Nano-scale/nanostructured Si coating on valve metal substrate for lib anodes

An improved structure of nano-scaled and nanostructured Si particles is provided for use as anode material for lithium ion batteries. The Si particles are prepared as a composite coated with MgO and metallurgically bonded over a conductive refractory valve metal support structure.

Skip to: Description  ·  Claims  ·  References Cited  · Patent History  ·  Patent History
Description
CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from US Provisional Application Ser. No. 62/382,696, filed Sep. 1, 2016, the contents of which are incorporated herein by reference.

FIELD OF INVENTION

The present invention relates to improvements in anode materials for use in lithium ion batteries, and will be described in connection with such utility, although other utilities are contemplated.

BACKGROUND OF THE INVENTION

Silicon is a promising material for high capacity anodes in lithium ion batteries (LIB). When alloyed with lithium, the specific capacity (mAh/g) of silicon is an order of magnitude higher than conventional graphite anode materials. However, silicon exhibits a large volume change (up to 400% expansion and contraction) during lithiation (charging) and delithiation (discharging), respectively. For bulk silicon, this creates structural stress gradients within the silicon and results in fractures and mechanical stress failure (pulverization) thereby decreasing effective electrical contact and lifetime of the silicon anode.

Considerable efforts have been undertaken to overcome this intrinsic issue by controlling the morphology and limiting the size of silicon particles to a size below which silicon is less likely to fracture, approximately 50 nm.

Various attempts to avoid the physical damage caused by silicon's expansion/contraction have included nanoscaled and nanostructured silicon in forms such as thin films; nanowires; nanotubes; nanoparticles; mesoporous materials; and nanocomposites. Most of these approaches do not provide viable, cost effective solutions.

One promising method utilizes Si—MgO composites formed by mechanical alloying/solid phase reaction of SiO2 and magnesium according to the reaction:
2Mg(s)+SiO2(s)→2MgO(s)+Si(s)  (Formula I)
The MgO matrix has shown to buffer the effects of volumetric changes; however, these composites have relatively low electrical conductivity rendering them poorly effective as anode material.

Sub-micron scale, electrochemically active particles dispersed on conductive substrates and supports have long been used for electrochemical cells including fuel cells and batteries. This support structure is an important component with regard to cell efficiency and lifetime. Valve (or refractory) metals particularly, (specifically: Titanium, Niobium, Tantalum, and their alloys) have been used as substrates for electrochemically active materials for over 70 years in application of chemical processing and cathodic protection. These applications utilize the formation of a passivating oxide film over the exposed valve metal areas, as a means of creating a conductive and electrochemically stable support structure for the active material.

Mg has long been used as a magnesiothermic reducing agent for purification of refractory metals. This process is common in production of high capacity, high surface tantalum powders for capacitor applications occurring via the vapor/solid phase reaction:
5Mg(g)+Ta2O5(s)→5MgO(s)+2Ta(s)  (Formula II)
The resulting magnesium oxide forms a surface coating over the host Ta particles, and is removed using mineral acids.

In one aspect the present invention provides electrically active electrode material for use with a lithium ion cell, the electrochemically active material electrode material comprising a valve metal substrate material formed of filaments or particles of a valve metal not larger than about 10 microns in cross section, and coated with metallurgically bonded silicon particles.

In a preferred 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 preferred embodiment, the valve metal filaments have a thickness of less than about 5-10 microns, and preferably have a thickness below about 1 micron.

In one aspect the silicon coating is comprised of nanoscaled nanoparticles.

In another aspect the silicon particles are coated on the valve metal substrate in a stabilizing MgO matrix.

In still another aspect, electrically active electrode material as above described 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: (a) providing valve metal substrate material formed of filaments or particles of a valve metal not larger than about 10 microns in cross section; and, (b) coating the valve metal substrate material with metallurgically bonded silicon formed by a magnesiothermic reaction of magnesium with silica and the valve metal.

In one aspect of the method, the magnesiothermic reaction is conducted under vacuum or in an inert gas at elevated temperature, preferably an elevated temperature selected from a group consisting of 800-1200° C., 900-1100° C. and 950-1050° C.

In another aspect of the method, the magnesiothermic reaction is conducted for time selected from 2-10 hours, 4-8 hours and 5-6 hours.

In yet another aspect of the method includes the step of removing at least some of the magnesium oxide following the reaction by acid etching.

In one preferred aspect of the method, 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 preferred aspect of the method, the filaments or fibers have a thickness of less than about 5-10 microns, and preferably a thickness below about 1 micron.

In another aspect of the method, the electrochemically active material comprises silicon nanoparticles.

The present invention also provides a lithium ion battery comprising a case containing an anode and a cathode separated from one another, and an electrolyte, wherein the anode is formed of electrically active electrode material comprising the steps of: (a) providing valve metal substrate material formed of filaments or particles of a valve metal not larger than about 10 microns in cross section; and, (b) coating the valve metal substrate material with metallurgically bonded silicon formed by a magnesiothermic reaction of magnesium with silicon and the valve metal.

In yet another aspect of the cell, the valve metal is selected from the group consisting of tantalum, niobium, an alloy of tantalum, an alloy of niobium, hafnium, titanium and aluminum.

