Use of subfluorinated carbon nano-objects as an electrode material of primary lithium batteries with strong capabilities

1. A process for the manufacture of a lithium battery electrode, said process comprising the formation of a lithium battery electrode with micrometric grains made of subfluorinated carbon with a graphite crystalline structure, the greatest dimension of which is between 1 and 10 μm, said micrometric grains comprising:

a central part made of nonfluorinated carbon which represents from 0.8 to 30% by volume of the total volume of the grain, and

a peripheral part made of fluorinated carbon of formula CF X , where x represents the F/C atomic ratio and is such that 0.25<x<1.1, and the 19 F MAS NMR spectrum of which exhibits a single isotropic peak between −150 and −190 ppm/CFCl 3 , rotational bands excluded, and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band,

the electrode obtained having a capacity greater than 100% of the theoretical capacity of the micrometric grain.

2. The process as claimed in claim 1 , in which the formation of a lithium battery electrode with micrometric grains made of subfluorinated carbon is carried out by mixing 80% by weight of these micrometric grains with 20% by weight of a mixture of a binding agent and carbon, with respect to the total weight of the electrode formed.

3. The process as claimed in claim 2 , wherein the binding agent is PVDF (polyvinylidene fluoride).

4. The process as claimed in claim 1 , in which the formation of a lithium battery electrode with micrometric grains made of subfluorinated carbon is carried out by mixing 80% by weight of these micrometric grains with 10% by weight of PVDF and 10% by weight of carbon, with respect to the total weight of the electrode formed.

5. The process as claimed in claim 1 , in which the micrometric grains are as a mixture with one or more nano-objects chosen from:

a stack of subfluorinated carbon nanodisks with a diameter of between 0.6 and 2.8 μm, preferably with a diameter of 1.5 μm, and with a thickness of between 12 and 123 nm, preferably with a thickness of 62 nm, the central part of which made of nonfluorinated carbon represents from 6 to 14% by volume of the total volume of the stack of nanodisks and the peripheral part of formula CFx, where x represents the F/C atomic ratio and is such that 0.25<x<1.1 and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band;

double-walled subfluorinated carbon nanotubes with a diameter of between 1 and 2.7 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 45 to 65% by volume, preferably 60% by volume, of the total volume of the nanotubes and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS (tetramethylsilane); and

multi-walled subfluorinated carbon nanotubes with a diameter of between 1.8 and 54 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 3 to 60% by volume of the total volume of the multi-walled nanotubes, comprising less than 30 walls, and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS.

6. The process as claimed in claim 2 , in which the micrometric grains are as a mixture with one or more nano-objects chosen from:

a stack of subfluorinated carbon nanodisks with a diameter of between 0.6 and 2.8 μm, preferably with a diameter of 1.5 μm, and with a thickness of between 12 and 123 nm, preferably with a thickness of 62 nm, the central part of which made of nonfluorinated carbon represents from 6 to 14% by volume of the total volume of the stack of nanodisks and the peripheral part of formula CFx, where x represents the F/C atomic ratio and is such that 0.25<x<1.1 and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band;

double-walled subfluorinated carbon nanotubes with a diameter of between 1 and 2.7 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 45 to 65% by volume, preferably 60% by volume, of the total volume of the nanotubes and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS (tetramethylsilane); and

multi-walled subfluorinated carbon nanotubes with a diameter of between 1.8 and 54 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 3 to 60% by volume of the total volume of the multi-walled nanotubes, comprising less than 30 walls, and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS.

7. The process as claimed in claim 3 , in which the micrometric grains are as a mixture with one or more nano-objects chosen from:

a stack of subfluorinated carbon nanodisks with a diameter of between 0.6 and 2.8 μm, preferably with a diameter of 1.5 μm, and with a thickness of between 12 and 123 nm, preferably with a thickness of 62 nm, the central part of which made of nonfluorinated carbon represents from 6 to 14% by volume of the total volume of the stack of nanodisks and the peripheral part of formula CFx, where x represents the F/C atomic ratio and is such that 0.25<x<1.1 and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band;

double-walled subfluorinated carbon nanotubes with a diameter of between 1 and 2.7 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 45 to 65% by volume, preferably 60% by volume, of the total volume of the nanotubes and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS (tetramethylsilane); and

multi-walled subfluorinated carbon nanotubes with a diameter of between 1.8 and 54 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 3 to 60% by volume of the total volume of the multi-walled nanotubes, comprising less than 30 walls, and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS.

8. The process as claimed in claim 4 , in which the micrometric grains are as a mixture with one or more nano-objects chosen from:

a stack of subfluorinated carbon nanodisks with a diameter of between 0.6 and 2.8 μm, preferably with a diameter of 1.5 μm, and with a thickness of between 12 and 123 nm, preferably with a thickness of 62 nm, the central part of which made of nonfluorinated carbon represents from 6 to 14% by volume of the total volume of the stack of nanodisks and the peripheral part of formula CFx, where x represents the F/C atomic ratio and is such that 0.25<x<1.1 and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band;

double-walled subfluorinated carbon nanotubes with a diameter of between 1 and 2.7 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 45 to 65% by volume, preferably 60% by volume, of the total volume of the nanotubes and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS (tetramethylsilane); and

multi-walled subfluorinated carbon nanotubes with a diameter of between 1.8 and 54 nm and with a length of between 5 and 20 the central nanotube of which made of nonfluorinated carbon represents from 3 to 60% by volume of the total volume of the multi-walled nanotubes, comprising less than 30 walls, and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS.

