CA2811941C - Stabilized, pure lithium metal powder and method for producing the same - Google Patents
Stabilized, pure lithium metal powder and method for producing the same Download PDFInfo
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C24/00—Alloys based on an alkali or an alkaline earth metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- 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
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- 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
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- 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
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- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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Abstract
The invention relates to a stabilized lithium metal powder and to a method for producing the same, the stabilized, pure lithium metal powder having been passivated in an organic inert solvent under dispersal conditions with fatty acids or fatty acid esters according to the general formula (I) R-COOR', in which R stands for C10-C29 groups and R' for H or C1-C8 groups.
Description
Stabilized, pure lithium metal powder and method for producing the same FIELD
Described are a stabilized lithium metal powder and a method for producing stabilized, pure lithium metal powder by dispersion in an organic, inert solvent in the presence of fatty acids or fatty acid esters.
BACKGROUND
Lithium is an alkali metal. As with the heavy element homologues of the first main group, it is characterized by strong reactivity relative to a plurality of materials. It reacts violently, often igniting, with water, alcohols and other materials containing protic hydrogen. Exposed to air, it is unstable reacting with oxygen, nitrogen and carbon dioxide. This is why it is usually handled under an inert gas (noble gases, such as argon) and stored under a protective layer of paraffin oil.
Furthermore, it reacts with many functionalized solvents, even if these do not contain any protic hydrogen. For example, cyclic ethers such as THE are opened by ring cleaving, ester and carbonyl compounds are generally lithiated and/or reduced. The reaction of the named chemicals and/or environmental materials is often catalyzed by water. Correspondingly, lithium metal can be stored and processed over longer periods of time in dry air, because it generates a somewhat stable passivation layer that prevents any further corrosion from occurring. Similar comments apply for functionalized solvents, for example N-methyl-2-pyrrolidone, that are substantially less reactive relative to lithium in a water-free form than, for example, with water contents of > several 100 ppm.
A number of corrosion-reducing coating methods was developed to improve the storage life of lithium metal and security during processing. Correspondingly, US
5,567,474 and US 5,776,369, for example, disclose treating lithium metal with CO2. For the coating, liquid lithium in an inert hydrocarbon is typically brought in contact with at least 0.3% CO2 for at least 1 minute. However, the protection that is thus achieved is insufficient for many applications, especially for the prelithiation of battery electrode materials in a N-methyl-2-pyrrolidone (NMP) suspension.
A further method for stabilizing lithium metal provides for heating the same in excess of the melting point thereof, stirring the melted lithium and bringing it into contact with a fluorinating agent, for example perfluoropentylamine (WO
2007/005983A2). Disadvantageously, however, fluorinating agents are often toxic or caustic, which is why they are used with great caution in industrial practice.
A further method for a protective surface treatment of lithium metal envisions providing the same with a wax layer, for example a polyethylene wax layer (WO
2008/045557A1). It is disadvantageous, however, that this method requires the use of quite a large quantity of coating agent. The examples that are listed in the mentioned patent application specify approximately 1%.
US 2008/0283155A1 discloses a method for stabilizing lithium metal that is characterized by the following steps: a) heating lithium metal powder in excess of the melting point thereof in order to produce melted lithium metal; b) dispersing the melted lithium metal; and c) bringing the melted lithium metal in contact with a phosphor-containing substance in order to generate a substantially continuous protective layer of lithium phosphate on the lithium metal powder. Handling acidic, caustic materials (phosphoric acid) is generally disadvantageous, but particularly in the presence of lithium metal: upon being brought in contact with each other, both materials react violently releasing an enormous amount of heat.
Furthermore, explosive hydrogen gas is generated when reacting lithium metal with phosphoric acid.
Described are a stabilized lithium metal powder and a method for producing stabilized, pure lithium metal powder by dispersion in an organic, inert solvent in the presence of fatty acids or fatty acid esters.
BACKGROUND
Lithium is an alkali metal. As with the heavy element homologues of the first main group, it is characterized by strong reactivity relative to a plurality of materials. It reacts violently, often igniting, with water, alcohols and other materials containing protic hydrogen. Exposed to air, it is unstable reacting with oxygen, nitrogen and carbon dioxide. This is why it is usually handled under an inert gas (noble gases, such as argon) and stored under a protective layer of paraffin oil.
Furthermore, it reacts with many functionalized solvents, even if these do not contain any protic hydrogen. For example, cyclic ethers such as THE are opened by ring cleaving, ester and carbonyl compounds are generally lithiated and/or reduced. The reaction of the named chemicals and/or environmental materials is often catalyzed by water. Correspondingly, lithium metal can be stored and processed over longer periods of time in dry air, because it generates a somewhat stable passivation layer that prevents any further corrosion from occurring. Similar comments apply for functionalized solvents, for example N-methyl-2-pyrrolidone, that are substantially less reactive relative to lithium in a water-free form than, for example, with water contents of > several 100 ppm.
