The present disclosure relates to electrochemical cells and electrodes used in electrochemical cells. In particular, the present disclosure relates to electrodes and electrochemical cells for use in batteries, including methods of forming electrodes and electrochemical cells.
A lithium ion battery typically includes a separator and/or electrolyte between an anode and a cathode. In one class of batteries, the separator, cathode and anode materials are individually formed into sheets or films. Sheets of the cathode, separator and anode are subsequently stacked or rolled with the separator separating the cathode and anode (e.g., electrodes) to form the battery. For the cathode, separator and anode to be rolled, each sheet must be sufficiently deformable or flexible to be rolled without failures, such as cracks, brakes, mechanical failures, etc. Typical electrodes include electro-chemically active material layers on electrically conductive metals (e.g., aluminum and copper). For example, electrochemically active material can be deposited onto a current collector along with an inactive binder material. Electrodes can be rolled or cut into pieces which are then layered into stacks. The stacks are of alternating electro-chemically active materials with the separator between them.
Example methods of forming electrodes are provided. The method can include providing a current collector, providing a substantially solid layer of electrode attachment substance on a side of the current collector, and providing electrochemically active material adjacent the substantially solid layer of the electrode attachment substance. The electrochemically active material can be provided in powder form. The method can also include adhering the electrochemically active material to the side of the current collector via the electrode attachment substance.
In various methods, providing the electrochemically active material adjacent the layer of electrode attachment substance can comprise sandwiching the layer of electrode attachment substance between the electrochemically active material and the current collector. Some such methods can further comprise providing a second layer of electrode attachment substance adjacent the electrochemically active material such that the electrochemically active material is sandwiched between the two layers of electrode attachment substance. In some methods, providing the electrochemically active material adjacent the layer of electrode attachment substance can comprise sandwiching the electrochemically active material between the layer of electrode attachment substance and the current collector.
In some methods, the layer of electrode attachment substance can comprise a thermoplastic film. The layer of electrode attachment substance can be insoluble in solvent at a temperature below about 200° C. The layer of electrode attachment substance can comprise a polyphenylene sulfide film, a polyether ether ketone film, a polyether sulfone film, a polysulfone film, or a polyethylene terephthalate film.
The electrochemically active material can comprise a silicon carbon composite material. In some examples, the electrochemically active material can include at least about 50% to about 100% by weight of silicon. For instance, the electrochemically active material can include the silicon at about 60% to about 100% by weight, at about 70% to about 100% by weight, or at about 80% to about 100% by weight.
In some methods, adhering can comprise applying pressure to the electrode attachment substance and/or the electrochemically active material to adhere the electrochemically active material to the current collector. In some methods, adhering can comprise applying heat to the electrode attachment substance and/or the electrochemically active material to adhere the electrochemically active material to the current collector. In some methods, adhering can include an extrusion process. The current collector can be provided in roll form. The layer of electrode attachment substance can be provided in roll form. The method can comprise a roll to roll process.
Various methods can further include providing a second layer of electrode attachment substance on second side of the current collector, providing a second electrochemically active material adjacent the second layer of electrode attachment substance, and adhering the second electrochemically active material to the second side of the current collector via the second layer of electrode attachment substance. In some methods, providing the second electrochemically active material adjacent the second layer of electrode attachment substance can comprise sandwiching the second layer of electrode attachment substance between the second electrochemically active material and the current collector. The methods can further include providing a third layer of electrode attachment substance adjacent the second electrochemically active material such that the second electrochemically active material is sandwiched between the two layers of electrode attachment substance. In some methods, providing the second electrochemically active material adjacent the second layer of electrode attachment substance can comprise sandwiching the second electrochemically active material between the second layer of electrode attachment substance and the current collector.
In some methods, the second layer of electrode attachment substance can be provided in a substantially solid state. The second layer of electrode attachment substance can comprise a thermoplastic film. The second layer of electrode attachment substance can be insoluble in solvent at a temperature below about 200° C. The second layer of electrode attachment substance can comprise a polyphenylene sulfide film, a polyether ether ketone film, a polyether sulfone film, a polysulfone film, or a polyethylene terephthalate film.
