The demand for high capacity rechargeable batteries is strong and increasing each year. Many applications, such as aerospace, medical devices, portable electronics, and automotive applications, require high gravimetric and/or volumetric capacity cells. Lithium ion electrode technology can provide significant improvements in this area. However, to date, lithium ion cells employing graphite, is limited to theoretical specific energy density of only 372 mAh/g.
Silicon, germanium, tin, and many other materials are attractive active materials because of their high electrochemical capacity. For example, silicon has a theoretical capacity of about 4200 mAh/g, which corresponds to the Li.sub.4.4Si phase. Yet, many of these materials are not widely used in commercial lithium ion batteries. One reason is that some of these materials exhibit substantial changes in volume during cycling. For example, silicon swells by as much as 400% when charged to its theoretical capacity. Volume changes of this magnitude can cause substantial stresses in the active material structures, resulting in fractures and pulverization, loss of electrical and mechanical connections within the electrode, and capacity fading.
Conventional electrodes include polymer binders that are used to hold active materials on the substrate. Most polymer binders are not sufficiently elastic to accommodate the large swelling of some high capacity materials. As a result, active material particles tend to separate from each other and the current collector. Overall, there is a need for improved applications of high capacity active materials in battery electrodes that minimize the drawbacks described above.
The foregoing discussion of the prior art derives from U.S. Pat. Nos. 8,257,866 and 8,450,012 in which the inventors propose addressing the elasticity and swelling problems of prior art materials by providing electrochemically active electrode materials comprising a high surface area template containing a metal silicide and a layer of high capacity active material deposited over the template. The template reportedly serves as a mechanical support for the active material and/or an electrical conductor between the active material and, for example, a substrate. According to the inventors, due to the high surface area of the template, even a thin layer of the active material can provide sufficient active material loading and corresponding electrode capacity per surface area. As such, the thickness of the active material layer may be maintained sufficiently small to be below its fracture threshold to preserve its structural integrity during battery cycling. The thickness and/or composition of the active layer may also be specifically profiled to reduce swelling near the substrate interface and preserve the interface connection.
The present invention overcomes the aforesaid and other disadvantages of the prior art by providing electrodes formed of extremely fine filaments of the valve metal tantalum or other valve metals produced following the teachings of my prior U.S. Pat. Nos. 5,034,857 and 8,673,025, the contents of which are incorporated herein by reference.
In my prior U.S. Pat. No. 5,034,857, I disclose an approach to the production of extremely fine valve metal filaments, such as tantalum, for capacitor use. The benefits of fine filaments relative to fine powders are higher purity, lower cost, uniformity of cross section, and ease of dielectric infiltration, while still maintaining high surface area for anodization. The uniformity of cross section results in capacitors with high specific energy density, lower ESR and ESL, and less sensitivity to forming voltage and sintering temperature as compared to fine powder compacts.
As disclosed in my aforesaid '857 U.S. patent, valve metal filaments, preferably tantalum, are fabricated by combining filaments of the valve metal with a ductile metal so as to form a billet. The second, ductile metal is different from the metal that forms the filaments. The filaments are substantially parallel, and are separated from each other and from the billet surface by the second, ductile metal. The billet is reduced by conventional means—e.g., extrusion and wire drawing—to the point where the filament diameter is in the range of 0.2 to 5.0 microns in diameter. At that point, the second, ductile metal is removed, preferably by leaching in mineral acids, leaving the valve metal filaments intact. The filaments are suitable for use in tantalum capacitor fabrication.
Other patents involving valve metal filaments and fibers, their fabrication, or articles made therefrom include U.S. Pat. No. 3,277,564, (Webber), U.S. Pat. No. 3,379,000 (Webber), U.S. Pat. No. 3,394,213, (Roberts), U.S. Pat. No. 3,567,407 (Yoblin), U.S. Pat. No. 3,698,863 (Roberts), U.S. Pat. No. 3,742,369 (Douglass), U.S. Pat. No. 4,502,884 (Fife), U.S. Pat. No. 5,217,526 (Fife), U.S. Pat. No. 5,306,462 (Fife), U.S. Pat. No. 5,284,531 (Fife), and U.S. Pat. No. 5,245,514 (Fife).