A number of corrosion-reducing coating methods was developed to improve the storage life of lithium metal and security during processing. Correspondingly, US
5,567,474 and US 5,776,369, for example, disclose treating lithium metal with CO2. For the coating, liquid lithium in an inert hydrocarbon is typically brought in contact with at least 0.3% CO2 for at least 1 minute. However, the protection that is thus achieved is insufficient for many applications, especially for the prelithiation of battery electrode materials in a N-methyl-2-pyrrolidone (NMP) suspension.
A further method for stabilizing lithium metal provides for heating the same in excess of the melting point thereof, stirring the melted lithium and bringing it into contact with a fluorinating agent, for example perfluoropentylamine (WO
2007/005983A2). Disadvantageously, however, fluorinating agents are often toxic or caustic, which is why they are used with great caution in industrial practice.
A further method for a protective surface treatment of lithium metal envisions providing the same with a wax layer, for example a polyethylene wax layer (WO
2008/045557A1). It is disadvantageous, however, that this method requires the use of quite a large quantity of coating agent. The examples that are listed in the mentioned patent application specify approximately 1%.
US 2008/0283155A1 discloses a method for stabilizing lithium metal that is characterized by the following steps: a) heating lithium metal powder in excess of the melting point thereof in order to produce melted lithium metal; b) dispersing the melted lithium metal; and c) bringing the melted lithium metal in contact with a phosphor-containing substance in order to generate a substantially continuous protective layer of lithium phosphate on the lithium metal powder. Handling acidic, caustic materials (phosphoric acid) is generally disadvantageous, but particularly in the presence of lithium metal: upon being brought in contact with each other, both materials react violently releasing an enormous amount of heat.
Furthermore, explosive hydrogen gas is generated when reacting lithium metal with phosphoric acid.
2 Finally, US2009/0061321 proposes the preparation of a stabilized lithium metal powder with a substantially continuous polymer coating. The polymer can be selected from the group comprising polyurethanes, PTFE, PVC, polystyrol, etc.
Disadvantageously, this method provides the protected lithium metal with an undefined surface coating of organic substances that could interfere during any subsequent use thereof, for example the prelithiation of electrode materials.
SUMMARY
An object of the invention seeks to provide a method for preparing lithium metal powder with a passivating cover layer = that does not require the use of gaseous or acidic, caustic or toxic passivation agents;
= that does not result in the formation of undefined organics, especially not in organic polymers; and = that causes the formation of a passivating protective layer made of an inorganic, poorly soluble salt film on the lithium surface; and = the surface coating of which does not interfere with any use, for example, as prelithiation agent for anode materials.
Another object of the invention seeks to provide a method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (I),
Disadvantageously, this method provides the protected lithium metal with an undefined surface coating of organic substances that could interfere during any subsequent use thereof, for example the prelithiation of electrode materials.
SUMMARY
An object of the invention seeks to provide a method for preparing lithium metal powder with a passivating cover layer = that does not require the use of gaseous or acidic, caustic or toxic passivation agents;
= that does not result in the formation of undefined organics, especially not in organic polymers; and = that causes the formation of a passivating protective layer made of an inorganic, poorly soluble salt film on the lithium surface; and = the surface coating of which does not interfere with any use, for example, as prelithiation agent for anode materials.
Another object of the invention seeks to provide a method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (I),
3 wherein R denotes Cio-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises at least one of an ethylate, a propanolate and a butylate.
Another object of the invention seeks to provide a method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (I), wherein R denotes Cio-C29 moieties and R' stands for H or Ci-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises an ester of at least one unsaturated fatty acid selected from the group consisting of oleic acid, stearic acid, palmitic acid, lauric acid, myristinic acid, margaric acid, palmitoleic acid, linolic acid and linolenic acid.
Another object of the invention seeks to provide a method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (I), 3a wherein R denotes Clo-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content <200 ppm, and wherein the passivation agent comprises a triglyceride.
A lithium powder of this kind should be stable for days up to approximately 50 C
and in the presence of polar, reactive solvents, such as are used in the preparation of electrode coatings (for example, NMP).
According to the invention, the object is achieved by using saturated and/or unsaturated fatty acids and/or fatty acid esters according to the general formula I
R-COOR' (I) as passivation agent, wherein R denotes C10-C29 moieties, while R' stands for H
or C1-C8 moieties. A pure lithium, meaning particularly a lithium quality poor in sodium, is used as lithium source. Surprisingly, it was found that using a lithium metal that is poor in sodium, it is possible to obtain especially stable products that 3b are safe to handle.
In one aspect, there is provided a stabilized lithium metal powder which does not show any run-away phenomenon when in contact with N-methyl-2-pyrrolidone having a water content of less than about 200 ppm at a minimum of 15 hours storage at 50 C, and wherein the same was passivated in an organic, inert solvent under dispersal conditions with a fatty acid or fatty acid ester according to formula 1 R-COOR' (I), wherein R denotes C10-C29 moieties and R' stands for H or Ci-C8 moieties, and wherein the lithium metal powder has less than 200 ppm of metallic contamination.
In another aspect, there is provided a method for preparing a stabilized lithium metal powder which does not show any run-away phenomenon when in contact with N-methyl-2-pyrrolidone having a water content of less than about 200 ppm at a minimum of 15 hours storage at 50 C, the method comprising: reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula 1 R-000R' (I), wherein R denotes Cio-C29 moieties and R' stands for H or Ci-C8 moieties.