In some instances, the second layer of electrode attachment substance can comprise a different material than the substantially solid layer of electrode attachment substance. The second electrochemically active material can be provided in powder form. The second electrochemically active material can comprise a silicon carbon composite material. In some examples, the second electrochemically active material can include at least about 50% to about 100% by weight of silicon. For instance, the second electrochemically active material can include the silicon at about 60% to about 100% by weight, at about 70% to about 100% by weight, or at about 80% to about 100% by weight.
In some methods, adhering the electrochemically active material and adhering the second electrochemically active material can occur simultaneously. The electrode can be a negative electrode.
Additional example methods of forming electrodes are provided. The method can include providing a current collector, providing a layer comprising electrochemically active material on a side of the current collector, and providing a substantially solid layer of electrode attachment substance adjacent the layer comprising electrochemically active material such that the electrochemically active material is between the substantially solid layer of electrode attachment substance and the current collector. The method can also include adhering the electrochemically active material to the side of the current collector via the electrode attachment substance.
Various methods can further comprise providing a second substantially solid layer of electrode attachment substance between the layer comprising electrochemically active material and the current collector such that the electrochemically active material is sandwiched between both of the provided layers of electrode attachment substance. The electrochemically active material can be provided in powder form. The electrochemically active material can be provided as a film. The film can comprise a silicon carbon composite film. In some examples, the electrochemically active material can comprise at least about 50% to about 100% by weight of silicon. For instance, the electrochemically active material can include the silicon at about 60% to about 100% by weight, at about 70% to about 100% by weight, or at about 80% to about 100% by weight.
In some methods, the layer of electrode attachment substance can comprise a thermoplastic film. The layer of electrode attachment substance can be insoluble in solvent at a temperature below about 200° C. The layer of electrode attachment substance can comprise a polyphenylene sulfide film, a polyether ether ketone film, a polyether sulfone film, a polysulfone film, or a polyethylene terephthalate
In some methods, adhering can comprise applying pressure to the electrode attachment substance and/or the electrochemically active material to adhere the electrochemically active material to the current collector. In some methods, adhering can comprise applying heat to the electrode attachment substance and/or the electrochemically active material to adhere the electrochemically active material to the current collector. In some methods, adhering can include an extrusion process. The current collector can be provided in roll form. The layer of electrode attachment substance can be provided in roll form. The layer of electrochemically active material can be provided in roll form. The method can comprise a roll to roll process.
Various methods can further include providing a layer comprising a second electrochemically active material on a second side of the current collector, providing a substantially solid layer of a second electrode attachment substance adjacent the layer comprising the second electrochemically active material such that the second electrochemically active material is between the second electrode attachment substance and the current collector, and adhering the second electrochemically active material to the second side of the current collector via the second electrode attachment substance. The methods can further include providing a substantially solid layer of a third electrode attachment substance between the layer comprising the second electrochemically active material and the current collector such that the second electrochemically active material is sandwiched between the second and third electrode attachment substance.
In some methods, the second electrochemically active material can be provided in powder form. The second electrochemically active material can be provided as a film. In some instances, the second electrochemically active material can comprise a silicon carbon composite film. In some examples, the second electrochemically active material can include at least about 50% to about 100% by weight of silicon. For instance, the second electrochemically active material can include the silicon at about 60% to about 100% by weight, at about 70% to about 100% by weight, or at about 80% to about 100% by weight.
In some methods, the second electrode attachment substance can comprise a thermoplastic film. The second electrode attachment substance can comprise a different material than the electrode attachment substance.
In some methods, adhering the electrochemically active material and adhering the second electrochemically active material can occur simultaneously. The electrode can be a negative electrode.
Commercial lithium-ion battery electrodes are commonly fabricated by casting a slurry onto a metallic current collector. The slurry typically includes active material, conductive additive (e.g., carbon), and binder in a solvent (e.g., N-Methyl-2-pyrrolidone (NMP)). In general, the slurry after being uniformly mixed is cast onto the current collector and the solvent is dried off. The drying process time can be consuming and costly, with the added cost of the sacrificial solvent which in most cases can come with risks of pollution and/or safety hazards. In addition, the use of a cast slurry as electrode material can limit the number of binders that can be used to fabricate such electrode. For example, generally, the binder must be chemically inert to the electrolyte within the battery, but at the same time, it needs to be fairly easily dissolvable in the solvent used for the slurry mix.
