Lithium secondary battery comprising electrode active material containing surfactant

• US 8,383,265 B2
• Filed: 02/01/2007
• Issued: 02/26/2013
• Est. Priority Date: 02/06/2006
• Status: Active Grant

• Current Assignee: LG Energy Solution Limited (LG Corporation)
• Original Assignee: LG Chem Limited (LG Corporation)
• Inventors: Kang, Eun Ju, Lee, Hyang Mok, Hong, Kichul, Woo, Jung Kyu
• Primary Examiner(s): HENDRICKSON, STUART L
• Application Number:
  US12/223,688
• Publication Number:
  US 20100009257A1
• Time in Patent Office: 2,217 Days
• Field of Search: 429/215
• US Class Current: 429/215
• 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 10/0562 Solid materials
• CPC Class Codes: H01M 10/0566 Liquid materials
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/1393 of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 4/624 Electric conductive fillers
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Provided is a lithium secondary battery comprising a lithium transition metal compound-containing cathode and a graphitized carbon-containing anode with addition of a surfactant to the cathode and/or the anode, whereby the addition of the surfactant improves the wettability of an electrolyte on the electrode, thereby increasing the battery capacity and improving rate properties and cycle properties of the battery, in conjunction with a significant reduction of a manufacturing process time of the battery.

Claims

1. A lithium secondary battery comprising:

(A) a cathode comprising layered lithium-containing cobalt or nickel oxide compounds, or such layered compounds substituted with one or more transition metals;

lithium manganese oxides selected from the group consisting of Li_l+xMn<sub>2−

x</sub>O₄ (0≦

x≦

0.33), LiMnO₃, LiMn₂O₃ and LiMnO₂;

lithium copper oxide (Li₂CuO₂);

vanadium oxides selected from the group consisting of LiV₃O₈, V₂O₅ and Cu₂V₂O₇;

Formula LiNi<sub>1−

x</sub>M_xO₂ (M═

Co, Mn, Al, Cu, Fe, Mg, B or Ga, and 0.01≦

x≦

0.3);

lithium manganese composite oxides of Formula LiMn<sub>2−

x</sub>M_xO₂ (M═

Co, Ni, Fe, Cr, Zn or Ta, and 0.01≦

x≦

0.1), or Formula Li₂Mn₃MO₈ (M═

Fe, Co, Ni, Cu or Zn);

LiMn₂O₄ wherein a portion of Li is substituted with alkaline earth metal ions or disulfide compounds;

Fe₂(MoO₄)₃, or LiFe₃O₄;

(B) a hydrophobic anode comprising non-graphitizing carbon;

graphite-based carbon;

metal composite oxides selected from the group consisting of Li_xFe₂0 ₃ (0≦

x≦

1), Li_xWO₂ (0≦

x≦

1) and Sn_xMe<sub>l−

x</sub>Me′

_yO_z (Me;

Mn, Fe, Pb or Ge;

Me′

;

Al, B, P, Si, Group I, Group II and Group III elements of the Periodic Table of the Elements, or halogens;

0<

x≦

1;

1≦

y≦

3; and

1≦

z≦

8);

lithium metals;

lithium alloys;

silicon-based alloys;

tin-based alloys;

metal oxides wherein the metal is selected from the group consisting of Sn, Pb, Sb, Ge and Bi;

conductive polymers;

or Li—

Co—

Ni containing materials; and

(C) a hydrophilic electrolyte;

wherein;

(i) a surfactant is incorporated into the anode for improvement of the wettability of the anode by the electrolyte;

(ii) the surfactant has a hydrophilic portion and a hydrophobic portion and is incorporated into the anode such that the hydrophilic portion of the surfactant exhibits an affinity for the hydrophilic electrolyte and the hydrophobic portion of the surfactant exhibits an affinity for the hydrophobic anode;

(iii) content of the surfactant is in the range of 0.01 to 20% by weight, based on the total weight of an anode mix used to fabricate the anode;

(iv) the surfactant is a nonionic surfactant, which is a block copolymer having a hydrophilic portion and a hydrophobic portion;

(v) the block copolymer is a PEO-PPO block copolymer wherein the PEO-PPO block copolymer is a PEO-PPO-PEO triblock copolymer; and

;

(vi) the content of PEO unit in the PEO-PPO-PEO triblock copolymer is in the range of 60 to 70% by weight, based on the total weight of the copolymer.

2. A lithium secondary battery comprising:

(A) a cathode comprising layered lithium-containing cobalt or nickel oxide compounds, or such layered compounds substituted with one or more transition metals;

lithium manganese oxides selected from the group consisting of Li_l+xMn<sub>2−

x</sub>O₄ (0≦

x≦

0.33), LiMnO₃, LiMn₂O₃ and LiMnO₂;

lithium copper oxide (Li₂CuO₂);

vanadium oxides selected from the group consisting of LiV₃O₈, V₂O₅ and Cu₂V₂O₇;

Formula LiNi<sub>1−

x</sub>M_xO₂ (M═

Co, Mn, Al, Cu, Fe, Mg, B or Ga, and 0.01≦

x≦

0.3);

lithium manganese composite oxides of Formula LiMn<sub>2−

x</sub>M_xO₂ (M═

Co, Ni, Fe, Cr, Zn or Ta, and 0.01≦

x≦

0.1), or Formula Li₂Mn₃MO₈ (M═

Fe, Co, Ni, Cu or Zn);

LiMn₂O₄ wherein a portion of Li is substituted with alkaline earth metal ions or disulfide compounds;

Fe₂(MoO₄)₃, or LiFe₃O₄;

(B) a hydrophobic anode comprising non-graphitizing carbon;

graphite-based carbon;

metal composite oxides selected from the group consisting of Li_xFe₂0₃ (0 ≦

x≦

l), Li_xWO₂ (0≦

x≦

l) and Sn_xMe<sub>1−

x</sub>Me′

_yO_z (Me;

Mn, Fe, Pb or Ge;

Me′

;

Al, B, P, Si, Group I, Group II and Group III elements of the Periodic Table of the Elements, or halogens;

0<

x≦

l;

1≦

y≦

3; and

1≦

z≦

8);

lithium metals;

lithium alloys;

silicon-based alloys;

tin-based alloys;

metal oxides wherein the metal is selected from the group consisting of Sn, Pb, Sb, Ge and Bi;

conductive polymers;

or Li—

Co—

Ni containing materials; and

a hydrophilic electrolyte;

wherein;

(i) a surfactant is incorporated into the anode for improvement of the wettability of the anode by the electrolyte;

(ii) the surfactant has a hydrophilic portion and a hydrophobic portion and is incorporated into the anode such that the hydrophilic portion of the surfactant exhibits an affinity for the hydrophilic electrolyte and the hydrophobic portion of the surfactant exhibits an affinity for the hydrophobic anode;

(iii) content of the surfactant is in the range of 0.01 to 20% by weight, based on the total weight of an anode mix used to fabricate the anode; and

(iv) the surfactant is perfluoroalkyl sulfonate.

3. The battery according to claim 2, wherein the surfactant is perfluorobutane sulfonate.