ELECTROLYTE FOR LITHIUM AIR BATTERY AND LITHIUM AIR BATTERY INCLUDING THE SAME

• US 20170149091A1
• Filed: 11/11/2016
• Published: 05/25/2017
• Est. Priority Date: 11/20/2015
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: KIM, Hyunjin, ROEV, Victor, IM, Dongmin
• Granted Patent: US 10,128,551 B2
• Time in Patent Office: Days
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2300/0028 characterised by the solvent
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 2300/0045 Room temperature molten salts comprising at least one organic ion
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An electrolyte for a lithium air battery including a deuterated compound, wherein the deuterated compound is a deuterated product of an organic compound, in which at least one hydrogen atom is substituted with a deuterium atom, wherein the organic compound has a carbon-hydrogen (C—H) bond dissociation energy of 337.2 kJ/mol or more.

Claims

1. An electrolyte for a lithium air battery, the electrolyte comprising a deuterated compound,

wherein the deuterated compound is a deuterated product of an organic compound, in which at least one hydrogen atom is substituted with a deuterium atom, wherein the organic compound has a carbon-hydrogen (C—

H) bond dissociation energy of 337.2 kilojoules per mole or more.

2. The electrolyte of claim 1, wherein the deuterated compound is at least one compound selected from deuterated N,N-dimethylacetamide, deuterated N-methylacetamide, a deuterated glyme compound, deuterated polyethylene oxide, and a compound represented by Formula 1:

3. The electrolyte of claim 2, wherein the deuterated glyme compound is at least one compound selected from deuterated dimethoxy ethane, deuterated ethylene glycol dimethyl ether (CH₃OCH₂CH₂OCH₃), deuterated diethylene glycol dimethyl ether (CH₃(OCH₂CH₂)₂OCH₃), deuterated diethylene glycol diethyl ether (C₂H₅(OCH₂CH₂)₂OC₂H₅), deuterated triethylene glycol dimethyl ether (CH₃(OCH₂CH₂)₃OCH₃), and deuterated triethylene glycol diethyl ether C₂H₅(OCH₂CH₂)₃OC₂H₅).

4. The electrolyte of claim 2, wherein the deuterated N,N-dimethylacetamide is at least one compound selected from CD₃CON(CD₃)₂, CH₃CON(CD₃)₂, CHD₂CON(CD₃)₂, CH₂DCON(CD₃)₂, CH₃CON(CD₃)(CH₃), CH₃CON(CD₂H)(CH₃), CH₃CON(CDH₂)(CH₃), CH₃CON(CD₂H)₂, CH₃CON(CDH₂)₂, CHD₂CON(CD₃)(CH₃), CHD₂CON(CD₂H)(CH₃), CHD₂CON(CDH₂)(CH₃), CHD₂CON(CD₂H)₂, CH₃CON(CDH₂)₂, CH₂DCON(CD₃)(CH₃), CH₂DCON(CD₂H)(CH₃), CH₂DCON(CDH₂)(CH₃), CH₂DCON(CD₂H)₂, and CH₂DCON(CDH₂)₂.

5. The electrolyte of claim 2, wherein the compound of Formula 1 comprises a cation selected from groups represented by Formula 2:

6. The electrolyte of claim 2, wherein in Formula 1, Y⁻

is selected from BF₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, AlCl₄⁻

, HSO₄⁻

, ClO₄⁻

, CH₃SO₃⁻

, CF₃CO₂⁻

, (CF₃SO₂)₂N⁻

, Cl⁻

, Br⁻

, I⁻

, BF₄⁻

, SO₄⁻

, PF₆⁻

, ClO₄⁻

, CF₃SO₃⁻

, CF₃CO₂—

, (FSO₂)₂N⁻

, (C₂F₅SO₂)₂N⁻

, (C₂F₅SO₂)(CF₃SO₂)N⁻

, and (CF₃SO₂)₂N⁻

.