Certain implementations described herein utilize one or more substantially solid layers of electrode attachment substance to adhere the electrochemically active material to the current collector. For example, a single solid film or multiple solid films (e.g., one or more thermoplastic films) can be used as the binder/adhesive of the electrode active material by binding together active material powders or other active material (e.g., an active material film) to the current collector. In various instances, using a solid film as adhesive/binder material for active material can allow fabrication of battery electrodes in a roll to roll process. In some embodiments, using a solid film as adhesive/binder material can also allow for fabrication without any solvent for slurry mixes and/or without coating of slurry mixes. By adhering active material to a current collector without the use of a slurry mix, there is no need to dissolve the binder materials in a solvent in order to make the slurry mix. Some such embodiments can be solvent free, e.g., solvent free roll to roll fabrication of battery electrodes, which can reduce production time and lower production cost (e.g., due to no solvent for slurry mixes, no coating of slurry mixes, and/or no drying of slurry mixes). Some such processes can be based on pressure and/or temperature to allow adhesion/binding.
With continued reference to
The electrode attachment substance 120 (e.g., adhesive) can be used to couple or adhere the electrochemically active material 130 to the current collector 110 (e.g., to prevent delamination between them). In various embodiments, the attachment substance 120 is in a substantially solid state. For example, the attachment substance 120 can be a thermoplastic film/foil. Since certain embodiments do not coat a slurry mix on a current collector, the attachment substance 120 is not limited to binders which are soluble in solvents. For example, the attachment substance 120 can include a polyphenylene sulfide (PPS) film, which typically is insoluble in solvent at a temperature below about 200° C./392° F. Some other examples of attachment substance 120 can include films/foils of polyether ether ketone (PEEK), polyether sulfone (PES), polysulfone (PSU), or polyethylene terephthalate (PET).
With continued reference to
The layer of electrochemically active material 130 can include electrode active material with or without additives. For example, the layer of electrochemically active material 130 can include from greater than 0% to about 100% by weight of electrochemically active material. For example, the amount of electrochemically active material by weight of the layer of electrochemically active material 130 can include any weight percent within this range (e.g., about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, etc.), or any range within this range such as any range formed by the example values (e.g., greater than about 0% to about 25% by weight, greater than about 0% to about 35% by weight, greater than about 0% to about 50% by weight, greater than about 0% to about 70% by weight, greater than about 0% to about 90% by weight, greater than about 0% to about 95% by weight, from about 10% to about 35% by weight, from about 10% to about 50% by weight, from about 10% to about 90% by weight, from about 10% to about 95% by weight, from about 10% to about 100% by weight, from about 30% to about 85% by weight, from about 30% to about 90% by weight, from about 30% to about 95% by weight, from about 30% to about 100% by weight, from about 50% to about 85% by weight, from about 50% to about 90% by weight, from about 50% to about 95% by weight, from about 50% to about 100% by weight, from about 60% to about 85% by weight, from about 60% to about 90% by weight, from about 60% to about 95% by weight, from about 60% to about 100% by weight, from about 70% to about 85% by weight, from about 70% to about 90% by weight, from about 70% to about 95% by weight, from about 70% to about 100% by weight, from about 80% to about 90% by weight, from about 80% to about 95% by weight, from about 80% to about 100% by weight, etc.).
As an example, the layer of electrochemically active material 130 can include at least about 50% to about 100% by weight of silicon, at least about 60% to about 100% by weight of silicon, at least about 70% to about 100% by weight of silicon, at least about 80% to about 100% by weight of silicon. In some examples, the layer of electrochemically active material 130 can include 100% silicon.
