Rechargeable non-aqueous lithium-air battery cell comprising a solid organic catalyst
A lithium-air battery cell wherein the positive electrode includes a solid p-type electroactive organic catalyst lithium salt and a battery pack including several lithium-air battery cells. The use of a battery pack as a rechargeable battery for vehicles, such as electric vehicles and hybrid vehicles, electronic devices, and stationary power generating devices. Finally, a vehicle, an electronic device, and a stationary power generating device, including a battery pack.
1. A lithium-air battery cell comprising:
a negative electrode containing a negative-electrode active material;
a positive electrode using oxygen as a positive-electrode active material; and
a non-aqueous electrolyte medium arranged between the negative electrode and the positive electrode;
wherein the positive electrode comprises a solid p-type electroactive organic catalyst lithium salt showing the following general structure (1):
wherein:
Ar is an aromatic or heteroaromatic ring selected from the group consisting of: benzene, naphthalene, perylene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzo[a]pyrene, corannulene, benzo[ghi]perylene, coronene, ovalene, benzo[c]fluorine, pyridine, quinolone, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, quinazoline, pyridazine, cinnoline, phthalazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine,
R 1 to R 4 are each independently selected from the group consisting of: H, aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy, amino-alkyl, amino-aryl, thio-alkyl, thio-aryl, alkyl phosphonate, aryl phosphonate, cyclodienyl, —OCR, —(O═)CHNR, —HN(O═)CR, —(O═)COR, —HN(O═)CHNR, —HN(O═)COR, —(HN═)CHNR, —HN(HN═)CHNR, —(S═)CHNR, —HN(S═)CHNR, with R being H or a C 1 -C 19 -alkyl group, the R 1 to R 4 groups comprising from 1 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom, the latter comprising from 4 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom,
R 5 and R 6 are each independently selected from the group consisting of: H, aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy, amino-alkyl, amino-aryl, thio-alkyl, thio-aryl, alkyl phosphonate, aryl phosphonate, cyclodienyl, —OCR, —(O═)CHNR, —HN(O═)CR, —(O═)COR, —HN(O═)CHNR, —HN(O═)COR, —(HN═)CHNR, —HN(HN═)CHNR, —(S═)CHNR, —HN(S═)CHNR, with R being H or a C 1 -C 19 -alkyl group, the R 5 and R 6 groups comprising from 1 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom,
Y and Y′ are anionic groups, each independently selected from the group consisting of carboxylate, thiocarboxylate, sulfonate, thiosulfonate, phosphonate, thiophosphonate, sulfate, amidate groups.
2. The lithium-air battery cell according to claim 1 , wherein the solid p-type electroactive organic catalyst lithium salt shows less than 0.148 g·L −1 solubility in lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) 1M in tetraethylene glycol dimethyl ether (TEGDME).
3. A lithium-air battery cell comprising:
a negative electrode containing a negative-electrode active material;
a positive electrode using oxygen as a positive-electrode active material; and
a non-aqueous electrolyte medium arranged between the negative electrode and the positive electrode;
wherein the positive electrode comprises a solid p-type electroactive organic catalyst lithium salt,
wherein the solid p-type electroactive organic catalyst lithium salt shows the following general structure (2):
wherein:
R 1 and R 3 are each independently selected from the group consisting of: H, aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy, amino-alkyl, amino-aryl, thio-alkyl, thio-aryl, alkyl phosphonate, aryl phosphonate, cyclodienyl, —OCR, —(O═)CHNR, —HN(O═)CR, —(O═)COR, —HN(O═)CHNR, —HN(O═)COR, —(HN═)CHNR, —HN(HN═)CHNR, —(S═)CHNR, —HN(S═)CHNR, with R being H or a C 1 -C 19 -alkyl group, the R 1 and R 3 groups comprising from 1 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom, the latter comprising from 4 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom,
R 5 and R 6 are each independently selected from the group consisting of: H, aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy, amino-alkyl, amino-aryl, thio-alkyl, thio-aryl, alkyl phosphonate, aryl phosphonate, cyclodienyl, —OCR, —(O═)CHNR, —HN(O═)CR, —(O═)COR, —HN(O═)CHNR, —HN(O═)COR, —(HN═)CHNR, —HN(HN═)CHNR, —(S═)CHNR, —HN(S═)CHNR, with R being H or a C 1 -C 19 -alkyl group, the R 5 and R 6 groups comprising from 1 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom.