In another aspect, there is provided a method for preparing a stabilized lithium metal powder, the method comprising: reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on the lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula 1 R-COOR' (I),
Another object of the invention seeks to provide a method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (I), wherein R denotes Cio-C29 moieties and R' stands for H or Ci-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises an ester of at least one unsaturated fatty acid selected from the group consisting of oleic acid, stearic acid, palmitic acid, lauric acid, myristinic acid, margaric acid, palmitoleic acid, linolic acid and linolenic acid.
Another object of the invention seeks to provide a method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (I), 3a wherein R denotes Clo-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content <200 ppm, and wherein the passivation agent comprises a triglyceride.
A lithium powder of this kind should be stable for days up to approximately 50 C
and in the presence of polar, reactive solvents, such as are used in the preparation of electrode coatings (for example, NMP).
According to the invention, the object is achieved by using saturated and/or unsaturated fatty acids and/or fatty acid esters according to the general formula I
R-COOR' (I) as passivation agent, wherein R denotes C10-C29 moieties, while R' stands for H
or C1-C8 moieties. A pure lithium, meaning particularly a lithium quality poor in sodium, is used as lithium source. Surprisingly, it was found that using a lithium metal that is poor in sodium, it is possible to obtain especially stable products that 3b are safe to handle.
In one aspect, there is provided a stabilized lithium metal powder which does not show any run-away phenomenon when in contact with N-methyl-2-pyrrolidone having a water content of less than about 200 ppm at a minimum of 15 hours storage at 50 C, and wherein the same was passivated in an organic, inert solvent under dispersal conditions with a fatty acid or fatty acid ester according to formula 1 R-COOR' (I), wherein R denotes C10-C29 moieties and R' stands for H or Ci-C8 moieties, and wherein the lithium metal powder has less than 200 ppm of metallic contamination.
In another aspect, there is provided a method for preparing a stabilized lithium metal powder which does not show any run-away phenomenon when in contact with N-methyl-2-pyrrolidone having a water content of less than about 200 ppm at a minimum of 15 hours storage at 50 C, the method comprising: reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula 1 R-000R' (I), wherein R denotes Cio-C29 moieties and R' stands for H or Ci-C8 moieties.
In another aspect, there is provided a method for preparing a stabilized lithium metal powder, the method comprising: reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on the lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula 1 R-COOR' (I),
4 wherein R denotes Cio-C29 moieties and R' stands for H or Ci-Ca moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and the passivation agent is used in quantities of 0. 1 g to 50 g per kg of the lithium metal.
In some implementations, the method described herein further comprises prelithiating an electrochemically active material with the stabilized lithium metal powder. In some implementations, the electrochemically active material is selected from the group consisting of graphite, alloy and a conversion anode for a lithium battery.
DETAILED DESCRIPTION
First, the lithium is heated under an inert gas (noble gas, for example dry argon) in an organic, inert solvent or solvent mixture (typically hydrocarbon-based) in excess of the temperature when melting occurs (180.5 C). This process is possible at standard pressure with the use of solvents having boiling temperatures > 180 C (for example, undecane, dodecane or the corresponding commercially available mineral oil mixtures, for example ShellsolsTm). If, on the other hand, more volatile hydrocarbons are used such as, for example, hexane, heptane, octane, decane, toluene, ethylbenzene or cumene, the melting process occurs in an enclosed vessel und under pressurized conditions.
The passivation agent is added when melting is complete, and operation of the agitator system that is used for preparing the dispersion (typically a dispersion disc) is started. The precise dispersion parameters (meaning mainly the rotation speed and the dispersion time) depend on the desired particle size. They further depend on the viscosity of the dispersion solvent as well as the individual geometric parameters of the agitation element (for example, diameter, precise position and toothing size). The person skilled in the art is easily able to conduct the corresponding experiments for delivering the desired particle size.
If lithium particles are to be prepared having a grain size in the range of between and 100 pm, the agitator frequency is generally between 1,000 and 25,000 upm, preferably 2,000 to 20,000 upm. The dispersion time, meaning the time period during which the dispersion tool operates at full power, is between 1 and 5a 30 minutes, preferably between 2 and 15 minutes.
The passivation agent therein can be added already together with the metal and solvent prior to the beginning of the heating phase. Preferably, however, it is only added after the metal has melted, meaning at temperatures > 180 C. The addition can be in an uncontrolled fashion (meaning in one portion) during the dispersion process. Preferably, the passivation agent is added over a time period of approximately 5 s to 1000 s, especially preferred 30 s to 500 s.
Fatty acids or fatty acid esters are used as passivation agents. These auxiliary agents have the advantage that they are commercially available and non-toxic, without remarkable steam pressure, and they do not generate a disturbing film made up of the elements oxygen, carbon and hydrogen on the metal surface.