With reference to block 210, the current collector (e.g., current collector 110 in
When provided in powder form, the electrochemically active material can be dispersed on the solid layer of electrode attachment substance (e.g., as in
As shown in
With reference to block 240, the electrochemically active material can be adhered to the side of the current collector via the electrode attachment substance (e.g., to form
Although
The electrode attachment substance can be the same as or different from the electrode attachment substance on the other side of the current collector. The electrode attachment substance can include any of the attachment substances described herein. For example, the electrode attachment substance can be provided in a substantially solid state. The attachment substance can be a thermoplastic film. In some instances, the attachment substance can be polyphenylene sulfide or any other polymer that is insoluble in a solvent e.g., at a temperature below about 200° C. Some other examples of attachment substance 120 can include films/foils of polyether ether ketone (PEEK), polyether sulfone (PES), polysulfone (PSL), or polyethylene terephthalate (PET).
The electrochemically active material can be the same as or different from the electrochemically active material on the other side of the current collector. The electrochemically active material can include any of the electrochemically active material described herein. For example, the electrochemically active material can be in powder or film form. The active material can include a silicon carbon composite material. In some examples, the active material can include at least about 50% to about 100% by weight of silicon, at least about 60% to about 100% by weight of silicon, at least about 70% to about 100% by weight of silicon, at least about 80% to about 100% by weight of silicon, or 100% by weight of silicon.
The electrochemically active material can be adhered to the current collector as described herein (e.g., by applying pressure and/or heat). In some instances, adhering the electrochemically active material on both sides of the current collector can occur simultaneously. In some instances, the electrochemically active material can be adhered sequentially on one side of the current collector and then on the other side of the current collector.
With reference to block 310, in some instances, the current collector (e.g., current collector 110 in
With reference to block 340, the electrochemically active material can be adhered to the side of the current collector via the electrode attachment substance (e.g., to form
The electrode attachment substance can be the same as or different from the electrode attachment substance on the other side of the current collector. The electrode attachment substance can include any of the attachment substances described herein. For example, the electrode attachment substance can be provided in a substantially solid state. The attachment substance can be a thermoplastic film. In some instances, the attachment substance can be polyphenylene sulfide or any other polymer that is insoluble in a solvent e.g., at a temperature below about 200° C. Some other examples of attachment substance 120 can include films/foils of polyether ether ketone (PEEK), polyether sultone (PES), polysulfone (PSU), or polyethylene terephthalate (PET).
The electrochemically active material can be the same as or different from the electrochemically active material on the other side of the current collector. The electrochemically active material can include any of the electrochemically active material described herein. For example, the electrochemically active material can be in powder or film form. The active material can include a silicon carbon composite material. In some examples, the active material can include at least about 50% to about 100% by weight of silicon, at least about 60% to about 100% by weight of silicon, at least about 70% to about 100% by weight of silicon, at least about 80% to about 100% by weight of silicon, or 100% by weight of silicon.
The electrochemically active material can be adhered to the current collector as described herein (e.g., by applying pressure and/or heat). In some instances, adhering the electrochemically active material on both sides of the current collector can occur simultaneously. In some instances, the electrochemically active material can be adhered sequentially on one side of the current collector and then on the other side of the current collector.
In various embodiments, after the electrode is formed, the electrode can be punched and processed. In certain embodiments, an electrode can be attached to a separator using an attachment substance similar to the electrode attachment substance described herein. For example, a separator and an electrode can be provided. A substantially solid layer of attachment substance can also be provided on the separator and/or the electrode. The separator and electrode can be adhered together via the attachment substance (e.g., by applying pressure and/or heat).
The following examples are provided to demonstrate the benefits of some embodiments of electrodes, electrochemical cells, and methods of forming the same. These examples are discussed for illustrative purposes and should not be construed to limit the scope of the disclosed embodiments.
Sample electrodes (e.g., anodes) were made in accordance with certain embodiments described herein. For example, two samples of silicon dominant electrochemically active material (i.e., carbon-silicon composite films made using pyrolyzed polymer and silicon material) were attached to copper foil using thermoplastic film (Torelina® 4 μm Polyphenylene sulfide (PPS) film) with a solvent free, high temperature and pressure method. The samples were pressed at about 28 MPa (e.g., about 4000 psi). The PPS film was adhered to the copper foil at about 220° C., and the silicon dominant electrochemically active material was adhered thereon at about 300° C. Electrodes were also made using binder in N-Methyl-2-pyrrolidone (NMP) solution. For example, two samples of the same silicon dominant electrochemically active material were attached to copper foil by coating it in a slurry of binder in NMP solution.
