Buffering zone for preventing lithium metallization on the anode of lithium ion batteries

• US 10,680,289 B2
• Filed: 04/06/2017
• Issued: 06/09/2020
• Est. Priority Date: 04/07/2016
• Status: Active Grant

• Current Assignee: StoreDot Ltd.
• Original Assignee: StoreDot Ltd.
• Inventors: Burshtain, Doron, Kedem, Nir, Sella, Eran, Aronov, Daniel
• Primary Examiner(s): Walls, Cynthia K
• Application Number:
  US15/480,888
• Publication Number:
  US 20170294687A1
• Time in Patent Office: 1,160 Days
• CPC Class Codes: C09D 179/02 Polyamines
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/387 Tin or alloys based on tin
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Improved anodes and cells are provided, which enable fast charging rates with enhanced safety due to much reduced probability of metallization of lithium on the anode, preventing dendrite growth and related risks of fire or explosion. Anodes and/or electrolytes have buffering zones for partly reducing and gradually introducing lithium ions into the anode for lithiation, to prevent lithium ion accumulation at the anode electrolyte interface and consequent metallization and dendrite growth. Various anode active materials and combinations, modifications through nanoparticles and a range of coatings which implement the improved anodes are provided.

Claims

1. An anode comprising anode active material particles, wherein the anode active material particles have, at a surface thereof, a buffering zone configured to receive lithium ions from an interface of the anode active material particles with an electrolyte, partly mask a positive charge of the received lithium ions, and enable the partly masked lithium ions to move into an inner zone of the anode active material particles for lithiation therein,

wherein the buffering zone comprises of a plurality of electron donating groups interspaced between non-electron donating groups at a numeral ratio of at least 1:

2,

wherein a gradient of the electron donating groups is provided in the buffering zone, and

wherein the electron donating groups comprise molecular groups which are at least partly negatively charged, comprising at least one of;

atoms N or O, having a lone pair of electrons, aromatic groups and/or conjugated systems, and wherein the non-electron donating groups lack free or conjugated electrons;

wherein the buffering zone comprises one or more of the following;

a medium electronic-conducting ionic conductor selected from the group consisting of borates, phosphates, polyphosphates and polypyrrole, wherein the medium electronic-conducting ionic conductor provides at least some of the electron donating groups and at least some of the non-electron donating groups;

or

a lithiated polymer selected from the group comprising;

lithium polyphosphate (Li_(n)PP or LiPP), lithium poly-acrylic acid (Li_(n)PAA or LiPAA), lithium carboxyl methyl cellulose (Li_(n)CMC or LiCMC), lithium alginate (Li_(n)Alg or LiAlg) and combinations thereof, with (n) denoting multiple attached Li, configured to provide at least some of the electron donating groups and at least some of the non-electron donating groups.

2. The anode of claim 1, wherein the buffering zone comprises a medium electronic-conducting ionic conductor selected from the group consisting of borates, phosphates, polyphosphates and polypyrrole, wherein the medium electronic-conducting ionic conductor provides at least some of the electron donating groups and at least some of the non-electron donating groups.

3. The anode of claim 1, wherein the buffering zone comprises a polymer configured to support, mechanically, a solid electrolyte interphase (SEI) at the interface during expansion and contraction of the solid electrolyte interphase, wherein the polymer comprises at least some of the electron donating groups and at least some of the non-electron donating groups.

4. The anode of claim 1, wherein the buffering zone comprises a lithiated polymer selected from the group comprising:

lithium polyphosphate (Li_(n)PP or LiPP), lithium poly-acrylic acid (Li_(n)PAA or LiPAA), lithium carboxyl methyl cellulose (Li_(n)CMC or LiCMC), lithium alginate (Li_(n)Alg or LiAlg) and combinations thereof, with (n) denoting multiple attached Li, configured to provide at least some of the electron donating groups and at least some of the non-electron donating groups.

5. The anode of claim 1, wherein the buffering zone contains anions providing at least some of the electron donating groups and cations providing at least some of the non-electron donating groups, wherein the anions are more mobile than the cations in the buffering zone.

