RECHARGEABLE ELECTROCHEMICAL BATTERY CELL

• US 20110287304A1
• Filed: 04/21/2011
• Published: 11/24/2011
• Est. Priority Date: 02/12/2010
• Status: Active Grant

• Current Assignee: Innolith Assets AG
• Original Assignee: Fortu Intellectual Property AG
• Inventors: Borck, Markus, Zinck, Laurent, Wollfahrt, Claudia, Pszolla, Christian, Ripp, Christiane
• Granted Patent: US 9,263,745 B2
• Time in Patent Office: Days
• US Class Current: 429/163
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0563 Liquid materials, e.g. for Li-SOCl2 cells
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2300/002 Inorganic electrolyte
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0435 Rolling or calendering
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/0473 Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
• CPC Class Codes: H01M 4/0478 with dispersions, suspensions or pastes
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/1397 of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 4/581 Chalcogenides or intercalation compounds thereof
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/5835 Comprising fluorine or fluoride salts
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/623 : fluorinated polymers
• CPC Class Codes: H01M 4/808 : Foamed, spongy materials
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

Rechargeable lithium battery cell having a housing, a positive electrode, a negative electrode and an electrolyte containing a conductive salt, wherein the electrolyte is based on SO2 and the positive electrode contains an active material in the composition LixM′yM″z(XO4)aFb, wherein

• M′ is at least one metal selected from the group consisting of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn,
• M″ is at least one metal selected from the group consisting of the metals of the groups II A, III A, IV A, V A, VI A, IB, IIB, IIIB, IVB, VB, VIB and VIIIB,
• X is selected from the group consisting of the elements P, Si and S,
• x is greater than 0,
• y is greater than 0,
• z is greater than or equal to 0,
• a is greater than 0 and
• b is greater than or equal to 0.

Claims

1. Rechargeable lithium battery cell having a housing, a positive electrode, a negative electrode and an electrolyte containing a conductive salt,

wherein

the electrolyte is based on SO₂ and

the positive electrode contains an active material having the composition Li_xM′

_yM″

_z(XO₄)_aF_b, wherein

M′

is at least one metal selected from the group consisting of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn,

M″

is at least one metal selected from the group consisting of the metals of the groups II A, III A, IV A, V A, VI A, IB, IIB, IIIB, IVB, VB, VIB and VIIIB,

X is selected from the group consisting of the elements P, Si and S,

x is greater than 0,

y is greater than 0,

z is greater than or equal to 0,

a is greater than 0 and

b is greater than or equal to 0.

2. Battery cell according to claim 1, characterized in that B is the element P, being wherein preferably M′

is the metal Fe and particularly preferably b is equal to 0.

3. Battery cell according to claim 1, characterized in that the positive electrode has a thickness of at least 0.25 mm, preferably at least 0.3 mm, further preferably at least 0.4 mm, further preferably at least 0.5 mm and particularly preferably at least 0.6 mm.

4. Battery cell according to claim 1, characterized in that the positive electrode contains a quantity of active material per unit area of at least 30 mg/cm², preferably at least 40 mg/cm², further preferably at least 60 mg/cm², further preferably at least 80 mg/cm², further preferably at least 100 mg/cm², further preferably at least 120 mg/cm² and particularly preferably at least 140 mg/cm².

5. Battery cell according to claim 1, characterized in that the positive electrode is porous, the porosity of the positive electrode being preferably no more than 50%, further preferably no more than 45%, further preferably no more than 40%, further preferably no more than 35%, further preferably no more than 30%, further preferably no more than 25% and particularly preferably no more than 20%.

6. Battery cell according to claim 1, characterized in that the positive electrode has a current collector element with a three-dimensional porous metal structure, preferably in the form of a metal foam.

7. Battery cell according to claim 6, characterized in that the porous metal structure extends essentially over the entire thickness of the positive electrode.

8. Battery cell according to claim 6, characterized in that the active metal is distributed essentially homogeneously in the positive metal structure.

9. Battery cell according to claim 1, characterized in that the negative electrode has a thickness of at least 0.2 mm, preferably at least 0.3 mm, further preferably at least 0.4 mm, further preferably at least 0.5 mm and particularly preferably at least 0.6 mm.

10. Battery cell according to claim 1, characterized in that the positive electrode contains a binding agent, preferably a fluorinated binding agent, most preferably a polyvinylidene fluoride and/or a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, wherein the concentration of the binding agent is preferably no more than 10%, further preferably no more than 7%, further preferably no more than 5% and particularly preferably no more than 2%.

11. Battery cell according to claim 1, characterized in that the negative electrode contains carbon for inserting lithium ions.

12. Battery cell according to claim 1, characterized in that the quantity of the active material of the negative electrode per unit area is at least 10 mg/cm², preferably at least 20 mg/cm², further preferably at least 40 mg/cm², further preferably at least 60 mg/cm², further preferably at least 80 mg/cm² and particularly preferably at least 140 mg/cm².

13. Battery cell according to claim 1, characterized in that the negative electrode is porous and its porosity is preferably no more than 50%, further preferably no more than 45%, further preferably no more than 40%, further preferably no more than 35% and particularly preferably no more than 30%.

14. Battery cell according to claim 1, characterized in that the negative electrode contains a binding agent, preferably a fluorinated binding agent, most preferably a polyvinylidene fluoride and/or a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, wherein the concentration of the binding agent is preferably no more than 5 wt. %, further preferably no more than 3 wt. % and particularly preferably no more than 1 wt. %.

15. Battery cell according to claim 1, characterized in that the electrolyte contains at least 2 mol SO₂, preferably at least 2.5 mol SO₂, further preferably at least 3 mol SO₂ and particularly preferably at least 4 mol SO₂ per mole of conductive salt.

16. Battery cell according to claim 1, characterized in that the electrolyte contains as conductive salt a halogenide, oxalate, borate, phosphate, arsenate or gallate, preferably a lithium tetrahalogenoaluminate, particularly preferably a lithium tetrachloroaluminate.

17. Battery cell according to claim 1, characterized in that the cell has a current carrying capacity per unit area of the positive electrode, of at least 10 mA/cm², preferably at least 50 mA/cm² and particularly preferably at least 150 mA/cm².

18. Battery cell according to claim 1, characterized in that it contains a lithium halogenide, preferably lithium chloride, preferably mixed with the active metal of the positive electrode.

19. Rechargeable lithium battery cell having a housing, a positive electrode, a negative electrode and an electrolyte containing a conductive salt,

in particular according to any one of the preceding claims,

wherein

the electrolyte is based on SO₂ and

at least one of the electrodes is an insertion electrode suitable for inserting lithium ions and pretreated to reduce covering layers.

20. Battery cell according to claim 19, characterized in that at least one electrode is pretreated to reduce covering layers by means of a surface coating of the active material, said surface coating preferably being applied by

atomic layer deposition (ALD), the surface coating preferably containing Al₂O₃ or SiO₂, or

dip coating, the surface coating preferably containing SiO₂.

21. Method for producing an electrode for a battery cell according to claim 1, characterized by the following steps:

producing a paste mass from the active material with optional admixture of a binding agent and/or a conductivity-improving material;

homogeneously incorporating the paste mass into a three-dimensional porous metal structure;

pressing the three-dimensional metal structure containing the paste mass in such a manner that its thickness is reduced, preferably by at least 20%.

22. Electrode produced according to the method of claim 21.