMBH reassignment ALBEMARLE GERMANY GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: Rockwood Lithium GmbH
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal 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
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/40—Alloys based on alkali metals
    • 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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • 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

  • the invention relates to particulate metal composite materials stabilized with alloy-forming elements of main groups 3 and 4 of the periodic table of elements as well as a method for producing the same by reacting lithium metal with film-forming element precursors in an organic inert solvent at temperatures between 50° C. and 300° C., preferably above the melting point of lithium.
  • Lithium is one of the alkali metals. Like the heavy element homologs of the first main group, lithium is characterized by a strong reactivity with a variety of substances. It thus reacts violently with water, alcohols and other substances containing protic hydrogen, often with ignition. It is unstable in air and reacts with oxygen, nitrogen and carbon dioxide. It is therefore normally handled under an inert gas (noble gases such as argon) and is stored under a protective layer of paraffin oil.
  • inert gas noble gases such as argon
  • Lithium also reacts with many functionalized solvents, even if they do not contain protic hydrogen. For example, cyclic ethers such as THF are opened by ring cleavage, esters and carbonyl compounds are lithiated and/or reduced in general. The reaction between the aforementioned chemicals and/or environmental substances is often catalyzed by water. Lithium metal can therefore be stored and processed in dry air for long periods of time because it forms a somewhat stable passivation layer that prevents most corrosion. This is also true of functionalized solvents, for example, N-methyl-2-pyrrolidone (NMP), which is much less reactive with lithium in anhydrous form than lithium with a water content of more than a few 100 ppm.
  • NMP N-methyl-2-pyrrolidone
  • molten lithium metal may be treated with CO 2 .
  • molten lithium in an inert hydrocarbon is typically brought in contact with at least 0.3% CO 2 for at least one minute.
  • NMP N-methyl-2-pyrrolidone
  • Another method for stabilizing lithium metal consists of heating it above its melting point, agitating the molten lithium and bringing it in contact with a fluorination agent, for example, perfluoropentylamine (WO 2007/005983 A2). It is a disadvantage that fluorinating agents are often toxic or caustic and therefore tend to be avoided in industrial practice.
  • a fluorination agent for example, perfluoropentylamine
  • Another method of protective surface treatment of lithium metal consists of coating it with a wax layer, for example, a polyethylene wax (WO 2008/045557 A1). It is a disadvantage that a relatively large amount of coating agent must be applied. This amount is approx. 1% in the examples in the patent application cited above.
  • US 2009/0061321 A1 proposes the production of a stabilized lithium metal powder having an essentially continuous polymer coating.
  • the polymer may be selected from the group of polyurethanes, PTFE, PVC, polystyrene, etc.
  • One disadvantage of this method is that the protected lithium metal has an undefined surface coating of organic substances which can interfere in its subsequent use, for example, for prelithiation of electrode materials.
  • an anode for an electrochemical cell containing a metallic material with an oxygen-based coating is formed with a (additional) protective layer which is formed by reaction of D- or P-block precursors with this layer containing oxygen (WO 2010/101856 A1, US 2007/0082268 A1, US 2009/0220857 A1).
  • the protective layer of the metal anode material is produced by treating a metallic material, which has a coating that contains oxygen, with at least two compounds, wherein the first compound is a large molecular compound and the second compound is a small molecular compound (U.S. Pat. No. 7,776,385 B2, US 2011/0104366 A1).
  • One disadvantage of this method is that it takes place in multiple steps, i.e., first the metallic material, for example, lithium metal, is provided with a layer containing oxygen and then is reacted with two different molecular compounds (D- or P-block precursors).
  • the object of the invention is to provide lithium metal impressions with a passivating top coat as well as a method for producing these metal impressions,
  • Such lithium metal impressions should be stable for several days at temperatures up to at least about 50° C. in the presence of polar reactive solvents such as those used for the production of electrode coatings, i.e., NMP, for example.
  • polar reactive solvents such as those used for the production of electrode coatings, i.e., NMP, for example.
  • the object is achieved by the fact that the lithium metal impression contains a core of metallic lithium, which is surrounded with an outer layer containing one or more elements of main groups 3 and/or 4 of the periodic table of elements that can be alloyed with lithium.
  • the lithium metal impressions according to the invention are produced by bringing them in contact with one or more passivating agents of general formulas I or II:
  • lithium halide In contact with lithium, compounds with halogen bonds can be cleaved, forming lithium halide in part.
  • the lithium halide may be deposited in the coating layer because it is not soluble in the inert hydrocarbon-based solvent that is used, i.e., forming a lithium that may also contain lithium halide in its surface.
  • the lithium halide dissolves and may then come in contact with all battery components. It is known that lithium halides, in particular LiCl, LiBr and LiI, have a corrosive effect on cathode current diverters made of aluminum.
  • the preferred lithium source is a pure grade, i.e., in particular a grade of lithium that has a very low sodium content.
  • Such metal grades are available commercially as “battery grade” lithium.
  • the Na content is preferably ⁇ 200 ppm and especially preferably ⁇ 100 ppm. It has surprisingly been found that when using lithium metal of a low sodium content, particularly stable products that can be handled safely can be produced.
