Lithium-doped pernigraniline-based materials

1. A lithium-doped Pernigraniline-based material (PN-Li), comprising

at least one polymer chain formed by the succession of C 6 H 4 rings and nitrogen atoms, each nitrogen atom being linked in para position relative to each C 6 H 4 ring;

n repeating units;

a total amount X of lithium cations (Li + );

an average amount of lithium cations (Li + ) per repeating unit, with x=X/n;

a total amount Y of anions (A m− );

an average amount y of charge provided by anions (A m− ) per repeating unit, with y=mY/n;

a charge q of each repeating unit,

a total charge Q of the polymer chain, with

Q

=

∑

n

⁢

q

i

mY−X since Q is compensated by the charges of Li + and A m− ;

Q/n represents the formal oxidation state and Q/n=y−x; and

wherein said PN-Li responds to the following formula (I):

in which:

* 4≤n≤500,000,

* q is equal to −1, 0 or +1,

* the mean atomic ratio hydrogen/nitrogen (H/N) for each repeating unit is such that 4≤H/N<4.5,

* −1≤Q/n<0,

* 0.5≤x≤1,

* 0≤y≤0.5.

2. A method for the preparation of a lithium-doped Pernigraniline-based material (PN-Li) as defined in claim 1 , wherein it comprises at least the following steps:

1) putting into contact Polyaniline (P) with a deprotonation solution to obtain a reaction mixture, said deprotonation solution comprising:

at least one aprotic solvent,

at least one lithium salt which is soluble in said aprotic solvent,

at least one lithiated organic compound (Li—OC 1 ) or a precursor of a lithiated organic compound Li—OC 1 , said Li—OC 1 or precursor being soluble in said aprotic solvent, and said Li—OC 1 being a strong Brönsted base able to deprotonate the amine groups present in Polyaniline (P),

2) leaving the reaction mixture optionally with mixing,

3) recovering lithium-doped Pernigraniline-based material (PN-Li).

3. The method according to claim 2 , wherein the deprotonation solution further comprises an organic compound OC 2 which is soluble in said aprotic solvent and which comprises an alkene functional group.

4. The method according to claim 2 , wherein the lithiated organic compound Li—OC 1 is selected from lithium amides, lithium enolates, lithium ester enolates, lithium acetylides, organolithium compounds, and mixtures thereof.

5. The method according to claim 2 , wherein the precursor PR 1 of the lithiated organic compound Li—OC 1 is metallic lithium (Li) and the precursor PR 2 of the lithiated organic compound Li—OC 1 is any one of the following conjugated acids of OC 1 : an amine, a keton, an ester, an alkyne or an alkyl halide.

6. A positive electrode material comprising:

at least one polymeric binder,

optionally a material conferring electronic conduction other than PN-Li,

optionally an active material other than PN-Li, and

wherein it further comprises a lithium-doped Pernigraniline material PN-Li as defined in claim 1 .

7. The positive electrode material according to claim 6 , wherein said positive electrode material is a lithium battery-type positive electrode material comprising with respect to the total weight of the positive electrode material:

from 60 weight % to 98 weight % of PN-Li,

from 1 weight % to 15 weight % of a material conferring electronic conduction other than PN-Li, and

from 1 weight % to 15 weight % of a polymeric binder; and

wherein said positive electrode material does not comprise any other active material than PN-Li.

8. The positive electrode material according to claim 6 , wherein said positive electrode material is a supercapacitor-type positive electrode material comprising with respect to the total weight of the positive electrode material:

from 35 weight % to 60 weight % of PN-Li,

from 15 weight % to 60 weight % of a material conferring electronic conduction other than PN-Li having a high specific surface area ranging from 400 m 2 /g to 3000 m 2 /g, and

from 1 weight % to 15 weight % of a polymeric binder;

and wherein said positive electrode material does not comprise any other active material than PN-Li.

9. The positive electrode material according to claim 6 , wherein it is a lithium battery-type composite positive electrode material comprising from 60 weight % to 96 weight % of an active material other than PN-Li with respect to the total weight of the positive electrode material.