7. The electrolyte of claim 1, wherein the deuterated compound has a deuterium substitution degree of about 50% to about 100%.

8. The electrolyte of claim 1, wherein an amount of the deuterated compound is from about 3 parts by weight to about 95 parts by weight based on 100 parts by weight of the electrolyte.

9. The electrolyte of claim 2, wherein the compound of Formula 1 is a deuterated product of a compound comprising:

at least one cation selected from tetramethyl ammonium cation, tetraethyl ammonium cation, trimethylpropyl ammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium cation, 1-butyl-1-methylpyrrolidinium cation, 1-methyl-1-(2-methoxyethyl)pyrrolidinium cation, 1-methyl-1-(3-methoxypropyl)pyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, N-propyl-N-methylpyrrolidinium cation, N-propyl-N-methylpiperidinium cation, and N-ethyl-N-methylpiperidinium cation; and

at least one anion selected from BF₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, AlCl₄⁻

, HSO₄⁻

, ClO₄⁻

, CH₃SO₃⁻

, CF₃CO₂⁻

, Cl⁻

, Br⁻

, I⁻

, CF₃SO₃⁻

, (FSO₂)₂N⁻

, (C₂F₅SO₂)₂N⁻

, (C₂F₅SO₂)(CF₃SO₂)N⁻

, and (CF₃SO₂)₂N⁻

.

10. The electrolyte of claim 1, further comprising a non-aqueous organic solvent.

11. The electrolyte of claim 10, wherein the non-aqueous organic solvent further comprises at least one compound selected from N,N-dimethylacetamide, N-methylacetamide dimethyl sulfoxide, methyl butyl ether, diethyl ether, ethyl butyl ether, dibutyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, cyclohexanone, dioxane, dimethoxy ethane, 2-methyltetrahydrofuran, 2,2-dimethyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, methyl formate, ethyl formate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, polyethylene carbonate, γ

-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, diglyme, triglyme, tetraglyme, acetonitrile, benzonitrile, nitromethane, nitrobenzene, triethyl amine, triphenyl amine, tetraethylene glycol diamine, dimethylformamide, diethylformamide, N-methylpyrrolidone, dimethyl sulfone, tetramethylene sulfone, triethylphosphine oxide, 1,3-dioxolane, and sulfolane.

12. The electrolyte of claim 1,

wherein the deuterated compound comprises a mixture of deuterated N,N-dimethylacetamide and N,N-dimethylacetamide,

wherein an amount of the deuterated N,N-dimethylacetamide in the mixture is from about 0.1 parts by weight to about 99.99 parts by weight based on a total weight (100 parts by weight) of the deuterated N,N-dimethylacetamide and N,N-dimethylacetamide.

13. The electrolyte of claim 12, wherein the amount of the deuterated N,N-dimethylacetamide in the mixture is from about 20 parts by volume to about 80 parts by volume based on the total volume (100 parts by volume) of the deuterated N,N-dimethylacetamide and N,N-dimethylacetamide.

14. The electrolyte of claim 1, further comprising a lithium salt.

15. The electrolyte of claim 14, wherein the lithium salt is at least one compound selected from LiNO₃, LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiN(SO₂C₂F₅)₂, Li(CF₃SO₂)₂N, LiC₄F₉SO₃, LiClO₄, LiAlO₂, LiAlC₄, LiN(C_xF_2x+1SO₂)(C_yF_2y+1SO₂) wherein x and y are natural numbers, LiF, LiBr, LiCl, LiOH, LiI, LiB(C₂O₄)₂, Li(FSO₂)₂N, Li(CF₃SO₂)₂N, Li(C₂F₅SO₂)₂N, LiN(C_pF_2p+1 SO₂)(C_qF_2q+1SO₂) wherein p and q are different numbers and are each independently an integer of 1 to 20, LiN((SO₂)₂C_pF_2p) wherein p is an integer of 1 to 10, Li(C₆F₅SO₂)₂N, Li(C₁₀F₇SO₂)₂N, Li(C₆F₅SO₂)(C₁₀F₇SO₂)N, LiN(C₆F₅SO₂)(C_pF_2p+1SO₂), wherein p is an integer of 1 to 10, and LiN(C₁₀F₇SO₂)(C_pF_2p+1SO₂), wherein p is an integer of 1 to 10.