6. The anode of claim 1, wherein the buffering zone is further configured to provides a mobility gradient for anions in the buffering zone.

7. A lithium ion cell comprising the anode of claim 1.

12. The anode of claim 1, wherein the electron donating groups are interspaced by 2-5 non-electron donating groups therebetween.

15. The anode of claim 1, wherein the buffering zone comprises a transition metal oxide(s) selected from the group comprising:

Al₂O₃, B₂O₃, TiO₂, ZrO₂ and MnO.

16. The anode of claim 1, wherein the buffering zone comprises boron oxide(s), phosphorus oxide(s), borate(s), phosphate(s) and combinations thereof.

8. A method comprising configuring anode active material particles to have, at a surface thereof, a buffering zone configured to receive lithium ions from an interface of the anode active material particles with an electrolyte, partially mask a positive charge of the received lithium ions, and enable the partially masked lithium ions to move into an inner zone of the anode active material particles for lithiation therein, wherein the buffering zone is further configured to comprise a plurality of electron donating groups interspaced between non-electron donating groups at a numeral ratio of at least 1:

2, wherein a gradient of the electron donating groups is provided in the buffering zone, wherein the electron donating groups comprise molecular groups which are at least partly negatively charged, comprising at least one of;

atoms N or O, having a lone pair of electrons, aromatic groups and/or conjugated systems, and wherein the non-electron donating groups lack free or conjugated electrons wherein the buffering zone comprises a medium electronic-conducting ionic conductor selected from the group consisting of borates, phosphates, polyphosphates and polypyrrole, wherein the medium electronic-conducting ionic conductor provides at least some of the electron donating groups and at least some of the non-electron donating groups.

9. The method of claim 8, further comprising configuring the buffering zone from a medium electronic-conducting ionic conductor selected from the group consisting of borates, phosphates, polyphosphates and polypyrrole, wherein the medium electronic-conducting ionic conductor provides at least some of the electron donating groups and at least some of the non-electron donating groups.

10. The method of claim 8, further comprising configuring the anode material particles to provide flexible support for a brittle SEI, wherein the flexible support comprises at least some of the electron donating groups and at least some of the non-electron donating groups.

11. The method of claim 8, further comprising lithiating the buffering zone by a lithiated polymer having at least some of the electron donating groups and at least some of the non-electron donating groups.

13. An anode comprising anode active material particles, wherein the anode active material particles have, at a surface thereof, a buffering zone configured to receive lithium ions from an interface of the anode active material particles with an electrolyte, partly mask a positive charge of the received lithium ions, and enable the partly masked lithium ions to move into an inner zone of the anode active material particles for lithiation therein, wherein the buffering zone comprises of a plurality of electron donating groups interspaced between non-electron donating groups at a numeral ratio of at least 1:

2, wherein a gradient of the electron donating groups is provided in the buffering zone, wherein the electron donating groups comprise molecular groups which are at least partly negatively charged, comprising at least one of;

atoms N or O, having a lone pair of electrons, aromatic groups and/or conjugated systems, and wherein the non-electron donating groups lack free or conjugated electrons;

wherein the buffering zone comprises a medium electronic-conducting ionic conductor selected from the group consisting of borates, phosphates, polyphosphates and polypyrrole, wherein the medium electronic-conducting ionic conductor provides at least some of the electron donating groups and at least some of the non-electron donating groups.

14. An anode comprising anode active material particles, wherein the anode active material particles have, at a surface thereof, a buffering zone configured to receive lithium ions from an interface of the anode active material particles with an electrolyte, partly mask a positive charge of the received lithium ions, and enable the partly masked lithium ions to move into an inner zone of the anode active material particles for lithiation therein, wherein the buffering zone comprises of a plurality of electron donating groups interspaced between non-electron donating groups at a numeral ratio of at least 1:

2,

wherein a gradient of the electron donating groups is provided in the buffering zone, and

wherein the buffering zone comprises a medium electronic-conducting ionic conductor selected from the group consisting of borates, phosphates, polyphosphates and polypyrrole, wherein the medium electronic-conducting ionic conductor provides at least some of the electron donating groups and at least some of the non-electron donating groups.