ELECTROLYTE SOLUTION FOR SECONDARY LITHIUM BATTERY AND SECONDARY LITHIUM BATTERY USING THE SAME

• US 20150104716A1
• Filed: 09/29/2014
• Published: 04/16/2015
• Est. Priority Date: 10/10/2013
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Kang, Yoonsok, Park, Insun, Mun, Junyoung, Park, Minsik, Park, Jinhwan, Choi, Byungjin
• Granted Patent: US 9,799,924 B2
• Time in Patent Office: Days
• US Class Current: 429/332
• 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 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An electrolyte for a lithium secondary battery including a lithium salt, a non-aqueous organic solvent, and a pyrrolidine derivative represented by Formula 1,

wherein, in Formula 1, X is hydrogen, a formyl group or a salt thereof, a carboxyl group or a salt thereof, a C₁-C₂₀ alkyl group, a C₁-C₂₀ hydroxyalkyl group, a C₁-C₂₀ aminoalkyl group, a C₁-C₂₀ thioalkyl group, or a C₁-C₂₀ cyanoalkyl group, and R₁ to R₄ are each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a thio group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a formyl group or a salt thereof, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C₁-C₂₀ hydroxyalkyl group, a C₂-C₂₀ heteroaryl group, or a C₆-C₂₀ aryl group.

Claims

1. An electrolyte for a lithium secondary battery, the electrolyte comprising:

a lithium salt;

a non-aqueous organic solvent; and

a pyrrolidine derivative represented by Formula 1,

2. The electrolyte of claim 1, wherein X is hydrogen, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, an aminomethyl group, an aminoethyl group, an aminopropyl group, a formyl group, or a carboxyl group.

3. The electrolyte of claim 1, wherein R₁ to R₄ are each independently, hydrogen, deuterium, a halogen atom, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a formyl group, a carboxyl group, a phenyl group, a napthyl group, a pyridyl group, a pyrimidyl group, or a quinolyl group.

4. The electrolyte of claim 1, wherein the pyrrolidine derivative comprises at least one of Compounds 1 to 6:

5. The electrolyte of claim 1, wherein the pyrrolidine derivative is contained in an amount of about 0.005 weight percent to about 5 weight percent, based on a total weight of the electrolyte.

6. The electrolyte of claim 1, wherein the lithium salt comprises LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiCF₃SO₃, Li(CF₃SO₂)₃C, Li(CF₃SO₂)₂N, LiC₄F₉SO₃, LiClO₄, LiAlO₄, LiAlCl₄, LiBPh₄, LiN(C_xF_2x+1SO₂)(C_xF_2y+1SO₂) wherein x and y are natural numbers, LiCl, Lil, lithium bisoxalate borate, or a combination thereof.

7. The electrolyte of claim 1, wherein the non-aqueous organic solvent is a carbonate, an ester, an ether, a ketone, and an alcohol, or a combination thereof.

8. A lithium secondary battery comprising:

a positive electrode comprising a positive electrode active material capable of incorporating and deincorporating lithium;

a negative electrode comprising a negative electrode active material capable of incorporating and deincorporating lithium; and

an electrolyte disposed between the positive electrode and the negative electrode, wherein

the electrolyte comprises a lithium salt, a non-aqueous organic solvent, and a pyrrolidine derivative represented by Formula 1;

9. The lithium secondary battery of claim 8, wherein X is hydrogen, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, an aminomethyl group, an aminoethyl group, an aminopropyl group, a formyl group, or a carboxyl group.

10. The lithium secondary battery of claim 8, wherein R₁ to R₄ are each independently hydrogen, deuterium, a halogen atom, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a formyl group, a carboxyl group, a phenyl group, a napthyl group, a pyridyl group, a pyrimidyl group, or a quinolyl group.

11. The lithium secondary battery of claim 8, wherein the pyrrolidine derivative comprises at least one of Compounds 1 to 6:

12. The lithium secondary battery of claim 8, wherein the positive electrode comprises a film formed on a surface of the positive electrode, wherein the film is derived from the pyrrolidine derivative.

13. The lithium secondary battery of claim 12, wherein the film has a thickness of about 0.05 nm to about 100 nm.

14. The lithium secondary battery of claim 8, wherein the positive electrode active material comprises LiCoO₂;

LiNi_1-xCo_xO₂ wherein 0≦

x<

1;

Li_1-xM_xO₂ wherein M is Mn or Fe and 0.03≦

x<

0.1;

Li[Ni_xCo_1-2xMn_x]O₂ wherein 0<

x<

0.5;

Li[Ni_xMn_x]O₂ wherein 0<

x≦

0.5;

Li_1+x(Ni_aCo_bMn_c)_1-yO_z wherein 0<

x≦

1, 0≦

y<

1, and 2≦

z≦

4 and 0<

a<

1, 0<

b<

1, and 0<

c<

1, LiM₂O₄ wherein M is Ti, V, or Mn, LiM_xMn_2-xO₄ wherein M is a transition metal;

LiFePO₄;

LiMPO₄ wherein M is Mn, Co, or Ni;

V₂O₅, V₂O₃, VO₂(B), V₆O₁₃, V₄O₉, V₃O₇, Ag₂V₄O₁₁, AgVO₃, LiV₃O₅,δ

-Mn_yV₂O₅,δ

-NH₄V₄O₁₀, Mn_{0. 8}V₇O₁₆, LiV₃O₈, Cu_xV₂O₅, Cr_XV₆O₁₃, M₂(X′

O₄)₃ wherein M is a transition metal and X′

is S, P, As, Mo, or W;

or Li₃M₂(PO₄)₃ wherein M is Fe, V, or Ti.

15. The lithium secondary battery of claim 8, wherein the positive electrode active material has a voltage in a range of about 3.0 V to about 5.5 V versus lithium.

16. The lithium secondary battery of claim 15, wherein the positive electrode active material is Li_1-x(Ni_aCo_bMn_c)_1-xO₂ wherein 0.05≦

x≦

0.2 or LiNi_0.5Mn_1.5O₄.

17. The lithium secondary battery of claim 8, wherein the negative electrode active material comprises a vanadium oxide, a lithium vanadium oxide;

Si;

SiO_x wherein 0<

x<

2;

a Si-Q alloy wherein Q is magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), Ra, scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), rutherfordium (Rf), vanadium (V), niobium (Nb), tantalum (Ta), dubnium (Db), chromium (Cr), molybdenum (Mo), tungsten (W), seaborgium (Sg), technetium (Tc), rhenium (Re), bohrium (Bh), iron (Fe), lead (Pb), ruthenium (Ru), osmium (Os), hassium (Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), Sn, In, titanium (Ti), Ge, phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), sulfur (S), selenium (Se), tellurium (Te), polonium (Po) or a combination thereof;

graphite;

a soft carbon;

a hard carbon;

a mesophase pitch carbide;

or calcined coke.

18. The lithium secondary battery of claim 8, wherein an amount of the pyrrolidine derivative is about 0.005 weight percent to about 5 weight percent, based on a total weight of the electrolyte.

19. The lithium secondary battery of claim 8, wherein the lithium salt is LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiCF₃SO₃, Li(CF₃SO₂)₃C, Li(CF₃SO₂)₂N, LiC₄F₉SO₃LiClO₄, LiAlO₄, LiAlCl₄, LiBPh₄, LiN(C_xF_2x+1SO₂)(C_xF_2y+1SO₂) wherein x and y are natural numbers, LiCl, Lil, lithium bisoxalate borate, or a combination thereof.

20. The lithium secondary battery of claim 8, further comprising a separator that electrically insulates the positive electrode and the negative electrode.