See also my earlier U.S. Pat. No. 5,869,196 in which I describe a process for fabrication of fine-valve metal filaments for use as porous metal compacts used in the manufacture of electrolytic capacitors. According to my '196 U.S. patent, a metal billet consisting of multiple filaments of a valve metal, preferably tantalum, is contained within and spaced apart by a ductile metal, preferably copper. The billet is reduced by conventional means, such as extrusion and wire drawing, the resulting composite product is cut into lengths, and the ductile metal separating the valve metal components is removed by leaching in acid. A similar compaction technique has been proposed to fabricate composites by providing continuous layers of tantalum and copper sheets layered together in a jellyroll. The jellyroll is then reduced to a small size by extrusion and drawing. Starting with sheets of tantalum and copper offers advantages over working with filaments. However, at reduced sizes, the copper cannot readily be leached out due to the presence of the continuous tantalum layers.
Also, in my prior U.S. Pat. No. 8,858,738, I describe improvements over the prior art much as described in my '196 U.S. patent by creating one or more open slots in the starting billet stage and filling the slots with ductile metal prior to extrusion and drawing. After extrusion and drawing to small size, the slots remain. As a result, the ductile metal readily may be leached and removed from between the tantalum layers. The resulting product is a series of compacted tantalum layers each progressively of smaller width. In one embodiment of the invention, continuous layers of tantalum and copper are layered together in a jellyroll and formed into a billet which is circular in cross-section, and the slots are concentrically evenly spaced radially around the billet. The resulting product is a series of concentric split tubes each progressively of smaller diameter towards the center.
As described in my '738 patent, employing a foil or sheet of tantalum as opposed to filaments greatly simplifies assembly of the billet. Employing sheet tantalum also ensures greater uniformity since the thickness of the starting sheet can be controlled more readily than using a multiple of separate filaments. This in turn produces substantially more uniform capacitor material resulting in substantially higher values of CV/g. See also my prior U.S. Pat. No. 8,257,866 and PCT/US2008/086460.
I have now found that electrodes formed of extremely fine valve metal filaments as described in my aforesaid U.S. Patents advantageously may be employed as electrode material for high capacity rechargeable batteries, particularly lithium ion rechargeable batteries.
The present invention in one aspect provides an electrically active electrode material for use with a lithium ion cell, the electrochemically active material electrode material comprising a sheet or mat formed of a valve metal material formed of filaments of a valve metal not larger than about 10 microns in cross section, and coated with an electrochemically active material.
In another embodiment the valve metal is selected from the group consisting of tantalum, niobium, an alloy of tantalum, an alloy of niobium, hafnium, titanium and aluminum
In another embodiment the filaments have a thickness of less than about 5-10 microns, preferably below about 1 micron.
In another embodiment the electrochemically active material comprises silicon nanoparticles.
In still yet another embodiment the electrode material is formed into an anode.
The present invention also provides a method of forming an electrode substrate useful for forming a lithium ion battery comprising the steps of:
In one embodiment the valve metal is selected from the group consisting of tantalum, niobium, an alloy of tantalum, an alloy of niobium, hafnium, titanium and aluminum.
In another embodiment the filaments have a thickness of less than about 5-10 microns, preferably below about 1 micron.
In still another embodiment, the electrochemically active material comprises silicon nanoparticles, germanium or tin.
In still yet another embodiment, the electrically active electrode material is formed into an anode.
The present invention also provides a lithium ion battery comprising an assembly containing an anode and a cathode separated from one another, and an electrolyte, wherein the anode is formed of electrically active electrode material as claimed in claim 1.
In one embodiment, the valve metal is selected from the group consisting of tantalum, niobium, an alloy of tantalum, an alloy of niobium, hafnium, titanium and aluminum.
In another embodiment the filaments have a thickness of less than about 5-10 microns, preferably below about 1 micron.