Examples of preferred passivation agents are: olein (oleic acid), stearic acid, palmitinic acid, lauric acid, myristinic acid, margaric acid, palmitoleinic acid, linolic acid, linolenic acid, either in pure form or as mixtures thereof. As another example, the passivation agent can be a triglyceride. Furthermore, the esters thereof can be used, for example fatty acid glycerides or the esters with monovalent alcohols, for example ethylates, propanolates or butylates. Natural products, such as rapeseed oil, olive oil, sunflower oil or linseed oil can especially preferably be used. Of the named passivation agents, generally 0.1 to 50 g are used per kg lithium metal. The use of 1 to 10 g passivation agent per kg lithium metal is preferred. The specific quantity depends on the concentration of the functional groups (these are, for example, carboxylic acid groups or carboxylate groups) inside the passivation agent, as well as on the degree of fineness of the metal powder that is to be generated: the higher the degree of fineness, the greater is the specific surface, and consequently the higher the need for passivation agent.
The lithium metal is used in the pure form thereof, meaning the metallic contaminations must be below 500 ppm in total. In particular, the sodium content , is limited to a maximum of 200 ppm. The Na content is preferably < 100 ppm, especially preferred < 50 ppm. Lithium metal powders correspondingly poor in sodium that have been passivated according to the above-described method by means of fatty acid or fatty acid esters surprisingly prove especially stable when they come in contact with reactive, polar solvents, for example N-methyl-2-pyrrolidone.
The mean particle size of the metal powder according to the invention is max.
200 pm, preferably max. 100 pm, and especially preferred max. 50 pm.
Within the meaning of the invention, it is also possible to stabilize metal powders, which have been passivated with fatty acids or fatty acid esters, even more strongly by the application of an additional coating. Expedient coating agents are, for example, phosphor-containing compounds (such as phosphoric acid, lithium tris(oxalato)phosphate), fluorinating agents (for example perfluoropentylamine), waxes (for example, polyethylene wax) or polymer coatings (for example, with PU, PTFE, PVC or polystyrol). Said additional passivation is done in a hydrocarbon solvent at temperatures below the melting point of lithium (meaning <180.5 C).
The lithium metal powder according to the invention demonstrates in the differential scanning calorimetry test (DSC test), when in suspension with N-methyl-2-pyrrolidone (water content < ca. 200 ppm) at a minimum of 15 hours storage at 50 C, and especially preferred at 100 C, no significant exothermal effect, particularly no "run-away phenomenon." This behavior is explained in further detail in the following examples.
Subsequently, the invention will be illustrated in further detail using an example, a comparison example and five figures without the claimed scope of protection intended to be limited in any way.
BRIEF DESCRIPTION OF THE FIGURES
Shown are in:
Figure 1: the thermal behavior during storage of the metal powder according to Example 1 in NMP at 80 C and 100 C furnace temperature (-) and sample temperature (+, A);
Figure 2: the thermal behavior during storage of the metal powder according to comparison example 1 in NMP at 50 C furnace temperature (-) and sample temperature (+);
Figure 3: the thermal behavior during storage of a metal powder (Na content 17 ppm) obtained according to Example 1 in NMP with a water content of 1%, furnace temperature (-) and sample temperature (+, A);
Figure 4: the thermal behavior during storage of a metal powder having an Na content of 55 ppm obtain according to Example 1 at 50 C and 100 C furnace temperature (-) and sample temperature (+, x) in NMP (148 ppm water content);
Figure 5: the thermal behavior during storage of a metal powder having an Na content of 55 ppm obtained according to Example 1 at 80 C
furnace temperature (-) and sample temperature (+) in NMP (200 ppm water content).
EXAMPLES AND COMPARATIVE EXAMPLES
Example 1: Preparation of a lithium metal powder poor in sodium and passivated with linseed oil 399 g ShellsolTM D 100 and 19.4 g lithium metal bar sections are filled into a dry 2 L noble metal double-jacket reactor that was rendered inert. The lithium has a sodium content of 17 ppm. Stirring very slowly (ca. 50 rpm), the jacket heater raises the inside temperature to 205 C. Using a syringe, 0.05 g linseed oil is then added. The agitation frequency is raised to 3600 rpm and maintained for 6 minutes. The agitator is then brought to a halt and the suspension cooled to room temperature.
The suspension is drained onto a vacuum filter, the filter residue is washed multiple times with hexane until it is fee of oil, then vacuum-dried.
Yield: 15.6 g (80% of the theory) Mean particle size: ca. 50 pm (image evaluation under SEM) Comparison Example 1: Preparation of lithium metal powder passivated with linseed oil 525 g ShellsolTM D 100 and 32.3 g lithium metal bar sections and 0.11 g sodium are filled into a dry 2 L noble metal double-jacket reactor that was rendered inert and is equipped with a dispersion agitation system. The lithium has a sodium content of 17 ppm. Stirring very slowly (ca. 50 rpm), the jacket heater raises the inside temperature to 205 C. Using a syringe, 0.09 g linseed oil is then added.
The agitation frequency is raised to 3600 rpm and maintained for 6 minutes.
The agitator is then brought to a halt and the suspension cooled to room temperature.
The suspension is drained onto a vacuum filter, the filter residue is washed multiple times with hexane until it is fee of oil, then vacuum-dried.