4. The lithium-air battery cell according to claim 3 , wherein R 1 and R 3 are phenyl (—C 6 H 5 ).
5. The lithium-air battery cell according to claim 1 , wherein the positive electrode further comprises a solid n-type electroactive organic catalyst lithium salt.
6. The lithium-air battery cell according to claim 5 , wherein the solid n-type electroactive organic catalyst lithium salt shows the following general structure (3):
wherein R 7 and R 8 are each independently selected from the group consisting of: H, aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy, amino-alkyl, amino-aryl, thio-alkyl, thio-aryl, alkyl phosphonate, aryl phosphonate, cyclodienyl, —OCR, —(O═)CHNR, —HN(O═)CR, —(O═)COR, —HN(O═)CHNR, —HN(O═)COR, —(HN═)CHNR, —HN(HN═)CHNR, —(S═)CHNR, —HN(S═)CHNR, with R being H or a C 1 -C 19 -alkyl group, the R 7 and R 8 groups comprising from 1 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom, the latter comprising from 4 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom.
7. The lithium-air battery cell according to claim 6 , wherein R 7 and R 8 are H.
8. The lithium-air battery cell according to claim 5 , wherein the weight ratio between solid p-type electroactive organic catalyst lithium salt and solid n-type electroactive organic catalyst lithium salt ranges from 0.1/99.9 to 100/0.
9. The lithium-air battery cell according to claim 1 , wherein the positive electrode further comprises carbon.
10. The lithium-air battery cell according to claim 9 , wherein the weight ratio between carbon and (solid p-type electroactive organic catalyst lithium salt+solid n-type electroactive organic catalyst lithium salt+carbon) is greater than or equal to 77%.
11. The lithium-air battery cell according to claim 1 , wherein the positive electrode further comprises a polymer binder selected from the group consisting of: polyethylene, polypropylene, polytetrafluoroethylene (PTFE), styrene-butadiene rubber, tetrafluoroethylene-hexafluoropropylene copolymers, tetrafluoroethylene-hexafluoropropylene copolymers (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers (PFA), vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-tetrafluoroethylene copolymers (ETFE resins), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymers, propylene-tetrafluoroethylene copolymers, ethylene-chlorotrifluoroethylene copolymers (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymers, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymers, ethylene-acrylic acid copolymers, and copolymers having sulfonate group-terminated perfluorovinyl ether groups attached to a poly(tetrafluoroethylene) backbone.
12. The lithium-air battery cell according to claim 11 , wherein the weight ratio between the polymer binder and (solid p-type electroactive organic catalyst lithium salt+solid n-type electroactive organic catalyst lithium salt+carbon+polymer binder) is lower than or equal to 20%.
13. The lithium-air battery cell according to claim 1 , wherein the non-aqueous electrolyte medium comprises one or more aprotic organic solvents selected from the group consisting of: chain carbonates, cyclic ester carbonates, chain ethers, cyclic ethers, glycol ethers, and nitrile solvents.
14. A battery pack comprising at least two assembled lithium-air battery cells according to claim 1 .
15. A method comprising applying the battery pack according to claim 14 to act as a rechargeable battery for electric vehicles and hybrid vehicles, electronic devices, and stationary power generating devices.
16. A vehicle, an electronic device, and a stationary power generating device, comprising a battery pack according to claim 14 .
17. The lithium-air battery cell according to claim 3 , wherein the positive electrode further comprises a solid n-type electroactive organic catalyst lithium salt.
18. The lithium-air battery cell according to claim 17 , wherein the solid n-type electroactive organic catalyst lithium salt shows the following general structure (3):
wherein R 7 and R 8 are each independently selected from the group consisting of: H, aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy, amino-alkyl, amino-aryl, thio-alkyl, thio-aryl, alkyl phosphonate, aryl phosphonate, cyclodienyl, —OCR, —(O═)CHNR, —HN(O═)CR, —(O═)COR, —HN(O═)CHNR, —HN(O═)COR, —(HN═)CHNR, —HN(HN═)CHNR, —(S═)CHNR, —HN(S═)CHNR, with R being H or a C 1 -C 19 -alkyl group, the R 7 and R 8 groups comprising from 1 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom, the latter comprising from 4 to 20 carbon atoms and being optionally substituted with at least one halogen, oxygen or sulphur atom.
19. The lithium-air battery cell according to claim 18 , wherein R 7 and R 8 are H.
20. The lithium-air battery cell according to claim 17 , wherein the weight ratio between solid p-type electroactive organic catalyst lithium salt and solid n-type electroactive organic catalyst lithium salt ranges from 0.1/99.9 to 100/0.