Electrolyte solution for secondary lithium battery and secondary lithium battery using the same

Patent metadata

Field	Value
Publication number	US-9799924-B2
Application number	US-201414499716-A
Country	US
Kind code	B2
Filing date	Sep 29, 2014
Priority date	Oct 10, 2013
Publication date	Oct 24, 2017
Grant date	Oct 24, 2017

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 C 1 -C 20 alkyl group, a C 1 -C 20 hydroxyalkyl group, a C 1 -C 20 aminoalkyl group, a C 1 -C 20 thioalkyl group, or a C 1 -C 20 cyanoalkyl group, and R 1 to R 4 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 C 1 -C 20 hydroxyalkyl group, a C 2 -C 20 heteroaryl group, or a C 6 -C 20 aryl group.

First claim

What is claimed is:

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,

wherein, in Formula 1,
X is hydrogen, a formyl group or a salt thereof, a carboxyl group or a salt thereof, a C 1 -C 20 alkyl group, a C 1 -C 20 hydroxyalkyl group, a C 1 -C 20 aminoalkyl group, a C 1 -C 20 thioalkyl group, or a C 1 -C 20 cyanoalkyl group, and
R 1 to R 4 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 C 1 -C 20 hydroxyalkyl group, a C 2 -C 20 heteroaryl group, or a C 6 -C 20 aryl group,
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.

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 R 1 to R 4 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 lithium salt comprises LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 3 C, Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 4 , LiAlCl 4 , LiBPh 4 , LiN(C x F 2x+1 SO 2 )(C x F 2y+1 SO 2 ) wherein x and y are natural numbers, LiCl, Lil, lithium bisoxalate borate, or a combination thereof.

6. 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.

7. 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:

wherein, in Formula 1,
X is hydrogen, a formyl group or a salt thereof, a carboxyl group or a salt thereof, a C 1 -C 20 alkyl group, a C 1 -C 20 hydroxyalkyl group, a C 1 -C 20 aminoalkyl group, a C 1 -C 20 thioalkyl group, or a C 1 -C 20 cyanoalkyl group, and
R 1 to R 4 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 C 1 -C 20 hydroxyalkyl group, a C 2 -C 20 heteroaryl group, or a C 6 -C 20 aryl group,
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.

8. The lithium secondary battery of claim 7 , 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.

9. The lithium secondary battery of claim 7 , wherein R 1 to R 4 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.

10. The lithium secondary battery of claim 7 , wherein the pyrrolidine derivative comprises at least one of Compounds 1 to 6:

11. The lithium secondary battery of claim 7 , wherein the positive electrode comprises a film formed on a surface of the positive electrode, wherein the film is derived from the pyrrolidine derivative.

12. The lithium secondary battery of claim 11 , wherein the film has a thickness of about 0.05 nm to about 100 nm.

13. The lithium secondary battery of claim 7 , wherein the positive electrode active material comprises LiCoO 2 ; LiNi 1-x Co x O 2 wherein 0≦x<1; Li 1-x M x O 2 wherein M is Mn or Fe and 0.03≦x<0.1; Li[Ni x Co 1-2x Mn x ]O 2 wherein 0<x<0.5; Li[Ni x Mn x ]O 2 wherein 0<x≦0.5; Li 1+x (Ni a Co b Mn c ) 1-y O z wherein 0<x≦1, 0≦y<1, and 2≦z≦4 and 0<a<1, 0<b<1, and 0<c<1, LiM 2 O 4 wherein M is Ti, V, or Mn, LiM x Mn 2-x O 4 wherein M is a transition metal; LiFePO 4 ; LiMPO 4 wherein M is Mn, Co, or Ni; V 2 O 5 , V 2 O 3 , VO 2 (B), V 6 O 13 , V 4 O 9 , V 3 O 7 , Ag 2 V 4 O 11 , AgVO 3 , LiV 3 O 5 ,δ—Mn y V 2 O 5 ,δ—NH 4 V 4 O 10 , Mn 0.8 V 7 O 16 , LiV 3 O 8 , Cu x V 2 O 5 , Cr X V 6 O 13 , M 2 (X′O 4 ) 3 wherein M is a transition metal and X′ is S, P, As, Mo, or W; or Li 3 M 2 (PO 4 ) 3 wherein M is Fe, V, or Ti.

14. The lithium secondary battery of claim 7 , wherein the positive electrode active material has a voltage in a range of about 3.0 V to about 5.5 V versus lithium.

15. The lithium secondary battery of claim 14 , wherein the positive electrode active material is Li 1-x (Ni a Co b Mn c ) 1-x O 2 wherein 0.05≦x≦0.2 , 0≦a≦1, 0≦b≦1 ,and 0≦c≦1 , or LiNi 0.5 Mn 1.5 O 4 .

16. The lithium secondary battery of claim 7 , 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.

17. The lithium secondary battery of claim 7 , wherein the lithium salt is LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , Li(CF 3 SO 2 )

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kang Yoonsok
• Park Insun
• Mun Junyoung
• Park Minsik
• Park Jinhwan
• Choi Byungjin

Classifications

• H01M10/0567 Primary

  characterised by the additives · CPC title

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• 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