Yield: 27.3 g (84% of the theory) Mean particle size: ca. 50 pm (image evaluation under SEM) Na content (FES): 0.3%
Example 2: Storage of a metal powder according to the invention from Example 1 in NMP at 80 C and 100 C (DSC test) Instrumentation by the company Systag, Switzerland (the Redex system) was used for the differential scanning calorimetry (DSC) testing. Under a protective gas atmosphere, approximately 2 g NMP and 0.1 g lithium metal powder were weighed into the sample vessels. Samples were stored at certain temperatures for 15 hours.
Comparison Example 2: Storage of the metal powder that is not according to the invention from Comparison Example 1 in NMP at 50 C (DSC test) Example 2 and Comparison Example 2 demonstrate the substantially improved stability of the lithium metal powder according to the invention in contact with NMP: while the product according to the invention did not cause any significant exothermal effects at storage at 80 C, nor at 100 C (the sample temperature remains visibly below the furnace temperature throughout the entire observation period), the metal powder that is not according to the invention shows already at storage at 50 C a visible exothermal reaction. This can be recognized in that the sample temperature clearly exceeds the furnace temperature.
Example 3: Storage of the metal powder according to the invention (Na content 17 ppm) from Example 1 in NMP having a water content of 1% (DSC test) The especially preferred Li metal powder having an Na content of 17 ppm proves kinetically stable even in water-rich NMP.
Example 4: Storage of a lithium metal power prepared according to the invention having an Na content of 55 ppm at 50 C and 100 C in NMP (148 ppm water content) (DSC test) Example 5: Storage of a lithium metal power prepared according to the invention having an Na content of 55 ppm at 80 C in NMP (200 ppm water content) (DSC
test).
The metal powder having a sodium content of 55 ppm is stable at storage temperatures of 50 C and 80 C; at 100 C, however, it shows an exothermal, but not a run-away effect. According to the DSC experiment at 100 C, 73% of the used lithium is still present in metallic form.
In some implementations, the method described herein further comprises prelithiating an electrochemically active material with the stabilized lithium metal powder. In some implementations, the electrochemically active material is selected from the group consisting of graphite, alloy and a conversion anode for a lithium battery.
DETAILED DESCRIPTION
First, the lithium is heated under an inert gas (noble gas, for example dry argon) in an organic, inert solvent or solvent mixture (typically hydrocarbon-based) in excess of the temperature when melting occurs (180.5 C). This process is possible at standard pressure with the use of solvents having boiling temperatures > 180 C (for example, undecane, dodecane or the corresponding commercially available mineral oil mixtures, for example ShellsolsTm). If, on the other hand, more volatile hydrocarbons are used such as, for example, hexane, heptane, octane, decane, toluene, ethylbenzene or cumene, the melting process occurs in an enclosed vessel und under pressurized conditions.
The passivation agent is added when melting is complete, and operation of the agitator system that is used for preparing the dispersion (typically a dispersion disc) is started. The precise dispersion parameters (meaning mainly the rotation speed and the dispersion time) depend on the desired particle size. They further depend on the viscosity of the dispersion solvent as well as the individual geometric parameters of the agitation element (for example, diameter, precise position and toothing size). The person skilled in the art is easily able to conduct the corresponding experiments for delivering the desired particle size.
If lithium particles are to be prepared having a grain size in the range of between and 100 pm, the agitator frequency is generally between 1,000 and 25,000 upm, preferably 2,000 to 20,000 upm. The dispersion time, meaning the time period during which the dispersion tool operates at full power, is between 1 and 5a 30 minutes, preferably between 2 and 15 minutes.
The passivation agent therein can be added already together with the metal and solvent prior to the beginning of the heating phase. Preferably, however, it is only added after the metal has melted, meaning at temperatures > 180 C. The addition can be in an uncontrolled fashion (meaning in one portion) during the dispersion process. Preferably, the passivation agent is added over a time period of approximately 5 s to 1000 s, especially preferred 30 s to 500 s.
Fatty acids or fatty acid esters are used as passivation agents. These auxiliary agents have the advantage that they are commercially available and non-toxic, without remarkable steam pressure, and they do not generate a disturbing film made up of the elements oxygen, carbon and hydrogen on the metal surface.
Examples of preferred passivation agents are: olein (oleic acid), stearic acid, palmitinic acid, lauric acid, myristinic acid, margaric acid, palmitoleinic acid, linolic acid, linolenic acid, either in pure form or as mixtures thereof. As another example, the passivation agent can be a triglyceride. Furthermore, the esters thereof can be used, for example fatty acid glycerides or the esters with monovalent alcohols, for example ethylates, propanolates or butylates. Natural products, such as rapeseed oil, olive oil, sunflower oil or linseed oil can especially preferably be used. Of the named passivation agents, generally 0.1 to 50 g are used per kg lithium metal. The use of 1 to 10 g passivation agent per kg lithium metal is preferred. The specific quantity depends on the concentration of the functional groups (these are, for example, carboxylic acid groups or carboxylate groups) inside the passivation agent, as well as on the degree of fineness of the metal powder that is to be generated: the higher the degree of fineness, the greater is the specific surface, and consequently the higher the need for passivation agent.
