Lithium-doped pernigraniline-based materials

Patent metadata

Field	Value
Publication number	US-10651473-B2
Application number	US-201515121293-A
Country	US
Kind code	B2
Filing date	Feb 23, 2015
Priority date	Dec 23, 2014
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The present invention relates to a new lithium-doped Pernigraniline-based material, a method for the preparation thereof, its use in various applications, an electrode comprising said lithium-doped Pernigraniline-based material and its preparation method, a membrane comprising said lithium-doped Pernigraniline-based material and its preparation method, and an electrochemical storage system comprising said electrode.

First claim

The invention claimed is:

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 depro

Assignees

• Centre Nat Rech Scient
• Univ Nantes
• Univ Picardie

Inventors

• Gaubicher Joël
• Guyomard Dominique
• Lestriez Bernard
• Bonnet Jean-Pierre
• Jimenez Manero Pablo

Classifications

• H01M4/606 Primary

  containing aromatic main chain polymers · CPC title

• C04B7/243 Primary

  Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators · CPC title

• H01G11/50

  specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation · CPC title

• H01M4/669

  Steels · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title