  • the reaction between the lithium metal and one or more of the passivating agents according to the invention takes place in the temperature range between 50 and 300° C., preferably between 100 and 280° C.
  • Molten lithium is most especially preferably used, i.e., the reaction temperature is at least 180.5° C. and spherical lithium particles (i.e., lithium powder or granules consisting of spherical particles) are produced and treated in the molten form with a passivating agent according to the invention.
  • the lithium is first heated to a temperature above the melting point of lithium (180.5° C.) under an inert gas (noble gas, for example, dry argon) in an organic inert solvent or solvent mixture (usually hydrocarbon based).
  • an inert gas for example, dry argon
  • organic inert solvent or solvent mixture usually hydrocarbon based
  • an emulsion of the metal in hydrocarbon is prepared.
  • this is accomplished by homogenization using agitating tools which yield the required shearing forces for the respective impression.
  • agitating tools which yield the required shearing forces for the respective impression.
  • a dispersing disk may be used, for example.
  • the precise dispersing parameters i.e., mainly the rotational speed and dispersing time
  • the agitating frequency is generally between 1000 and 25,000 revolutions per minute (rpm), preferably 2000 to 20,000 rpm.
  • the dispersing time i.e., the period of time within which the dispersing tool runs at full capacity is between 1 and 60 minutes, preferably 2 and 30 minutes. If particularly finely divided particles are desired, then extremely high-speed special tools may be used, for example, it is available commercially under the brand name Ultraturrax.
  • the passivating agent may be added together with the metal and the solvent before the start of the heating phase. However, the passivating agent is preferably added only after melting the metal, i.e., at temperatures >180.5° C. This addition may take place in an uncontrolled manner (i.e., in one portion) during the dispersion process, but the passivating agent is preferably added over a period of time over approx. 5 to 5000 sec, especially preferably 30 sec to 1000 sec.
  • the particle preparation can also be accomplished by an atomization process.
  • molten lithium is sprayed into an inert gas atmosphere.
  • an inert organic solvent usually a hydrocarbon
  • Suitable passivating agents include the molecular or “at” compounds of the general formulas I or II or polymers containing elements of main groups 3 and/or 4 of the periodic table of elements that can be alloyed with lithium.
  • Especially preferred compound are those of boron, aluminum, silicon and tin. Examples of particularly preferred passivating agents include:
  • the passivating agents either in pure form or dissolved in a solvent that is inert with respect to lithium metal (i.e., hydrocarbons, for example) or in a less reactive aprotic solvent (an ether, for example), are added to the mixture of lithium metal and the aprotic inert solvent. Addition of the passivating agent is followed by a post-reaction phase, during which the reaction is completed. The duration of the post-reaction phase depends on the reaction temperature and the reactivity of the selected passivating agent with respect to lithium metal.
  • the average particle size of the metal powder according to the invention is max. 5000 ⁇ m, preferably max. 1000 ⁇ m and especially preferably max. 300 ⁇ m.
  • the method according to the invention is also suitable for passivation of nonspherical lithium metal impressions, for example, lithium foil.
  • the passivation is performed with the film-forming precursors of main groups 3 and/or 4 of the periodic table of elements at temperatures below the melting point of lithium.
  • passivation may first be performed according to the prior art using fatty acids or fatty acid esters and the resulting particulate lithium metal can then be stabilized further by an additional coating with one of the passivating agents according to the invention.
  • This additional passivation is performed in a hydrocarbon solvent, preferably at temperature below the melting point of lithium (i.e., ⁇ 180.5° C.).
  • the amount of passivating agent used for the surface coating depends on the particle size, the chemical structure of the passivating agent and the desired layer thickness.
  • the molar ratio between Li metal and the passivating agent is 100:0.01 to 100:5, preferably 100:0.05 to 100:1.
  • lithium metal products having contents >95% preferably >97% are the result.
  • the passivated lithium metal impression according to the invention surprisingly contains the alloy-forming element A at least partially in elemental form or in the form of an alloy with lithium. Silicon is thus formed in the reaction of the passivating agents containing silicon according to the invention with metallic lithium, forming in a second step the Li-rich alloy Li 21 Si 5 . It is assumed that metallic lithium is formed by a redox process by using silicic acid esters as follows, for example:
  • the resulting metallic silicon forms one of the known crystalline Li alloys (mostly one of the existing alloys having the highest lithium content, i.e., Li 21 Si 5 ) in the case of Si.
  • the lithium alcoholate which is formed as a coupling product may react further depending on the selected synthesis conditions, forming lithium oxide, for example.
  • a multicomponent coating of the lithium impression consisting of an alloy layer and a salt-type layer containing Li is formed in this way.
  • Lithium metal powder that has a low sodium content and has been passivated according to the invention has surprisingly been proven to be particularly stable in contact with reactive polar solvents, for example, N-methyl-2-pyrrolidone.