The lithium metal is used in the pure form thereof, meaning the metallic contaminations must be below 500 ppm in total. In particular, the sodium content , is limited to a maximum of 200 ppm. The Na content is preferably < 100 ppm, especially preferred < 50 ppm. Lithium metal powders correspondingly poor in sodium that have been passivated according to the above-described method by means of fatty acid or fatty acid esters surprisingly prove especially stable when they come in contact with reactive, polar solvents, for example N-methyl-2-pyrrolidone.
The mean particle size of the metal powder according to the invention is max.
200 pm, preferably max. 100 pm, and especially preferred max. 50 pm.
Within the meaning of the invention, it is also possible to stabilize metal powders, which have been passivated with fatty acids or fatty acid esters, even more strongly by the application of an additional coating. Expedient coating agents are, for example, phosphor-containing compounds (such as phosphoric acid, lithium tris(oxalato)phosphate), fluorinating agents (for example perfluoropentylamine), waxes (for example, polyethylene wax) or polymer coatings (for example, with PU, PTFE, PVC or polystyrol). Said additional passivation is done in a hydrocarbon solvent at temperatures below the melting point of lithium (meaning <180.5 C).
The lithium metal powder according to the invention demonstrates in the differential scanning calorimetry test (DSC test), when in suspension with N-methyl-2-pyrrolidone (water content < ca. 200 ppm) at a minimum of 15 hours storage at 50 C, and especially preferred at 100 C, no significant exothermal effect, particularly no "run-away phenomenon." This behavior is explained in further detail in the following examples.
Subsequently, the invention will be illustrated in further detail using an example, a comparison example and five figures without the claimed scope of protection intended to be limited in any way.
BRIEF DESCRIPTION OF THE FIGURES
Shown are in:
Figure 1: the thermal behavior during storage of the metal powder according to Example 1 in NMP at 80 C and 100 C furnace temperature (-) and sample temperature (+, A);
Figure 2: the thermal behavior during storage of the metal powder according to comparison example 1 in NMP at 50 C furnace temperature (-) and sample temperature (+);
Figure 3: the thermal behavior during storage of a metal powder (Na content 17 ppm) obtained according to Example 1 in NMP with a water content of 1%, furnace temperature (-) and sample temperature (+, A);
Figure 4: the thermal behavior during storage of a metal powder having an Na content of 55 ppm obtain according to Example 1 at 50 C and 100 C furnace temperature (-) and sample temperature (+, x) in NMP (148 ppm water content);
Figure 5: the thermal behavior during storage of a metal powder having an Na content of 55 ppm obtained according to Example 1 at 80 C
furnace temperature (-) and sample temperature (+) in NMP (200 ppm water content).
EXAMPLES AND COMPARATIVE EXAMPLES
Example 1: Preparation of a lithium metal powder poor in sodium and passivated with linseed oil 399 g ShellsolTM D 100 and 19.4 g lithium metal bar sections are filled into a dry 2 L noble metal double-jacket reactor that was rendered inert. The lithium has a sodium content of 17 ppm. Stirring very slowly (ca. 50 rpm), the jacket heater raises the inside temperature to 205 C. Using a syringe, 0.05 g linseed oil is then added. The agitation frequency is raised to 3600 rpm and maintained for 6 minutes. The agitator is then brought to a halt and the suspension cooled to room temperature.
The suspension is drained onto a vacuum filter, the filter residue is washed multiple times with hexane until it is fee of oil, then vacuum-dried.
Yield: 15.6 g (80% of the theory) Mean particle size: ca. 50 pm (image evaluation under SEM) Comparison Example 1: Preparation of lithium metal powder passivated with linseed oil 525 g ShellsolTM D 100 and 32.3 g lithium metal bar sections and 0.11 g sodium are filled into a dry 2 L noble metal double-jacket reactor that was rendered inert and is equipped with a dispersion agitation system. The lithium has a sodium content of 17 ppm. Stirring very slowly (ca. 50 rpm), the jacket heater raises the inside temperature to 205 C. Using a syringe, 0.09 g linseed oil is then added.
The agitation frequency is raised to 3600 rpm and maintained for 6 minutes.
The agitator is then brought to a halt and the suspension cooled to room temperature.
The suspension is drained onto a vacuum filter, the filter residue is washed multiple times with hexane until it is fee of oil, then vacuum-dried.
Yield: 27.3 g (84% of the theory) Mean particle size: ca. 50 pm (image evaluation under SEM) Na content (FES): 0.3%
Example 2: Storage of a metal powder according to the invention from Example 1 in NMP at 80 C and 100 C (DSC test) Instrumentation by the company Systag, Switzerland (the Redex system) was used for the differential scanning calorimetry (DSC) testing. Under a protective gas atmosphere, approximately 2 g NMP and 0.1 g lithium metal powder were weighed into the sample vessels. Samples were stored at certain temperatures for 15 hours.