As described herein, new binders/adhesives (e.g., insoluble in solvents) can be tested and used to prepare battery electrodes. Certain embodiments described herein can attach electrochemically active material to a current collector using a roll to roll process and in some instances, be solvent free. Various embodiments can reduce manufacturing time and costs by not requiring a solvent in a slurry mix, coating of a slurry mix, and/or drying of a slurry mix.
Various embodiments have been described above. Although the invention has been described with reference to these specific embodiments, the descriptions are intended to be illustrative and are not intended to be limiting. Various modifications and applications may occur to those skilled in the art without departing from the true spirit and scope of the invention as defined in the appended claims.
This application claims the benefit of U.S. Provisional Application No. 62/596,035, filed Dec. 7, 2017. The entirety of the above referenced application is hereby incorporated by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3990098 | Mastrangelo | Nov 1976 | A |
| 5468358 | Ohkawa et al. | Nov 1995 | A |
| 5624606 | Wilson et al. | Apr 1997 | A |
| 5682288 | Wani | Oct 1997 | A |
| 5981107 | Hamano | Nov 1999 | A |
| 6103423 | Itoh et al. | Aug 2000 | A |
| 6287728 | Kajiura et al. | Sep 2001 | B1 |
| 6300013 | Yamada et al. | Oct 2001 | B1 |
| 6413672 | Suzuki et al. | Jul 2002 | B1 |
| 6432579 | Tsuji et al. | Aug 2002 | B1 |
| 6436576 | Hossain | Aug 2002 | B1 |
| 6489061 | Hossain | Dec 2002 | B1 |
| 6589696 | Matsubara et al. | Jul 2003 | B2 |
| 6770399 | Umeno et al. | Aug 2004 | B2 |
| 6946223 | Kusumoto et al. | Sep 2005 | B2 |
| 6949314 | Hossain | Sep 2005 | B1 |
| 7037581 | Aramata et al. | May 2006 | B2 |
| 7202000 | Iriyama et al. | Apr 2007 | B2 |
| 7303838 | Morita et al. | Dec 2007 | B2 |
| 7316792 | Kosuzu et al. | Jan 2008 | B2 |
| 7615314 | Kawakami et al. | Nov 2009 | B2 |
| 7670970 | Ko | Mar 2010 | B2 |
| 8603683 | Park et al. | Dec 2013 | B2 |
| 8709653 | Lee et al. | Apr 2014 | B2 |
| 9178208 | Park et al. | Nov 2015 | B2 |
| 9397338 | Park et al. | Jul 2016 | B2 |
| 9553303 | Park et al. | Jan 2017 | B2 |
| 9583757 | Park et al. | Feb 2017 | B2 |
| 9620809 | Turon Teixidor et al. | Apr 2017 | B2 |
| 9647259 | Park et al. | May 2017 | B2 |
| 9806328 | Park et al. | Oct 2017 | B2 |
| 9941509 | Park et al. | Apr 2018 | B2 |
| 9997765 | Park | Jun 2018 | B2 |
| 10103378 | Park et al. | Oct 2018 | B2 |
| 10388943 | Bonhomme et al. | Aug 2019 | B2 |
| 10431808 | Park et al. | Oct 2019 | B2 |
| 10461366 | Anderson et al. | Oct 2019 | B1 |
| 10516155 | Park et al. | Dec 2019 | B2 |
| 20040137327 | Gross et al. | Jul 2004 | A1 |
| 20050266304 | Honda et al. | Dec 2005 | A1 |
| 20060035149 | Nanba | Feb 2006 | A1 |
| 20060040182 | Kawakami et al. | Feb 2006 | A1 |
| 20060051670 | Aramata et al. | Mar 2006 | A1 |
| 20060051675 | Musha et al. | Mar 2006 | A1 |