In still yet another embodiment electrochemically active material comprises silicon nanoparticles.
Further features and advantages of the present invention will be seen from the following detailed description, taken in conjunction with the accompanying drawings, wherein,
Referring to
Etching in acid removes the copper from between the tantalum filaments. After etching, one is left with a plurality of short filaments of tantalum. The tantalum filaments are then washed in water in a washing station 20, and the wash water is partially decanted to leave a slurry of tantalum filaments in water. The slurry of tantalum filaments in water is then cast as a thin sheet using, for example, a Doctor Blade at casting station 22. Excess water is removed, for example, by rolling at a rolling station 24. The resulting mat is then further compressed and dried at a drying station 26.
As an alternative to “Doctor Blade formation”, the thin sheet may be formed by spray casting the slurry onto to a substrate, excess water removed and the resulting mat pressed and dried as before.
There results a highly porous thin sheet of tantalum filaments substantially uniform in thickness.
As reported in my aforesaid PCT application, an aqueous slurry of chopped filaments will adhere together sufficiently so that the fibers may be cast as a sheet which can be pressed and dried into a stable mat. This is surprising in that the metal filaments themselves do not absorb water. Notwithstanding, as long as the filaments are not substantially thicker than about 10 microns, they will adhere together. On the other hand, if the filaments are much larger than about 10 microns, they will not form a stable mat or sheet. Thus, it is preferred that the filaments have a thickness of less than about 10 microns, and preferably below 1 micron thick. To ensure an even distribution of the filaments, and thus ensure production of a uniform mat, the slurry preferably is subjected to vigorous mixing by mechanical stirring or vibration.
The density of the resulting tantalum mat may be varied simply by changing the final thickness of the mat.
Also, if desired, multiple layers may be stacked to form thicker mats 30 that may be desired, for example, for high density applications.
The resulting tantalum mat comprises a porous mat of sub-micron size tantalum fi laments in contact with one another, whereby to form a conductive mat.
Referring to
While the invention has been described in connection with the use of tantalum disposed within a copper matrix, valve metals other than tantalum, such as niobium, an alloy of tantalum or niobium, hafnium, titanium and its alloys can be used. Similarly, ductile metal matrix materials other than copper, such as copper-based alloys, also may successfully be employed in the practice of the invention. Still other changes may be made without departing from the spirit and scope of the invention.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/US2016/032751 | 5/16/2016 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2016/187143 | 11/24/2016 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
3277564 | Webber et al. | Oct 1966 | A |
3379000 | Webber et al. | Apr 1968 | A |
3394213 | Roberts et al. | Jul 1968 | A |
3567407 | Yoblin | Mar 1971 | A |