Comparison Example 2: Storage of the metal powder that is not according to the invention from Comparison Example 1 in NMP at 50 C (DSC test) Example 2 and Comparison Example 2 demonstrate the substantially improved stability of the lithium metal powder according to the invention in contact with NMP: while the product according to the invention did not cause any significant exothermal effects at storage at 80 C, nor at 100 C (the sample temperature remains visibly below the furnace temperature throughout the entire observation period), the metal powder that is not according to the invention shows already at storage at 50 C a visible exothermal reaction. This can be recognized in that the sample temperature clearly exceeds the furnace temperature.
Example 3: Storage of the metal powder according to the invention (Na content 17 ppm) from Example 1 in NMP having a water content of 1% (DSC test) The especially preferred Li metal powder having an Na content of 17 ppm proves kinetically stable even in water-rich NMP.
Example 4: Storage of a lithium metal power prepared according to the invention having an Na content of 55 ppm at 50 C and 100 C in NMP (148 ppm water content) (DSC test) Example 5: Storage of a lithium metal power prepared according to the invention having an Na content of 55 ppm at 80 C in NMP (200 ppm water content) (DSC
test).
The metal powder having a sodium content of 55 ppm is stable at storage temperatures of 50 C and 80 C; at 100 C, however, it shows an exothermal, but not a run-away effect. According to the DSC experiment at 100 C, 73% of the used lithium is still present in metallic form.
Claims (18)
1. A method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180°C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (1), wherein R denotes C10-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises at least one of an ethylate, a propanolate and a butylate.
reacting lithium metal having less than 200 ppm of metallic contamination above 180°C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula I
R-COOR' (1), wherein R denotes C10-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises at least one of an ethylate, a propanolate and a butylate.
2. The method according to claim 1, wherein the passivation agent comprises an ethylate.
3. The method according to claim 1, wherein the passivation agent comprises a propanolate.
4. The method according to claim 1, wherein the passivation agent comprises a butylate.
5. The method according to any one of claims 1 to 4, wherein the organic, inert solvent is one or more hydrocarbons, selected from the group consisting of hexane, heptane, octane, decane, undecane, dodecane, toluene, ethyl benzene, cumene, and mixtures thereof.
6. The method according to any one of claims 1 to 5, further comprising prelithiating an electrochemically active material with the stabilized lithium metal powder.
7. The method according to claim 6, wherein the electrochemically active material is selected from the group consisting of graphite, alloy and a conversion anode for a lithium battery.
8. The method according to any one of claims 1 to 7, wherein the passivation agent is used in quantities of 0.1 g to 50 g per kg of the lithium metal.
9. A method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula l R-COOR' (l), wherein R denotes C10-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises an ester of at least one unsaturated fatty acid selected from the group consisting of oleic acid, stearic acid, palmitic acid, lauric acid, myristinic acid, margaric acid, palmitoleic acid, linolic acid and linolenic acid.
reacting lithium metal having less than 200 ppm of metallic contamination above 180 C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula l R-COOR' (l), wherein R denotes C10-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises an ester of at least one unsaturated fatty acid selected from the group consisting of oleic acid, stearic acid, palmitic acid, lauric acid, myristinic acid, margaric acid, palmitoleic acid, linolic acid and linolenic acid.
10. The method according to claims 9, wherein the organic, inert solvent is one or more hydrocarbons, selected from the group consisting of hexane, heptane, octane, decane, undecane, dodecane, toluene, ethyl benzene, cumene, and mixtures thereof.
11. The method according to claim 9 or 10, further comprising prelithiating an electrochemically active material with the stabilized lithium metal powder.
12. The method according to any one of claims 9 to 11, wherein the electrochemically active material is selected from the group consisting of graphite, alloy and a conversion anode for a lithium battery.
13. The method according to any one of claims 9 to 12, wherein the passivation agent is used in quantities of 0.1 g to 50 g per kg of the lithium metal.
14. A method for preparing a stabilized lithium metal powder, the method comprising:
reacting lithium metal having less than 200 ppm of metallic contamination above 180°C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula l R-COOR' (l), wherein R denotes C10-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises a triglyceride.
reacting lithium metal having less than 200 ppm of metallic contamination above 180°C in an organic, inert solvent under dispersal conditions with a passivation agent to form a passivation protective coating on a lithium surface, the passivation agent containing one or a plurality of fatty acids and/or one or a plurality of fatty acid esters according to formula l R-COOR' (l), wherein R denotes C10-C29 moieties and R' stands for H or C1-C8 moieties, the stabilized lithium metal powder has a sodium content < 200 ppm, and wherein the passivation agent comprises a triglyceride.
15. The method according to claims 15, wherein the organic, inert solvent is one or more hydrocarbons, selected from the group consisting of hexane, heptane, octane, decane, undecane, dodecane, toluene, ethyl benzene, cumene, and mixtures thereof.
16. The method according to claim 15 or 15, further comprising prelithiating an electrochemically active material with the stabilized lithium metal powder.
17. The method according to any one of claims 15 to 16, wherein the electrochemically active material is selected from the group consisting of graphite, alloy and a conversion anode for a lithium battery.
18. The method according to any one of claims 15 to 17, wherein the passivation agent is used in quantities of 0.1 g to 50 g per kg of the lithium metal.