16. A lithium air battery comprising an anode, a cathode, and at least one selected from the electrolyte according to claim 1 and a reaction product thereof.

17. The lithium air battery of claim 16, wherein the electrolyte is partially or completely impregnated in the cathode.

18. The lithium air battery of claim 16, further comprising a lithium ion conductive layer comprising a plurality of ion conductive inorganic particles disposed between the anode and the electrolyte.

19. The lithium air battery of claim 18, wherein the ion conductive inorganic particles are at least one selected from a glassy active metal ion conductor, an amorphous active metal ion conductor, a ceramic active metal ion conductor, and a glass-ceramic active metal ion conductor.

20. The lithium air battery of claim 18, wherein the ion conductive inorganic particles are at least one selected from Li_1+x+y Al_xTi₂₋

xSi_yP<sub>3−

y</sub>O₁₂ wherein 0<

x<

2 and 0≦

y<

3, BaTiO₃, Pb(Zr,Ti)O₃, Pb<sub>1−

x</sub>La_xZr<sub>1−

y</sub>Ti_yO₃ wherein 0≦

x<

1 and 0≦

y<

1, PB(Mg₃Nb_2/3)O₃—

PbTiO₃, HfO₂, SrTiO₃, SnO₂, CeO₂, Na₂O, MgO, NiO, CaO, BaO, ZnO, ZrO₂, Y₂O₃, Al₂O₃, TiO₂, SiO₂, SiC, lithium phosphate, lithium titanium phosphate (Li_xTi_y(PO₄)₃ wherein 0<

x<

2 and 0<

y<

3), lithium aluminum titanium phosphate (Li_xAl_yTi_z(PO₄)₃ wherein 0<

x<

2, 0<

y<

1, and 0<

z<

3), Li_1+x+y(Al, Ga)_x(Ti, Ge)<sub>2−

x</sub>SiP<sub>3−

y</sub>O₁₂ wherein 0≦

x≦

1 and 0≦

y≦

1, lithium lanthanum titanate (Li_xLa_yTiO₃ wherein 0<

x<

2 and 0<

y<

3), lithium germanium thiophosphate (Li_xGe_yP_zS_w wherein 0<

x<

4, 0<

y<

1, 0<

z<

1, and 0<

w<

5), lithium nitride (Li_xN_y wherein 0<

x<

4 and 0<

y<

2), SiS₂(Li_xSi_yS_z) glass wherein 0<

x<

3, 0<

y<

2, and 0<

z<

4, P₂S₅(Li_xP_yS_z) glass wherein 0<

x<

3, 0<

y<

3, and 0<

z<

7, Li₂O, LiF, LiOH, Li₂CO₃, LiAlO₂, Li₂O—

Al₂O₃—

SiO₂—

P₂O₅—

TiO₂—

GeO₂-based ceramics, and Garnet-based ceramics (Li_3+xLa₃M₂O₁₂ wherein 0≦

x≦

5 and M=Te, Nb, or Zr).

21. The lithium air battery of claim 18, further comprising a second electrolyte disposed between the anode and the lithium ion conductive layer.

22. The lithium air battery of claim 21, wherein the second electrolyte is a solid polymer electrolyte or an inorganic solid electrolyte.

23. The lithium air battery of claim 16, wherein a ratio (E_D/E_H) of an initial charge/discharge efficiency (E_D) of the lithium air battery comprising the corresponding deuterated compound to an initial charge/discharge efficiency (E_H) of the lithium air battery comprising a compound having not been deuterated is about 1.05 or more.