Electrolyte additive and metal included in composite electrode containing Mg, Al, Cu, and Cr for alkali metal storage system

Patent metadata

Field	Value
Publication number	US-10297863-B2
Application number	US-201715483357-A
Country	US
Kind code	B2
Filing date	Apr 10, 2017
Priority date	Oct 9, 2014
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

An alkali metal-based energy storage system, having at least one composite electrode containing an active material, and an electrolyte containing a lithium salt dissolved in an aprotic organic solvent, an ionic fluid and/or a polymer matrix. The electrolyte further contains an additive selected from a cation or a compound of a metal selected from Mg, Al, Cu and/or Cr. The metal selected from Mg, Al, Cu and/or Cr is applied onto the active material and/or the active material of the composite electrode is partially replaced by the metal selected from Mg, Al, Cu and/or Cr in the form of a metal powder or a metal salt.

First claim

What is claimed is:

1. A composite electrode for an alkali metal-based energy storage system, the composite electrode comprising:
a support bearing at least one applied or deposited active material,
wherein a metal selected from the group consisting of Mg, Al, Cu and Cr is applied onto the active material and/or the active material in the composite electrode is partially replaced by the metal selected from the group consisting of Mg, Al, Cu and Cr in the form of a metal powder or a metal salt, and
wherein the composite electrode is a cathode which is an electrode that accepts electrons on connection to a consumer and the alkali metal is lithium.

2. The composite electrode of claim 1 , wherein the active material is a material stable to high voltage of ≥4.4 V and is selected from lithium nickel manganese cobalt mixed oxide, lithium metal manganese oxide or lithium-rich transition-metal oxides.

3. An alkali metal-based energy storage system, the system comprising:
at least one composite electrode comprising an active material, wherein the composite electrode is a cathode which is an electrode that accepts electrons on connection to a consumer, and
an electrolyte comprising an alkali metal salt dissolved in an aprotic organic solvent, an ionic liquid and/or a polymer matrix,
wherein the electrolyte further comprises an additive selected from a cation or a compound of a metal selected from the group consisting of Mg, Al, Cu and Cr,
wherein the metal selected from the group consisting of Mg, Al, Cu and Cr is applied onto the active material, and/or the active material in the composite electrode is partially replaced by the metal selected from the group consisting of Mg, Al, Cu and Cr in the form of a metal powder or a metal salt, and
wherein the alkali metal is lithium.

4. The system of claim 3 , wherein the metal for the additive selected from the group consisting of Mg, Al, Cu and Cr takes the form of a cation of a magnesium, aluminum, copper and/or chromium salt in conjunction with an anion selected from AsF 6 − , ClO 4 − , SbF 6 − , PtCl 6 − , AlCl 4 − , GaCl 4 − , SCN − , AlO 4 − , CF 3 CF 2 SO 3 − , (CF 3 )SO 3 − , C(SO 2 CF 3 ) 3 − , PF 6 − , PF 3 (CF 3 ) 3 − , PF 4 (C 2 O 4 ) − , BF 4 − , B(C 2 O 4 ) 2 − , BF 2 (C 2 O 4 ) − , B(C 2 O 4 )(C 3 O 4 ) − , (C 2 F 5 BF 3 ) − , B 12 F 12 2− , N(SO 2 CF 3 ) 2 − , N(FSO 2 ) 2 − or N(SO 2 C 2 F 5 ) 2 − .

5. The system of claim 4 , wherein the additive comprises the magnesium, aluminum, copper and/or chromium salt in the range from ≥0.1 ppm to ≤10 wt %, based on a total electrolyte weight of 100 wt %.

6. The system of claim 4 , wherein the additive comprises the magnesium, aluminum, copper and/or chromium salt in the range from ≥0.01 wt % to ≤5 wt %, based on a total electrolyte weight of 100 wt %.

7. The system of claim 4 , wherein the additive comprises the magnesium, aluminum, copper and/or chromium salt in the range from ≥0.1 wt % to ≤2 wt %, based on a total electrolyte weight of 100 wt %.

8. The system of claim 4 , wherein the additive is magnesium (II) bis(trifluoromethanesulfonyl)imide or aluminum (III) trifluoromethanesulfonate.

9. A method for increasing the cycling stability of an alkali metal-based energy storage system comprising at least one composite electrode having an active material, and an electrolyte comprising a lithium salt dissolved in an aprotic organic solvent, an ionic liquid and/or a polymer matrix, the method comprising the steps of:
admixing the electrolyte with an additive selected from a cation or a compound of a metal selected from the group consisting of Mg, Al, Cu and Cr,
applying the metal selected from the group consisting of Mg, Al, Cu and Cr onto the active material, wherein the active material is selected from lithium nickel manganese cobalt mixed oxide, lithium nickel manganese oxide or lithium-rich transition-metal oxides, and/or
partially replacing the active material by the metal selected from the group consisting of Mg, Al, Cu and Cr in the form of a metal powder or a metal salt, and
wherein the composite electrode is a cathode which is an electrode that accepts electrons on connection to a consumer and the alkali metal is lithium.

10. The method of claim 9 , wherein the metal selected from the group consisting of Mg, Al, Cu and Cr is applied onto the active material of the cathode by sputtering.

11. The method of claim 9 , wherein the composite electrode is made from a collector and an active-material suspension comprising introducing the metal powder or the metal salt, into the active-material suspension by drying, and wherein no metal oxides are formed during the drying of the active-material suspension.

12. The method of claim 11 , wherein the metal is magnesium.

13. The method of claim 11 , wherein the metal powder or the metal salt is introduced into the active material suspension in an amount of 0.1 to 10 wt %.

14. The method of claim 11 , wherein the metal powder or the metal salt is introduced into the active material suspension in an amount of 0.5 to 5 wt %.

15. The method of claim 11 , wherein the metal powder or the metal salt is introduced into the active material suspension in an amount of 1 to 3 wt %.

Assignees

• Bayerische Motoren Werke Ag

Inventors

• JIMENEZ Antonia Reyes
• Winter Martin
• Kasnatscheew Johannes
• Amereller Marius
• Schmitz Raphael Wilhelm
• Wagner Ralf
• Gallus Dennis
• Streipert Benjamin
• Hoffmann Bjoern
• Roeser Stephan
• Badillo Jimenez Juan Pablo
• Kraft Vadim

Classifications

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M10/0567 Primary

  characterised by the additives · CPC title