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| PCT/EP2011/066858 WO2012052265A2 (en) | 2010-09-28 | 2011-09-28 | Stabilized, pure lithium metal powder and method for producing the same |
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| DE102013225734A1 (en) | 2012-12-19 | 2014-06-26 | Rockwood Lithium GmbH | Lithium powder anode and galvanic element containing a lithium powder anode |
| DE102014207396A1 (en) | 2013-04-19 | 2014-10-23 | Rockwood Lithium GmbH | Stabilized nitrogen-containing shell-coated lithium metal impressions and methods of making the same |
| KR102204928B1 (en) | 2013-05-16 | 2021-01-18 | 알베마를 저머니 게엠베하 | Active lithium reservoir for lithium-ion batteries |
| 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 |
| US20160351893A1 (en) | 2014-02-13 | 2016-12-01 | Rockwood Lithium GmbH | Galvanic Cells and (Partially) Lithiated Lithium Battery Anodes with Increased Capacity and Methods for Producing Synthetic Graphite Intercalation Compounds |
| CN106537666B (en) | 2014-07-14 | 2020-02-28 | 住友金属矿山株式会社 | Coated lithium-nickel composite oxide particles and method for producing coated lithium-nickel composite oxide particles |
| CN104157463A (en) * | 2014-08-15 | 2014-11-19 | 万星光电子(东莞)有限公司 | Negative electrode sheet and preparation method thereof, lithium ion supercapacitor |
| CN105762328B (en) * | 2014-12-15 | 2019-03-29 | 比亚迪股份有限公司 | A kind of passivation of lithium powder and preparation method thereof adds the positive electrode and battery of the passivation of lithium powder |
| DE102015202612A1 (en) | 2015-02-13 | 2016-08-18 | Rockwood Lithium GmbH | Stabilized (partially) lithiated graphite materials, process for their preparation and use for lithium batteries |
| CN104835652A (en) * | 2015-03-24 | 2015-08-12 | 中航锂电（洛阳）有限公司 | Lithium-intercalation negative pole piece used for lithium super-capacitor battery, method for preparing same, and lithium super-capacitor battery |
| CN106001585A (en) * | 2015-03-31 | 2016-10-12 | Tdk株式会社 | Stable lithium powder and lithium ion secondary battery using same |
| CN106756105B (en) * | 2016-12-19 | 2018-10-30 | 天齐锂业股份有限公司 | The drop of nitride removes method in lithium metal or lithium alloy |
| CN107058761B (en) * | 2016-12-19 | 2019-06-11 | 天齐锂业股份有限公司 | The method that drop removes nitride in lithium metal or lithium alloy |
| KR20190106638A (en) | 2018-03-09 | 2019-09-18 | 주식회사 엘지화학 | Lithium Secondary Battery |
| CN108923046B (en) * | 2018-07-03 | 2021-08-31 | 江苏乐能电池股份有限公司 | A kind of preparation method of nanoporous lithium-rich lithium iron phosphate material |
| US12555796B2 (en) | 2021-02-03 | 2026-02-17 | A123 Systems Llc | Passivated lithium nitride as cathode pre-lithiation reagent |
| CN115249787A (en) * | 2021-04-28 | 2022-10-28 | 株式会社村田制作所 | A lithium ion secondary battery negative electrode, a preparation method thereof, and a lithium ion secondary battery |
| CN116422878A (en) * | 2023-04-19 | 2023-07-14 | 哈尔滨工业大学 | A Method for Stabilizing Al-Li Alloy Powders by Coating with Organic Matters |
| DE102024205641A1 (en) | 2024-06-19 | 2025-12-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Processes for the production of metal powder, as well as metal powder and its use |
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| JP2699026B2 (en) * | 1993-02-18 | 1998-01-19 | エフ エム シー コーポレーション | Alkali metal dispersion |
| JPH0811694B2 (en) * | 1994-01-27 | 1996-02-07 | リチウム コーポレーション オブ アメリカ | Production method of crystalline antimonic acid |
| AU6723896A (en) * | 1995-08-15 | 1997-03-12 | Fmc Corporation | Alkali metal dispersions |
| US20050130043A1 (en) * | 2003-07-29 | 2005-06-16 | Yuan Gao | Lithium metal dispersion in electrodes |
| US7588623B2 (en) * | 2005-07-05 | 2009-09-15 | Fmc Corporation Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
| US20090035663A1 (en) | 2006-10-13 | 2009-02-05 | Fmc Corporation, Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
| JP4317571B2 (en) * | 2007-04-27 | 2009-08-19 | Ｔｄｋ株式会社 | Active material, electrode, battery, and method for producing active material |
| US8021496B2 (en) * | 2007-05-16 | 2011-09-20 | Fmc Corporation | Stabilized lithium metal powder for Li-ion application, composition and process |
| US20090061321A1 (en) | 2007-08-31 | 2009-03-05 | Fmc Corporation, Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
| CN101418406A (en) * | 2008-11-18 | 2009-04-29 | 天津中能锂业有限公司 | Purification lithium and purification method |
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| BR112013007687A2 (en) | 2016-08-09 |
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