| 20060127773 | Kawakami et al. | Jun 2006 | A1 |
| 20060134516 | Im et al. | Jun 2006 | A1 |
| 20060147802 | Yasuda et al. | Jul 2006 | A1 |
| 20060148191 | Mitchell et al. | Jul 2006 | A1 |
| 20060275668 | Peres et al. | Dec 2006 | A1 |
| 20070054190 | Fukui et al. | Mar 2007 | A1 |
| 20070054193 | Ota | Mar 2007 | A1 |
| 20070072084 | Katsushi et al. | Mar 2007 | A1 |
| 20070077490 | Kim et al. | Apr 2007 | A1 |
| 20070154811 | Oh et al. | Jul 2007 | A1 |
| 20070212610 | Sonobe et al. | Sep 2007 | A1 |
| 20070243469 | Kim et al. | Oct 2007 | A1 |
| 20080020282 | Kim et al. | Jan 2008 | A1 |
| 20080145757 | Mah et al. | Jun 2008 | A1 |
| 20080145761 | Petrat et al. | Jun 2008 | A1 |
| 20080160409 | Ishida et al. | Jul 2008 | A1 |
| 20080280207 | Patoux et al. | Nov 2008 | A1 |
| 20080286657 | Hasegawa et al. | Nov 2008 | A1 |
| 20090004566 | Shirane et al. | Jan 2009 | A1 |
| 20090023065 | Hwang | Jan 2009 | A1 |
| 20090029256 | Mah et al. | Jan 2009 | A1 |
| 20090053608 | Choi et al. | Feb 2009 | A1 |
| 20090061319 | Kim et al. | Mar 2009 | A1 |
| 20090087743 | Kim et al. | Apr 2009 | A1 |
| 20090117467 | Zhamu et al. | May 2009 | A1 |
| 20090117468 | Eom | May 2009 | A1 |
| 20090181304 | Miyamoto et al. | Jul 2009 | A1 |
| 20090202911 | Fukuoka et al. | Aug 2009 | A1 |
| 20090246632 | Fukui et al. | Oct 2009 | A1 |
| 20090269667 | Antonietti et al. | Oct 2009 | A1 |
| 20090280414 | Koh et al. | Nov 2009 | A1 |
| 20090283875 | Garandet et al. | Nov 2009 | A1 |
| 20090325072 | Maeda et al. | Dec 2009 | A1 |
| 20100015530 | Katayama et al. | Jan 2010 | A1 |
| 20100068628 | Ueda | Mar 2010 | A1 |
| 20100078599 | Kumta et al. | Apr 2010 | A1 |
| 20100119955 | Abe et al. | May 2010 | A1 |
| 20100143798 | Zhamu et al. | Jun 2010 | A1 |
| 20100216027 | Fujii | Aug 2010 | A1 |
| 20100233534 | Iwama et al. | Sep 2010 | A1 |
| 20100255376 | Park et al. | Oct 2010 | A1 |
| 20100285352 | Juzkow et al. | Nov 2010 | A1 |
| 20100297497 | Takahata | Nov 2010 | A1 |
| 20110020701 | Park et al. | Jan 2011 | A1 |
| 20110177393 | Park | Jul 2011 | A1 |
| 20110206974 | Inoue et al. | Aug 2011 | A1 |
| 20110236761 | Endo et al. | Sep 2011 | A1 |
| 20120156562 | Kobayashi et al. | Jun 2012 | A1 |
| 20130202960 | Kim | Aug 2013 | A1 |
| 20130260205 | Kwon | Oct 2013 | A1 |
| 20130302666 | Park | Nov 2013 | A1 |
| 20140057170 | Cha et al. | Feb 2014 | A1 |
| 20140170451 | Iwasaki et al. | Jun 2014 | A1 |
| 20140170475 | Park | Jun 2014 | A1 |
| 20140170498 | Park | Jun 2014 | A1 |
| 20140295290 | Park et al. | Oct 2014 | A1 |
| 20150010830 | Park et al. | Jan 2015 | A1 |
| 20150137822 | Joe et al. | May 2015 | A1 |
| 20160064731 | Jung et al. | Mar 2016 | A1 |
| 20160359164 | Mui et al. | Dec 2016 | A1 |
| 20170040598 | Wang et al. | Feb 2017 | A1 |
| 20170133664 | Park | May 2017 | A1 |
| 20170133665 | Park | May 2017 | A1 |
| 20170155126 | Park | Jun 2017 | A1 |
| 20170170510 | Turon Teixidor et al. | Jun 2017 | A1 |
| 20170222278 | Kwon | Aug 2017 | A1 |
