Additives to enhance electrode wetting and performance and methods of making electrodes comprising the same

Patent metadata

Field	Value
Publication number	US-2017047581-A1
Application number	US-201615334240-A
Country	US
Kind code	A1
Filing date	Oct 25, 2016
Priority date	Feb 11, 2014
Publication date	Feb 16, 2017
Grant date	—

Abstract

Electrodes having nanostructure and/or utilizing nanoparticles of active materials and having high mass loadings of the active materials can be made to be physically robust and free of cracks and pinholes. The electrodes include nanoparticles having electroactive material, which nanoparticles are aggregated with carbon into larger secondary particles. The secondary particles can be bound with a binder to form the electrode. The electrodes can further comprise additives that enhance electrode wetting thereby improving overall electrode performance.

First claim

We claim:

1 . A thick electrode, comprising:
secondary particles comprising an aggregate of nanoparticles that are coated and joined together by a conductive carbon material; an electroactive material; a binder that binds the secondary particles together; and a salt additive, a solvent additive, or a combination thereof.

2 . The thick electrode of claim 1 , comprising the salt additive in an amount ranging from 1 wt % to 20 wt %.

3 . The thick electrode of claim 1 , comprising the solvent additive in an amount ranging from 1 wt % to 20 wt %.

4 . The thick electrode of claim 1 , wherein the electroactive material is present in an amount ranging from about 2 mg/cm 2 to about 8 mg/cm 2 .

5 . The thick electrode of claim 1 , wherein the salt additive is a lithium ion-based salt, a non-lithium ion-based salt, an inorganic salt, an organic salt, or a combination thereof.

6 . The thick electrode of claim 5 , wherein the lithium ion-based salt has a formula LiX, wherein X is an anion selected from PF 6 − , FSI − , TFSI − , BOB − , BF 4 − , AsF 6 − , and ClO 4 − .

7 . The thick electrode of claim 5 , wherein the non-lithium ion-based salt has a formula AX n , wherein A is selected from Na + , K + , Cs + , Rb + , Mg 2+ , Ca 2+ , and NH 4 + ; X is an anion selected from PF 6 − , FSI − , TFSI − , BOB − , BF 4 − , AsF 6 − , and ClO 4 − ; and n is 1 or 2.

8 . The thick electrode of claim 5 , wherein the inorganic salt has a composition satisfying a formula BY m , wherein B is selected from Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ti 4+ , V 3+ , Cr 3+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ , Cu 2+ , and Zn 2+ ; Y is selected from F − , Cl − , Br − , I − , SO 4 2− , CO 3 2− , and PO 4 3− ; and m is an integer selected from 1, 2, and 3.

9 . The thick electrode of claim 5 , wherein the organic salt has a composition satisfying a formula BZ p , wherein B is selected from Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ti 4+ , V 3+ , Cr 3+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ , Cu 2+ , and Zn 2+ ; Z is an anion of an organic acid selected from citric acid, acetic acid, and formic acid; and p is an integer selected from 1 to 4.

10 . The thick electrode of claim 1 , wherein the salt additive is LiTFSI.

11 . The thick electrode of claim 1 , wherein the solvent additive is a high boiling point solvent.

12 . The thick electrode of claim 11 , wherein the high boiling point solvent is a carbonate solvent having a structure satisfying a formula R 1 —O(C═O)OR 2 , wherein R 1 and R 2 independently are selected from aliphatic or aryl; an ester solvent having a structure satisfying a formula (R 1 —O(C═O)—R 2 ), wherein R 1 and R 2 independently are selected from aliphatic or aryl; an ether solvent having a structure satisfying a formula R 1 —O—R 2 , wherein R 1 and R 2 independently are selected from aliphatic or aryl; or a combination thereof.

13 . The thick electrode of claim 1 , wherein the nanoparticles comprise carbon or silicon.

14 . The thick electrode of claim 1 , wherein the electroactive material is selected from phosphates, sulfides, sulfates, transition metal oxides, and combinations thereof.

15 . The thick electrode of claim 1 , wherein the electroactive material is sulfur.

16 . A cell, comprising:
a thick electrode made of secondary particles comprising an aggregate of nanoparticles that are coated and joined together by a conductive carbon material; an electroactive material; a binder that binds the secondary particles together; and a salt additive, a solvent additive, or a combination thereof; a second electrode; and an electrolyte;
wherein the cell exhibits improved performance relative to a cell lacking an electrode comprising a salt additive, a solvent additive, or a combination thereof.

17 . The cell of claim 16 , wherein improved performance is determined by:
(a) an open circuit voltage (OCV) of the cell relative to an open circuit voltage (OCV) of the cell lacking an electrode comprising a salt additive, a solvent additive, or a combination thereof; (b) an electrode areal capacity as a function of increasing electroactive material loading of the thick electrode of the cell relative to an electrode areal capacity as a function of increasing electroactive material loading of an electrode in the cell lacking an electrode comprising a salt additive, a solvent additive, or a combination thereof; (c) a discharge capacity of the cell relative to a discharge capacity of the cell lacking an electrode comprising a salt additive, a solvent additive, or a combination thereof; and/or (d) a cell capacity of the cell after 300 cycles relative to a cell capacity of the cell lacking an electrode comprising a salt additive, a solvent additive, or a combination thereof after 300 cycles.

18 . The cell of claim 17 , wherein OCV of the cell is 10% greater than that of the cell lacking an electrode comprising a salt additive, a solvent additive, or a combination thereof.

19 . The cell of claim 17 , wherein the electrode areal capacity of the thick electrode increases as the electroactive material loading increases.

20 . The cell of claim 17 , wherein the discharge capacity of the thick electrode is 20% to 50% higher than that of the cell lacking an electrode comprising a salt additive, a solvent additive, or a combination thereof.

21 . The cell of claim 17 , wherein the cell maintains 80% of its cell capacity after 300 cycles.

22 . A thick electrode, comprising:
nanoparticles comprising an electroactive material; a conductive carbon material; a binder; and a salt additive, a solvent additive, or a combination thereof.

23 . A method of making the thick electrode of claim 22 , comprising:
mixing the conductive carbon material with the binder to obtain a conductive carbon-binder dispersion; mixing the electroactive material with the conductive carbon-binder dispersion to form a homogenous slurry; mixing the salt additive, the solvent additive, or combination thereof with the homogeneous slurry to form a viscous slurry; depositing the viscous slurry onto a surface of a current collector, thereby forming a casted slurry layer on the surface of the current collector; and drying the casted slurry layer to form the thick electrode.

Assignees

• Battelle Memorial Institute
• Battelle Memorial Institute

Inventors

• Lu Dongping
• Li Qiuyan
• Zhang Jiguang
• Graff Gordon L
• Liu Jun
• Liu Jian
• Xiao Jie

Classifications

• H01M4/364 Primary

  as mixtures · CPC title

• H01M4/48

  of inorganic oxides or hydroxides · CPC title

• H01M4/5815

  Sulfides · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/0404

  by coating on electrode collectors · CPC title