9. A primary lithium battery electrode, wherein it comprises micrometric grains made of subfluorinated carbon with a graphite crystalline structure, the greatest dimension of which is between 1 and 10 said grains comprising:

a central part made of nonfluorinated carbon which represents from 0.8 to 30% by volume of the total volume of the grain, and

a peripheral part made of fluorinated carbon of formula CF X , where x represents the F/C atomic ratio and is such that 0.25<x<1.1, and the 19 F MAS NMR spectrum of which exhibits a single isotropic peak between −150 and −190 ppm/CFCl 3 , rotational bands excluded, and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band,

the primary battery having a capacity greater than 100% of the theoretical capacity of the micrometric grain.

10. The electrode as claimed in claim 9 , in which the micrometric grains are as a mixture with one or more nano-objects chosen from:

a stack of subfluorinated carbon nanodisks with a diameter of between 0.6 and 2.8 μm, preferably with a diameter of 1.5 and with a thickness of between 12 and 123 nm, preferably with a thickness of 62 nm, the central part of which made of nonfluorinated carbon represents from 6 to 14% by volume of the total volume of the stack of nanodisks and the peripheral part of formula CFx, where x represents the F/C atomic ratio and is such that 0.25<x<1.1 and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band;

double-walled subfluorinated carbon nanotubes with a diameter of between 1 and 2.7 nm and with a length of between 5 and 20 the central nanotube of which made of nonfluorinated carbon represents from 45 to 65% by volume, preferably 60% by volume, of the total volume of the nanotubes and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS (tetramethylsilane); and

multi-walled subfluorinated carbon nanotubes with a diameter of between 1.8 and 54 nm and with a length of between 5 and 20 the central nanotube of which made of nonfluorinated carbon represents from 3 to 60% by volume of the total volume of the multi-walled nanotubes, comprising less than 30 walls, and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS.

11. A primary lithium battery, wherein it comprises an electrode obtained by a process comprising

forming a lithium battery electrode with micrometric grains made of subfluorinated carbon with a graphite crystalline structure, the greatest dimension of which is between 1 and 10 μm, said micrometric grains comprising:

a central part made of nonfluorinated carbon which represents from 0.8 to 30% by volume of the total volume of the grain, and

a peripheral part made of fluorinated carbon of formula CF X , where x represents the F/C atomic ratio and is such that 0.25<x<1.1, and the 19 F MAS NMR spectrum of which exhibits a single isotropic peak between −150 and −190 ppm/CFCl 3 , rotational bands excluded, and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band,

wherein the electrode obtained having a capacity greater than 100% of the theoretical capacity of the micrometric grain.

12. The primary lithium battery as claimed in claim 11 ,

wherein the forming of the lithium battery electrode with micrometric grains made of subfluorinated carbon is carried out by mixing 80% by weight of these micrometric grains with 20% by weight of a mixture of a binding agent and carbon, with respect to the total weight of the electrode formed.

13. The primary lithium battery as claimed in claim 12 , wherein the binding agent is PVDF (polyvinylidene fluoride).

14. The primary lithium battery as claimed in claim 11 , wherein the forming of a lithium battery electrode with micrometric grains made of subfluorinated carbon is carried out by mixing 80% by weight of these micrometric grains with 10% by weight of PVDF, and 10% by weight of carbon, with respect to the total weight of the electrode formed.

15. The primary lithium battery as claimed in claim 11 , wherein the micrometric grains are as a mixture with one or more nano-objects chosen from:

a stack of subfluorinated carbon nanodisks with a diameter of between 0.6 and 2.8 μm, preferably with a diameter of 1.5 μm, and with a thickness of between 12 and 123 nm, preferably with a thickness of 62 nm, the central part of which made of nonfluorinated carbon represents from 6 to 14% by volume of the total volume of the stack of nanodisks and the peripheral part of formula CFx, where x represents the F/C atomic ratio and is such that 0.25<x<1.1 and the electron paramagnetic resonance spectrum of which exhibits 7 signals between 3200 and 3800 G in the X band;

double-walled subfluorinated carbon nanotubes with a diameter of between 1 and 2.7 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 45 to 65% by volume, preferably 60% by volume, of the total volume of the nanotubes and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS (tetramethylsilane); and

multi-walled subfluorinated carbon nanotubes with a diameter of between 1.8 and 54 nm and with a length of between 5 and 20 μm, the central nanotube of which made of nonfluorinated carbon represents from 3 to 60% by volume of the total volume of the multi-walled nanotubes, comprising less than 30 walls, and the 13 C MAS NMR spectrum of which exhibits a band at 120 ppm/TMS.

16. A primary lithium battery, wherein it comprises an electrode as claimed in claim 9 , and an electrolyte.

17. A primary lithium battery, wherein it comprises an electrode as claimed in claim 10 , and an electrolyte.