| 20170279093 | Park | Sep 2017 | A1 |
| 20180062154 | Park et al. | Mar 2018 | A1 |
| 20180198114 | Bonhomme et al. | Jul 2018 | A1 |
| 20180219211 | Park et al. | Aug 2018 | A1 |
| 20180226642 | Wang et al. | Aug 2018 | A1 |
| 20180287129 | Park | Oct 2018 | A1 |
| 20190178944 | Rango et al. | Jun 2019 | A1 |
| 20190181426 | Park et al. | Jun 2019 | A1 |
| 20190181434 | Lee et al. | Jun 2019 | A1 |
| 20190181440 | Park et al. | Jun 2019 | A1 |
| 20190181441 | Ji et al. | Jun 2019 | A1 |
| 20190181491 | Park et al. | Jun 2019 | A1 |
| 20190181492 | Liu et al. | Jun 2019 | A1 |
| 20190181500 | Ji et al. | Jun 2019 | A1 |
| 20190181501 | Ji et al. | Jun 2019 | A1 |
| 20190181502 | Ji et al. | Jun 2019 | A1 |
| 20190190069 | Ji et al. | Jun 2019 | A1 |
| 20190190070 | Ji et al. | Jun 2019 | A1 |
| 20190355966 | Kamath et al. | Nov 2019 | A1 |
| 20190372088 | Bonhomme et al. | Dec 2019 | A1 |
| Number | Date | Country |
|---|---|---|
| 1667855 | Sep 2005 | CN |
| 102834955 | Dec 2012 | CN |
| 0 949 702 | Oct 1999 | EP |
| 1 054 462 | Nov 2000 | EP |
| 1 722 429 | Nov 2006 | EP |
| 2 113 955 | Nov 2009 | EP |
| 2 400 583 | Dec 2011 | EP |
| 3 382 776 | Oct 2018 | EP |
| 2 483 372 | Mar 2012 | GB |
| 2000-106218 | Apr 2000 | JP |
| 2000-133274 | May 2000 | JP |
| 2000-173667 | Jun 2000 | JP |
| 2000-272911 | Oct 2000 | JP |
| 2001-006682 | Jan 2001 | JP |
| 2002-151157 | May 2002 | JP |
| 2002-246013 | Aug 2002 | JP |
| 2002-367601 | Dec 2002 | JP |
| 2003-165715 | Jun 2003 | JP |
| 2004-006285 | Jan 2004 | JP |
| 2004-095198 | Mar 2004 | JP |
| 2004-103405 | Apr 2004 | JP |
| 2004-327319 | Nov 2004 | JP |
| 2005-158721 | Jun 2005 | JP |
| 2007-073334 | Mar 2007 | JP |
| 2007-123141 | May 2007 | JP |
| 2007-165061 | Jun 2007 | JP |
| 2007-531245 | Nov 2007 | JP |
| 2008-153006 | Jul 2008 | JP |
| 2009-026760 | Feb 2009 | JP |
| 2009-037842 | Feb 2009 | JP |
| 2009-176540 | Aug 2009 | JP |
| 2010-146901 | Jul 2010 | JP |
| 2012-014866 | Jan 2012 | JP |
| 2012-028322 | Feb 2012 | JP |
| 2012-527085 | Nov 2012 | JP |
| 2012-252962 | Dec 2012 | JP |
| 2013-045759 | Mar 2013 | JP |
| 2017107851 | Jun 2017 | JP |
| 2001-0081928 | Aug 2001 | KR |
| 2009-0011888 | Feb 2009 | KR |
| 2009-0109225 | Oct 2009 | KR |
| WO 98028804 | Jul 1998 | WO |
| WO 2010092977 | Aug 2010 | WO |
| WO 2011088472 | Jul 2011 | WO |
| WO 2012050407 | Apr 2012 | WO |
| 2014163986 | Oct 2014 | WO |
| WO 2019113340 | Jun 2019 | WO |
| WO 2019113346 | Jun 2019 | WO |
| WO 2019113349 | Jun 2019 | WO |
| Entry |
|---|
| International Search Report and Written Opinion for International Application No. PCT/US2018/064301, dated Feb. 26, 2019 in 52 pages. |
| Gao et al., “Engineered Si Sandwich Electrode: Si Nanoparticles/Graphite Sheet Hybrid on Ni Foam for Next-Generation High-Performance Lithium-Ion Batteries”, ACS Applied Materials & Interfaces, 2015, vol. 7, No. 3, pp. 1693-1698. |
| Kamali et al., “Review on Carbon and Silicon Based Materials as Anode Materials for Lithium Ion Batteries”, Journal of New Materials for Electrochemical Systems, 2010, vol. 13, pp. 147-160. |