  • the lithium metal powder according to the invention surprisingly does not have any significant exothermic effect in the DSC test in suspension with N-methyl-2-pyrrolidone (water content less than approx. 200 ppm) when stored for at least 15 hours at 50° C. and especially preferably at 80° C. and in particular it does not exhibit any “runaway” phenomenon.
  • N-methyl-2-pyrrolidone water content less than approx. 200 ppm
  • the passivated lithium metal impressions according to the invention may be used for prelithiation of electrochemically active materials, e.g., graphite, alloy or conversion anodes for lithium batteries or after a suitable mechanical physicochemical pretreatment (pressing, mixing with binder materials, etc.) for the production of metal anodes for lithium batteries.
  • electrochemically active materials e.g., graphite, alloy or conversion anodes for lithium batteries
  • suitable mechanical physicochemical pretreatment pressing, mixing with binder materials, etc.
  • the product stability is determined by means of DSC (differential scanning calorimetry). An apparatus from the Systag company in Switzerland (the Radex system) was used. Approx. 2 g NMP and 0.1 g lithium metal powder were weighed into the sample containers. Samples were stored for 15 hours at certain temperatures. The particle size distribution was determined using the Lasentec FBRM inline analyzer from Mettler-Toledo.
  • FIG. 1 shows an x-ray diffractogram of the metal powder from example 1, passivated with a layer containing Si
  • FIG. 2 shows an x-ray diffractogram of the metal powder from Example 2 passivated with a layer containing Si
  • the suspension is poured onto a glass suction filter.
  • the filter residue is washed several times with hexane until free of oil and then vacuum dried.
  • Average particle size 140 pm (FBRM particle size analyzer from Mettler-Toledo);
  • Metal content 99.5% (gas volumetric);
  • the suspension is poured onto a glass suction filter.
  • the filter residue is washed several times with hexane until free of oil and then vacuum dried.
  • Average particle size 101 ⁇ m (FBRM particle size analyzer from Mettler-Toledo);
  • the suspension is poured onto a glass suction filter.
  • the filter residue is washed several times with hexane until free of oil and then vacuum dried.
  • Average particle size 51 ⁇ m (FBRM particle size analyzer from Mettler-Toledo);
  • Metal content 99% (gas volumetric);
  • Lithium Metal Powder with a Low Sodium Content Passivated with a Layer Containing Boron (Lithium Bis(Oxalate)Borate, LiBOB) as the Passivating Agent
  • the suspension is poured onto a glass suction filter.
  • the filter residue is washed several times with hexane until free of oil and then vacuum dried.
  • Average particle size 43 ⁇ m (FBRM particle size analyzer from Mettler-Toledo);
  • the suspension is poured onto a glass suction filter.
  • the filter residue is washed several times with hexane until free of oil and then vacuum dried.
  • Average particle size 125 ⁇ m (FBRM particle size analyzer from Mettler-Toledo);
  • Stability in NMP, water content 167 ppm stable for 15 hours at 80° C.; stable for 15 hours at 100° C.; runaway after a few minutes at 120° C.;

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
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US14/371,922 2012-01-13 2013-01-14 Stabilized lithium metal impressions coated with alloy-forming elements and method for production thereof Abandoned US20150010826A1 (en)

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DE102012200479.3 2012-01-13
DE102012200479 2012-01-13
PCT/EP2013/050570 WO2013104787A1 (de) 2012-01-13 2013-01-14 Stabilisierte mit legierungsbildenden elementen beschichtete lithiummetallabformungen und verfahren zu deren herstellung

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EP (1) EP2802430B1 (enExample)
JP (1) JP6284488B2 (enExample)
KR (1) KR102059396B1 (enExample)
CN (1) CN104185522B (enExample)
BR (1) BR112014017192B1 (enExample)
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DE (1) DE102013200416A1 (enExample)
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US10522819B2 (en) 2014-02-13 2019-12-31 Albemarle Germany Gmbh Stabilised (partially) lithiated graphite materials, methods for the production thereof and use for lithium batteries
EP3706225A4 (en) * 2018-03-09 2021-01-13 Lg Chem, Ltd. LITHIUM SECONDARY BATTERY
CN113299887A (zh) * 2021-05-20 2021-08-24 清华大学深圳国际研究生院 金属锂负极的制备方法、金属锂负极及锂金属电池
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US9985283B2 (en) * 2014-07-16 2018-05-29 Prologium Holding Inc. Active material
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US20190393497A1 (en) 2015-01-28 2019-12-26 Albemarle Germany Gmbh Lithiated silicon/carbon composite materials and method for producing the same
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CN108538642A (zh) * 2018-01-26 2018-09-14 南昌大学 一种稳定化金属锂粉的制备方法
WO2019172637A2 (ko) * 2018-03-09 2019-09-12 주식회사 엘지화학 리튬 이차전지
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KR102200268B1 (ko) * 2018-11-27 2021-01-08 한국과학기술연구원 리튬 기반의 하이브리드 음극재료, 이의 제조방법 및 이를 포함하는 리튬금속 이차전지
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US11018334B2 (en) 2021-05-25
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BR112014017192B1 (pt) 2019-07-09
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