Composite battery electrode structures comprising high-capacity materials and polymers and methods of forming thereof
Described herein are composite battery electrode structures and methods of forming such structures. Composite battery electrode structures comprise active electrode material structures and polymer structures such that at least a portion of the polymer structures at least partially protrudes into some of the high capacity structures. Some of these polymer structures may be fully enclosed by the active electrode material structures. Other polymer structures may only partially extend inside the active electrode material structures. Furthermore, additional polymer structures may be bound to the external surface of the active electrode material structures. Composite battery electrode structures may be formed using low-temperature deposition techniques, such as solvent-thermal synthesis, direct chemical reduction, and electrochemical deposition. More specifically, composite battery electrode structures may be formed from a solution comprising active electrode material precursors and polymer precursors, e.g., dissolved polymers, monomers, and/or conductive polymers electrically coupled to the working electrodes.
1 . A method of fabricating composite battery electrode structures, the method comprising:
synthesizing active electrode material structures using one or more low-temperature techniques selected from the group consisting of electrochemical deposition, solvent-thermal synthesis, and direct chemical reduction, wherein:
the composite battery electrode structures comprise the active electrode material structures and polymer structures, and
at least a first portion of the polymer structures is at least partially incorporated into a second portion of the active electrode material structures while synthesizing the active electrode material structures such that at least the first portion of the polymer structures partially protrudes into and is at least partially surrounded by at least a second portion of the active electrode material structures.
2 . The method of claim 1 , further comprising forming the polymer structures simultaneously with electrochemically depositing the active electrode material structures.
3 . The method of claim 2 , wherein forming the polymer structures comprises adsorbing a polymer material on the active electrode material structures while the active electrode material structures are being electrochemically deposited.
4 . The method of claim 3 , wherein the polymer material is dissolved in a solution comprising one or more components used for electrochemically depositing the active electrode material structures.
5 . The method of claim 3 , wherein the polymer material comprises at least one of poly (acrylic acid) (PAA), polyvinylalcohol (PVA), polyvinylidene difluoride (PVDF), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polypyrrole (PPy), or pyrene-polyacrylic acid (PR-PAA).
6 . The method of claim 2 , wherein forming the polymer structures comprises polymerizing a monomer material while synthesizing the active electrode material structures.
7 . The method of claim 6 , wherein the monomer material comprises at least one of 2,5-dibromo-3,4-ethylenedioxythiophene monomer, 2,5-dichloro-3,4-ethylenedioxythiophene monomer, aniline monomer, acrylonitrile monomer, styrene monomer, ethylene oxide monomer, butadiene monomer, pyrrole monomer, and glucose monomer.
8 . The method of claim 6 , wherein the monomer material comprises at least one of polyacrylic acid (PAA) monomer, vinyl acetate monomer, and methyl methacrylate monomer.
9 . The method of claim 1 , wherein the polymer structures comprise a conductive polymer and are mechanical and electrically coupled to a working electrode used for electrochemically depositing the active electrode material structures such that the active electrode material structures electrochemically deposit on the surface of the polymer structures.
10 . The method of claim 9 , wherein the conductive polymer comprises one or more of polyaniline (PANI), polypyrrole (PPy), and poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS).
11 . The method of claim 10 , wherein:
the active electrode material structures comprise silicon,
the active electrode material structures are formed using the electrochemical deposition performed in an electrodeposition solution, and
the electrodeposition solution comprises one or more silicon tetrachloride (SiCl 4 ), silicon tetrabromide (SiBr 4 ), silicon tetraiodide (SiI 4 ), trichlorosilane (HSiCl 3 ), dichlorosilane (H 2 SiCl 2 ), tetraethyl orthosilicate (Si (OC 2 H 5 ) 4), methyltrichlorosilane (CH 3 SiCl 3 ), germanium tetrachloride (GeCl 4 ), and tin tetrachloride (SnCl 4 ).
12 . The method of claim 1 , wherein the composite battery electrode structures have a mean particle size of between 5 nanometers and 100 micrometers.
13 . The method of claim 1 , further comprising, simultaneously with synthesizing the active electrode material structures, forming the polymer structures.
14 . The method of claim 1 , wherein the active electrode material structures comprise at least one of silicon (Si), germanium (Ge), tin (Sn), aluminum (Al), silicon oxide (SiO x ), silicon carbide (SiC), and silicon oxycarbide (SiO x C y ).
15 . The method of claim 13 , wherein:
forming the polymer structures is performed by introducing a reducing agent or a Lewis acid into a base solution,
the reducing agent is selected from the group consisting of sodium metal, lithium metal, potassium metal, and lithium biphenyl, and
the Lewis acid is selected from the group consisting of aluminum chloride (AlCl 3 ), silicon tetrachloride (SiCl 4 ), and titanium tetrachloride (TiCl 4 ).
16 . The method of claim 13 , wherein forming the polymer structures is performed in a mixture comprising silicon tetrachloride (SiCl 4 ), polyacrylic acid (PAA), and a base solvent selected from the group consisting of tetrahydrofuran (THF), acetonitrile, propylene carbonate (PC), diglyme, monoglyme, and tetraglyme.
17 . The method of claim 16 , wherein the base solvent is tetrahydrofuran (THF).
18 . The method of claim 1 , wherein the active electrode material structures are synthesized using the electrochemical deposition in an electrochemical plating solution comprising silicon tetrachloride (SiCl 4 ), tetrabutylammonium chloride (TBACl), and tetrahydrofuran (THF).
19 . The method of claim 1 , wherein the active electrode material structures are synthesized using the direct chemical reduction by adding sodium naphthalenide (C 10 H 7 Na), operable as a reducing agent, to a base solution comprising a high-capacity material precursor.
20 . The method of claim 19 , wherein the high-capacity material precursor is selected from the group consisting of silicon tetrachloride (SiCl 4 ), silicon tetrabromide (SiBr 4 ), silicon tetraiodide (SiI 4 ), trichlorosilane (HSiCl 3 ), dichlorosilane (H 2 SiCl 2 ), tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ), methyltrichlorosilane (CH 3 SiCl 3 ), germanium tetrachloride (GeCl 4 ), and tin tetrachloride (SnCl 4 ).