| Choi et al., “Enhanced Electrochemical Properties of a Si-based Anode Using an Electrochemically Active Polyamide Imide Binder”, Journal of Power Sources, 2008, vol. 177, pp. 590-594. |
| Cui et al., “Inorganic Glue Enabling High Performance of Silicon Particles as Lithium Ion Battery Anode”, Journal of the Electrochemical Society, 2011, vol. 158, No. 5, A592-A596. |
| Datta, et al., “Silicon, Graphite and Resin Based Hard Carbon Nanocomposite Anodes for Lithium Ion Batteries”, Journal of Power Sources, Feb. 10, 2007, vol. 165, No. 1, pp. 368-378. |
| Du et al., “Electrochemistry of CuxSi1-x Alloys in Li Cells”, Journal of the Electrochemical Society, 2016, vol. 163, No. 7, pp. A1275-A1279. |
| International Search Report and Written Opinion for International Application No. PCT/US2014/019669, dated Aug. 28, 2014 in 13 pages. |
| International Preliminary Report on Patentability and Written Opinion for International Application No. PCT/US2014/019669, dated Sep. 24, 2015 in 10 pages. |
| Ji et al., “Electrospun Carbon Nanofibers Containing Silicon Particles as an Energy-Storage Medium”, Carbon, Nov. 2009, vol. 47, No. 14, pp. 3219-3226. |
| Lee et al., “Graphene-Silicon Composite for Li-Ion Battery Anodes”, http://apps.aiche.org/proceedings/Abstracts.aspx?PaperiD=162914, dated Sep. 11, 2009 [Retrieved Jun. 23, 2011]. |
| Lee et al., “Silicon Nanoparticles-Graphene Paper Composites for Li ion Battery Anodes”, Chemical Communications, 2010, vol. 46, No. 12, pp. 2025-2027. |
| Li et al., “Copper Deposition and Thermal Stability Issues in Copper-Based Metallization for ULSI Technology”, Materials Science Reports, vol. 9, No. 1, 1992, pp. 1-51. |
| Ludwig et al., “Solvent-Free Manufacturing of Electrodes for Lithium-ion Batteries”, Scientific Reports, Mar. 17, 2016, 6:23150, pp. 1-10. |
| Ma et al., “Si-Based Anode Materials for Li-Ion Batteries: A Mini Review”, Nano-Micro Letters, 2014, vol. 6, No. 4, pp. 347-358. |
| Mazouzi et al., “Very High Surface Capacity Observed Using Si Negative Electrodes Embedded in Copper Foam as 3D Current Collectors”, Advanced Energy Materials, 2014, vol. 4, 1301718, pp. 1-13. |
| Sufryd et al., “Experimental investigation of the Cu-Si phase diagram at x(Cu)>0.72”, Intermetallics, 2011, vol. 19, pp. 1479-1488. |
| Wolf, H. et al., “Carbon-Fiber-Silicon Nanocomposites for Lithium-Ion Battery Anodes by Microwave Plasma Chemical Vapor Deposition”, Journal of Power Sources, May 1, 2009, vol. 190, No. 1, pp. 157-161. |
| International Searching Authority, “Intenational Search Report and Written Opinion”, issued in connection with Application No. PCT/US2018/064301, Feb. 26, 2019, 13 pages. |
| Written Opinion for International Application No. PCT/US2018/064301, dated Dec. 3, 2019 in 5 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20190181431 A1 | Jun 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62596035 | Dec 2017 | US |