3698863 | Roberts et al. | Oct 1972 | A |
3742369 | Douglass | Jun 1973 | A |
3817746 | Tsuei | Jun 1974 | A |
4378330 | Verhoeven et al. | Mar 1983 | A |
4502884 | Fife | Mar 1985 | A |
4551220 | Oda | Nov 1985 | A |
5034857 | Wong | Jul 1991 | A |
5062025 | Verhoeven et al. | Oct 1991 | A |
5185218 | Brokman | Feb 1993 | A |
5217526 | Fife | Jun 1993 | A |
5245415 | Mimura | Sep 1993 | A |
5245514 | Fife et al. | Sep 1993 | A |
5284531 | Fife | Feb 1994 | A |
5306462 | Fife | Apr 1994 | A |
5635151 | Zhang et al. | Jun 1997 | A |
5869196 | Wong et al. | Feb 1999 | A |
5908715 | Liu et al. | Jun 1999 | A |
5910382 | Goodenough et al. | Jun 1999 | A |
6007945 | Jacobs et al. | Dec 1999 | A |
6143448 | Fauteux et al. | Nov 2000 | A |
6316143 | Foster et al. | Nov 2001 | B1 |
6475673 | Yamawaki et al. | Nov 2002 | B1 |
6524749 | Kaneda et al. | Feb 2003 | B1 |
6666961 | Skoczylas | Dec 2003 | B1 |
7073559 | O'Leary et al. | Jul 2006 | B2 |
7094499 | Hung | Aug 2006 | B1 |
8257866 | Loveness et al. | Sep 2012 | B2 |
8450012 | Cui et al. | May 2013 | B2 |
8603683 | Park et al. | Dec 2013 | B2 |
8637185 | Berdichevsky et al. | Jan 2014 | B2 |
8673025 | Wong | Mar 2014 | B1 |
8722226 | Chiang et al. | May 2014 | B2 |
8722227 | Chiang et al. | May 2014 | B2 |
8858738 | Wong | Oct 2014 | B2 |
8906447 | Zhamu | Dec 2014 | B2 |
8993159 | Chiang et al. | Mar 2015 | B2 |
9065093 | Chiang et al. | Jun 2015 | B2 |
9178208 | Park et al. | Nov 2015 | B2 |
9397338 | Park et al. | Jul 2016 | B2 |
20060237697 | Kosuzu et al. | Oct 2006 | A1 |
20070020519 | Kim et al. | Jan 2007 | A1 |
20070031730 | Kawakami et al. | Feb 2007 | A1 |
20070122701 | Yamaguchi | May 2007 | A1 |
20070148544 | Le | Jun 2007 | A1 |
20090176159 | Zhamu et al. | Jul 2009 | A1 |
20090269677 | Hirose | Oct 2009 | A1 |
20100047671 | Chiang et al. | Feb 2010 | A1 |
20100239915 | Hochgattrerer et al. | Sep 2010 | A1 |
20100255376 | Park et al. | Oct 2010 | A1 |
20100310941 | Kumta | Dec 2010 | A1 |
20110020701 | Park et al. | Jan 2011 | A1 |
20110086271 | Lee | Apr 2011 | A1 |
20110177393 | Park et al. | Jul 2011 | A1 |
20110189510 | Caracciolo et al. | Aug 2011 | A1 |
20110189520 | Carter et al. | Aug 2011 | A1 |
20110200848 | Chiang et al. | Aug 2011 | A1 |
20110229761 | Cui et al. | Sep 2011 | A1 |
20110274948 | Duduta et al. | Nov 2011 | A1 |
20110311888 | Garsuch | Dec 2011 | A1 |
20120164499 | Chiang et al. | Jun 2012 | A1 |
20120219860 | Wang et al. | Aug 2012 | A1 |
20130019468 | Ramasubramanian et al. | Jan 2013 | A1 |
20130055559 | Slocum et al. | Mar 2013 | A1 |
20130065122 | Chiang | Mar 2013 | A1 |
20130314844 | Chen et al. | Nov 2013 | A1 |
20130323581 | Singh et al. | Dec 2013 | A1 |
20130337319 | Doherty et al. | Dec 2013 | A1 |
20130344367 | Chiang et al. | Dec 2013 | A1 |
20140004437 | Slocum et al. | Jan 2014 | A1 |
20140030623 | Chiang et al. | Jan 2014 | A1 |
20140057171 | Sohn et al. | Feb 2014 | A1 |
20140065322 | Park et al. | Mar 2014 | A1 |
20140154546 | Carter et al. | Jun 2014 | A1 |
20140170498 | Park | Jun 2014 | A1 |
20140170524 | Chiang et al. | Jun 2014 | A1 |
20140234699 | Ling et al. | Aug 2014 | A1 |
20140248521 | Chiang et al. | Sep 2014 | A1 |
20140255774 | Singh et al. | Sep 2014 | A1 |
20140266066 | Turon Teixidor et al. | Sep 2014 | A1 |
