Stabilized lithium metal formations coasted with a shell containing nitrogen, and a method for the production of same
The invention relates to particulate lithium metal formations having a substantially spherical geometry and a core composed of metallic lithium, which are enclosed with an outer passivating but ionically conductive layer containing nitrogen. The invention further relates to a method for producing lithium metal formations by reacting lithium metal with one or more passivating agent(s) containing nitrogen, selected from the groups N 2 , N x H y with x=1 or 2 and y=3 or 4, or a compound containing only the elements C, H, and N, and optionally Li, at temperatures in the range between 60 and 300° C., preferably between 100 and 280° C., and particularly preferably above the melting temperature of lithium of 180.5° C., in an inert organic solvent under dispersion conditions or in an atmosphere that contains a gaseous coating agent containing nitrogen.
1. A method for producing a stabilized lithium metal form of granules, characterized in that lithium metal with a sodium content less than 200 ppm is brought into contact with one or more nitrogen-containing passivating agent(s) selected from the groups
N 2
N x H y with x=1 or 2 and y=3 or 4, or
a compound containing only the elements C, H, and N, and optionally Li at temperatures in the range above the melting point of lithium of 180.5° C.,
wherein the contacting between lithium metal and the one or more nitrogen-containing passivating agent(s) first takes place in an inert organic solvent under dispersion conditions and a molar ratio of Li metal to passivating agent is in a range of 100:0.01 to 100:10.
2. The method according to claim 1 , characterized in that said lithium metal has a sodium content less than 100 ppm.
3. The method according to claim 1 , characterized in that said lithium metal has a sodium content less than 50 ppm.
4. The method according to claim 1 , characterized in that gaseous sources of nitrogen, liquid compounds, or substances that are capable of releasing nitrogen are used as nitrogen-containing passivating agents.
5. The method according to claim 4 , characterized in that gaseous sources of nitrogen are selected from elemental nitrogen or ammonia.
6. The method according to claim 4 , characterized in that liquid nitrogen-containing passivating agent(s) is hydrazine.
7. The method according to claim 4 , characterized in that substances that are capable of releasing nitrogen are selected from lithium azide (LiN3) or organic azides (RN3).
8. The method according to claim 1 , characterized in that organic substances which contain no other chemical elements besides C, H, N, and optionally Li are used as nitrogen-containing coating agents selected from primary, secondary, or tertiary aliphatic amines NR 1 R 2 R 3 , where R 1 , R 2 independently stand for H or an aliphatic group containing 1 to 12 C atoms or an aromatic group containing at least 6 C atoms, and R 3 independently stands for an aliphatic group containing 1 to 12 C atoms or an aromatic group containing at least 6 C atoms; nitrogen-containing 3- to 6-membered heterocycles.
9. The method according to claim 8 , characterized in that nitrogen-containing 3- to 6-membered heterocycles are selected from azirines, aziridines, pyrrolidines, pyrroles, N-methylpyrrole, pyridines, imidazole.
10. The method according to claim 8 , characterized in that as organic substances which contain no other chemical elements besides C, H, N, and Li lithium salts are used of a primary or secondary aliphatic or aromatic amine, selected from lithium diisopropyl amide; lithium pyrrolidide.
11. The method according to claim 1 , characterized in that the molar ratio of Li metal to passivating agent is in the range of 100:0.05 to 100:5.
12. The method according to claim 1 , characterized in that hydrocarbons selected from the group comprising hexane, heptane, octane, decane, undecane, dodecane, toluene, ethylbenzene, and cumene, either in pure form or in a mixture as commercially available boiling fractions, are used as inert organic solvent.
13. A stabilized particulate lithium metal received by the method according to claim 1 characterized in that the stabilized particulate lithium metal has a granular form and a core composed of metallic lithium, and the core is enclosed by an outer passivating layer containing nitrogen wherein that outer passivating layer containing nitrogen has a thickness between 0.01 and 1 μm and contains or is composed of at least one lithium nitrogen compound selected from the group Li 3 N, Li 4 NH, Li 2 NH, LiNH 2 .
14. The stabilized particulate lithium metal according to claim 13 , characterized in that the stabilized particulate lithium metal contains in the range of 0.01 to 10% by weight nitrogen.
15. The stabilized particulate lithium metal according to claim 13 , characterized in that the stabilized particulate lithium metal has an average particle size of 5000 μm maximum.
16. The stabilized particulate lithium metal according to claim 15 , characterized in that the stabilized particulate lithium metal has an average particle size of 1000 μm maximum.
17. The stabilized particulate lithium metal according to claim 15 , characterized in that the stabilized particulate lithium metal has an average particle size of 300 μm maximum.
18. The stabilized particulate lithium metal according to claim 13 , characterized in that the stabilized particulate lithium metal does not exhibit a “runaway” phenomenon, when in contact with N-methyl-2-pyrrolidone, with a water content of approximately 200 ppm, for at least 15 hours at 50° C.
19. The stabilized particulate lithium metal according to claim 18 , characterized in that the stabilized particulate lithium metal does not exhibit a “runaway” phenomenon, when in contact with N-methyl-2-pyrrolidone, with a water content of approximately 200 ppm, for at least 15 hours at 80° C.