10. A method for the preparation of a positive electron material as defined in claim 6 wherein said method comprises at least the following steps:

A) preparing a composition comprising Polyaniline (P), at least one polymeric binder, optionally a material conferring electronic conduction other than PN-Li, and optionally an active material other than PN-Li, and

B) preparing a composition comprising at least one lithium-doped Pernigraniline-based material (PN-Li) from the composition of step A) according to the following steps:

1) putting into contact Polyaniline (P) with a deprotonation solution to obtain a reaction mixture, said deprotonation solution comprising:

at least one aprotic solvent,

at least one lithium salt which is soluble in said at least one aprotic solvent,

at least one lithiated organic compound (Li—OC 1 ) or a precursor of a lithiated organic compound Li—OC 1 , said Li—OC 1 or said precursor being soluble in said at least one aprotic solvent, and said Li—OC 1 being a strong Brönsted base able to deprotonate the amine groups in the Polyaniline (P),

2) leaving the reaction mixture optionally with mixing, and

3) recovering lithium-doped Pernigraniline-based material (PN-Li).

11. A lithium battery comprising:

a positive electrode material,

a negative electrode material,

a separator which acts as an electrical insulator and allows the transport of ions, and

a non-aqueous electrolyte comprising at least one lithium salt and an aprotic solvent, and

wherein the positive electrode material is a battery-type positive electrode material or a battery-type composite electrode material as defined in claim 7 .

12. A supercapacitor comprising:

a positive electrode material,

a negative electrode material,

a separator which acts as an electrical insulator and allows the transport of ions, and

a non-aqueous electrolyte comprising at least one lithium salt and an aprotic solvent, and

wherein the positive electrode material is a supercapacitor-type positive electrode material as defined in claim 8 .

13. A free-standing membrane comprising with respect to the total weight of the membrane:

from 2 weight % to 15 weight % of a polymeric binder, and

wherein the membrane further comprises from 85 weight % to 98 weight % of PN-Li as defined in claim 1 .

14. A method for the preparation of a membrane as defined in claim 13 , wherein said method comprises at least the following steps:

i) preparing a composition comprising Polyaniline (P), at least one polymeric binder in the form of a film, and

ii) preparing a composition comprising at least one lithium-doped Pernigraniline-based material (PN-Li) from the composition of step i) according to the following steps:

1) putting into contact Polyaniline (P) with a deprotonation solution to obtain a reaction mixture, said deprotonation solution comprising:

at least one aprotic solvent,

at least one lithium salt which is soluble in said at least one aprotic solvent,

at least one lithiated organic compound (Li—OC 1 ) or a precursor of a lithiated organic compound Li—OC 1 , said Li—OC 1 or said precursor being soluble in said at least one aprotic solvent, and said Li—OC 1 being a strong Brönsted base able to deprotonate the amine groups in the Polyaniline (P),

2) leaving the reaction mixture optionally with mixing, and

3) recovering lithium-doped Pernigraniline-based material (PN-Li).

15. A method for the preparation or the modification of a lithium-doped Pernigraniline-based material (PN-Li) as defined in claim 1 , wherein it comprises at least one step of submitting to a charge

a battery having

a positive electrode material,

a negative electrode material,

a separator which acts as an electrical insulator and allows the transport of ions, and

a non-aqueous electrolyte comprising at least one lithium salt and an aprotic solvent,

or a supercapacitor having

a positive electrode material,

a negative electrode material,

a separator which acts as an electrical insulator and allows the transport of ions, and

a non-aqueous electrolyte comprising at least one lithium salt and an aprotic solvent.

16. An active material in electrodes, or a binder, or a conducting agent, in any one of batteries, supercapacitors, electronic and/or optoelectronic devices like solar cells, photoconductors, light-emitting or electrochromic devices, field effect transistors, electromagnetic radiation absorbers, gas sensors, separation membranes, antistatic coatings, conducting molecular wires and anticorrosion coatings comprising:

a lithium-doped Pernigraniline-based material PN-Li as defined in claim 1 .