20140315097 | Tan et al. | Oct 2014 | A1 |
20140322595 | Zhang et al. | Oct 2014 | A1 |
20141315097 | Tan et al. | Oct 2014 | |
20150044553 | Chen | Feb 2015 | A1 |
20150099185 | Joo et al. | Apr 2015 | A1 |
20150129081 | Chiang et al. | May 2015 | A1 |
20160190599 | Kim et al. | Jun 2016 | A1 |
Number | Date | Country |
---|---|---|
104040764 | Sep 2014 | CN |
2014-116318 | Jun 2014 | JP |
2014-0097967 | Aug 2014 | KR |
189157 | May 2013 | SG |
WO2009082631 | Jul 2009 | WO |
WO 2012057702 | May 2012 | WO |
WO 2012138302 | Oct 2012 | WO |
WO 2014093876 | Jun 2014 | WO |
WO 2014208996 | Dec 2014 | WO |
WO 2015038076 | Mar 2015 | WO |
Entry |
---|
“Comparison of battery types” Wikipedia article https://en.wikipedia.prg/wiki/Comparison_of_battery_type, Jul. 8, 2015 (1pg). |
“Design of Highly Integrated Structures with Additive Manufacturing and Composites” pdlz Product Development Group Zurich, accessed Sep. 18, 2015 (2 pgs). |
“Lithium-ion battery” Wikipedia page https://wikipedia.org/wiki/Lithium-ion_battery#Materials_of_commercial_cells, Jul. 7, 2015 (27 pgs). |
“Ultra-fast charging batteries that can be 70% recharges in just two minutes” Nanyang Tehcnological University, dated Oct. 13, 2014 (3 pgs). |
Chandler, David L., “Printing transparent glass in 3-D” MIT News, Sep. 14, 2015 (3 pgs). |
Chemical Elements.com “Periodic Table: Transition Metals” accessed Aug. 7, 2015 (1 pg). |
Electrochemistry at the Nanoscale, edited by Patrik Schmuki, Sannakaisa Virtanen, Google Books print out, accessed Aug. 7, 2015 (1 pg). |
Fu, Kun et al., “Aligned Carbon Nanotube-Silicon Sheets: A Novel Nano-architecture for Flexible Lithium Ion Battery Electrodes” Advanced Materials ,2013, 25, 5109-5114 (6 pgs). |
Galatzer-Levy, Jeanne “Beyond the lithium ion, toward a better performing battery” University of Illinois, Chicago, Apr. 17, 2015 (3 pgs). |
International Preliminary Report on Patentability issued in application No. PCT/US2016/032751, dated Nov. 21, 2017 (5 pgs). |
International Search Report and Written Opinion issued in application No. PCT/US2016/032751, dated Sep. 22, 2016 (9 pgs). |
IntraMicron web page accessed Sep. 11, 2015 (9 pgs). |
Press Trust of India, “Lithium Ion Batteries May Soon Be Replaced With Magnesium Ion Tech” NDTV Gadget Beta, Jul. 8, 2015 (2 pgs). |
Tang, Yuxin et al., “Mechanical Force-Driven Growth of Elongated Bending TiO2-based Nanotubular Materials for Ultrafast Rechargeable Lithium Ion Batteries” Advanced Materials, 2014, 26, 6111-6118 (8 pgs). |
Templeton, Graham, “Magnesium-ion batteries could prove that two electrons are better than one” ExtremeTech.com, Nov. 5, 2014 (4 pgs). |
Yarris, Lynn, “Dispelling a Misconception About Mg-Ion Batteries: Supercomputer Simulations at Berkeley Lab Provide a Path to Better Designs” Oct. 16, 2014 (3 pgs). |
Zhao, Xin et al., “In-Plane Vacancy-Enabled High-Power Si-Graphene Composite Electrode for Lithium-Ion Batteries” Advanced Energy Materials, 1, 2011, p. 1079-1084 (6 pgs). |
U.S. Appl. No. 14/871,677, filed Sep. 30, 2015. |
European Search Report for corresponding EP Application Serial No. 16797109.2, dated Jan. 4, 2019 (9 pages). |
Number | Date | Country | |
---|---|---|---|
20180287163 A1 | Oct 2018 | US |
Number | Date | Country | |
---|---|---|---|
62162064 | May 2015 | US |