Polymer precursors for solid state electrolytes

Patent metadata

Field	Value
Publication number	US-12327871-B2
Application number	US-201917271244-A
Country	US
Kind code	B2
Filing date	Aug 30, 2019
Priority date	Aug 31, 2018
Publication date	Jun 10, 2025
Grant date	Jun 10, 2025

Abstract

A method of synthesizing a precursor for making a polymer, glass, or ceramic material is provided. The method includes reacting OPCl 3 with NH 3 or MNH 2 , where M is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form O═P(NH2) 3 . The method then includes either: (i) reacting the O═P(NH 2 ) 3 with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor; or (ii) heating the O═P(NH 2 ) 3 to form a branched or cyclomeric compound, and reacting the branched or cyclomeric compound with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor. The precursor is an oligomer or a polymer. Uses for the precursor and the polymer, glass, or ceramic material as binders, sintering aids, adhesives, and electrolytes in battery components are also provided.

First claim

What is claimed is:

1. A method of synthesizing a precursor for making a polymer, glass, or ceramic material, the method comprising:
reacting OPCl 3 with NH 3 or MNH 2 , where M is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form O═P(NH 2 ) 3 ; and either
i. reacting the O═P(NH 2 ) 3 with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor; or
ii. heating the O═P(NH 2 ) 3 to form a branched or cyclomeric compound; and

reacting the branched or cyclomeric compound with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor.

2. The method according to claim 1 , wherein the method comprises i. and the reacting the O═P(NH 2 ) 3 with the M1NH 2 is performed at a temperature of greater than or equal to about −50° C. to less than or equal to about 200° C. to form the precursor as the oligomer.

3. The method according to claim 2 , further comprising:
heating the oligomer to a temperature greater than or equal to about 40° C. to less than or equal to about 300° C. to increase the molecular weight of the oligomer.

4. The method according to claim 1 , wherein the method comprises i. and the reacting the O═P(NH 2 ) 3 with the M1NH 2 is performed at a temperature of greater than about 20° C. to less than or equal to about 500° C. to form the precursor as the polymer.

5. The method according to claim 4 , further comprising:
heating the polymer to a temperature greater than or equal to about 50° C. to less than or equal to about 400° C. to increase the ceramic yield of the polymer.

6. The method according to claim 1 , wherein the method comprises ii. and the reacting is performed at a temperature of greater than or equal to about 30° C. to less than or equal to about 150° C.

7. The method according to claim 1 , wherein the method comprises ii. and is performed on a surface of, and optionally in pores of, a solid-state battery component selected from the group consisting of a cathode, an anode, a solid electrode, and combinations thereof.

8. The method according to claim 1 , wherein the precursor has the formula M1 a M2 b P m H n N x O y S z , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof; M2 is Al, S, Se, C, Si, Ge, Sn, Zn, or combinations thereof; 1≤a≤10; 0≤b≤10; 0≤m≤50; and 0 ≤n≤60; 0≤x≤50; 0≤y≤20; and 0≤z≤20.

9. The method according to claim 8 , wherein the precursor is PON, Li x PON, Na x PON, SiPON, Li x SiPON, Na x SiPON, LiNaSiPON, or MgSiPON, where x is 1, 1.5, 3, or 6.

10. A method of making an ion-conducting polymer-precursor composite material, comprising:
adding the precursor formed according to the method of claim 1 to a solution comprising an ion-conducting polymer and a solvent to form a polymer-precursor solution;
casting the polymer-precursor solution on a plate; and
removing the solvent from the polymer-precursor solution to form the ion-conducting polymer-precursor composite material.

11. The method according to claim 10 , wherein the ion-conducting polymer is polyethylene oxide (PEO), polypropylene oxide (PPO), an ion-conducting carboxylate polymer, copolymers thereof, or mixtures thereof.

12. The method according to claim 10 , wherein the solvent is acetonitrile.

13. The method according to claim 10 , wherein the precursor is PON, Li x PON, Na x PON, SiPON, Li x SiPON, Na x SiPON, LiNaSiPON, or MgSiPON, where x is 1, 1.5, 3, or 6.

14. The method according to claim 10 , further comprising:
incorporating the ion-conducting polymer-precursor composite material into a solid-state battery as a solid composite electrolyte.

15. A method of synthesizing a precursor for making a polymer, glass, or ceramic material, the method comprising:
reacting OPCl 3 with NH 3 or MNH 2 , where M is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form O═P(NH 2 ) 3 , wherein the reacting is performed in a polar, aprotic solvent at a temperature of greater than or equal to about −50° C. to less than or equal to about 200° C.; and either
i. reacting the O═P(NH 2 ) 3 with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor; or
ii. heating the O═P(NH 2 ) 3 to form a branched or cyclomeric compound; and reacting the branched or cyclomeric compound with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor,

wherein the precursor is an oligomer or a polymer.

16. A method of making a polymer, glass, or ceramic material, the method comprising:
forming a precursor that is an oligomer or polymer by reacting OPCl 3 with NH 3 or MNH 2 , where M is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form O═P(NH 2 ) 3 ; and
either
i. reacting the O═P(NH 2 ) 3 with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor; or
ii. heating the O═P(NH 2 ) 3 to form a branched or cyclomeric compound; and reacting the branched or cyclomeric compound with M1NH 2 , where M1 is Li, Na, K, Mg, Ca, Ba, or combinations thereof, to form the precursor;

heating the precursor to a temperature of greater than or equal to about ambient temperature to less than or equal to about 1000° C. to form the polymer, glass, or ceramic material.

17. The method according to claim 16 , further comprising, prior to the heating:
applying the precursor that is an oligomer or polymer to at least a portion of a surface of a battery component selected from the group consisting of a cathode, an anode, a solid electrolyte, and combinations thereof,
wherein the applying is performed by a process selected from the group consisting of doctor blading, spreading, brushing, spin casting, pouring, pipetting, printing, spray coating, dip coating, and combinations thereof.

18. The method according to claim 16 , further comprising:
combining the precursor with at least one of an electrode active material, with a separator material, or with a solid-state electrolyte material to generate at least one of a composite electrode material, a composite separator material, or a composite solid-state electrolyte material.

Assignees

• Univ Michigan Regents

Inventors

• Laine Richard M
• Temeche Eleni
• Zhang Xinyu

Classifications

• H01M2300/0068

  inorganic · CPC title

• C01B21/082

  Compounds containing nitrogen and non-metals {and optionally metals}(C01B21/06, C01B21/08 take precedence) · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M50/434

  Ceramics · CPC title