SUMMARY OF THE INVENTION

The present invention provides a combination reaction (or co-reaction) of Mg de-oxidation of a refractory metal substrate and substantially simultaneous reduction of SiO2 (silica) to produce nanoscale coating of nanostructured Si inside a stabilizing MgO coating, both of which are metallurgically bonded to a valve metal substrate. The oxide impurities in the valve metal and the SiO2 react substantially concurrently to form a nanoscale nanostructure of pure Si which is firmly bonded to the valve metal substrate, e.g. tantalum (Ta) via the reaction:
9Mg(g)+2Ta2O5(s)+2SiO2→4Ta(s)+2Si(s)+9MgO(s)  (Formula III)
The overall process involves mixing valve metal particles, e.g., tantalum, with SiO2 nanoparticles of 4 to 200 micron size, preferably 10 to 100 micron size, more preferably 20 to 50 micron size in an aqueous based solution or gel. In one method, SiO2 particles are impregnated into a preformed, porous mat of tantalum fibers as an aqueous gel of SiO2 nanoparticles. In another method, loose particles of tantalum are mixed with SiO2 particles. The resulting mixture is then subjected to a magnesiothermic reduction via Formula III under vacuum or inert gas at temperatures between 900-1100° C. for 2 to 10 hrs. The magnesium reduces the silica and the oxide impurities within the tantalum fiber thereby permitting the silicon to metallurgically bond to the tantalum substrate. The magnesium oxide which results may remain, or be removed for example, by acid etching. The resulting structure is a spongy, high surface area conductive, electrochemically stable refractory metal substrate coated with a composite of sub-micron Si particles within a MgO coating.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features and advantages of the present invention will be seen from the following detailed description, taken in conjunction with the accompanying drawings, wherein:

FIG. 1 is a schematic block diagram of a process for providing anode material in accordance with the present invention;

FIGS. 2 and 3 are SEM photographs at two different magnifications showing nanoscaled nanostructure of Si particles metallurgically bonded to Ta support particles in accordance with the present invention;

FIG. 4 plots capacity versus time of anode material made in accordance with the present invention;

FIG. 5 plots coulomb efficiency versus time of anode material made in accordance with the present invention;

FIG. 6 plots differential capacity versus cell voltage for a lithium ion battery anode made in accordance with the present invention;

FIG. 7 is a cross-sectional view of a rechargeable battery in accordance with the present invention; and

FIG. 8 is a perspective view of a battery made in accordance with the present invention.

 DETAILED DESCRIPTION OF THE INVENTION

In one embodiment of the invention, the refractory metal is formed of micron size (e.g. not larger than about 10 microns in across) tantalum filaments formed as described for example, in my earlier U.S. Pat. Nos. 9,155,605, 5,869,196, 7,146,709, and PCT WO2016/187143 A1, the contents of which are incorporated herein by reference.

Referring to FIG. 1, the production process starts with the fabrication of valve metal filaments, preferably tantalum, by combining filaments or wires of tantalum with a ductile material, such as copper to form a billet at step 10. The billet is then sealed in an extrusion can in step 12, and extruded and drawn in step 14 following the teachings of my '196 U.S. patent. The extruded and drawn filaments are then cut or chopped into short segments, typically 1/16th-¼th inch long at a chopping station 16. Preferably the cut filaments all have approximately the same length. Actually, the more uniform the filament, the better. The chopped filaments are then passed to an etching station 18 where the ductile metal is leached away using a suitable acid. For example, where copper is the ductile metal, the etchant may comprise nitric acid.

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 particles in water is then mixed with fine, e.g. 4 to 200 micron size silica particles in water, in a coating station 22, forming a spongy mass. The coated spongy mass is then dried and subjected to magnesiothermic reaction by treating under vacuum or in an inert gas at 800 to 1200° C., preferably 900 to 1100° C., more preferably 950 to 1050° C., for 2 to 10 hours, preferably 4 to 8 hours, more preferably 5 to 6 hours at a reaction station 24. The magnesium reduces the silica and the oxide impurities within the tantalum fibers simultaneously permitting silicon to metallurgically bond to the tantalum fibers. Any magnesium oxide which results may remain, but preferably is removed for example by acid etching. On the other hand, it is not necessary to completely remove any copper which may be left over from the extrusion and drawings steps, since the copper also would metallurgically bond to the silicon. The resulting structure is a spongy, high surface area, conductive electrochemically stable tantalum metal substrate mass coated with a composite of sub-micron Si particles coated with a MgO matrix. The resulting spongy mass may then be mixed with water, and cast as a mat at a rolling station 26. The resulting mat is then further compressed and dried at a drying station 28.

As an alternative to coating and rolling a 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 Si/MgO composite or Si coated 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 or porosity 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 that may be desired, for example, for high density applications.

The resulting tantalum mat comprises a porous mat of sub-micron size Si or Si/MgO composite coated tantalum filaments in contact with one another, forming a conductive mat.

Alternatively, in a preferred embodiment of the invention, the raw tantalum filaments may be formed as mats of electrode material by casting and rolling above described are then coated with silicon nanoparticles by magnesiothermic reduction as above described, e.g., by dipping the tantalum mat into an aqueous based solution containing fine silica in water, and then heating under vacuum or inert gas as above described.

The Si/Ta structure as shown in FIGS. 2 and 3 is that of valve metal structure that is coated with a layer of nanoscaled nanostructure Si particles. The MgO can act as a stabilizing buffer against the degradation of the Si during cycling as the LIB anode. Although it is preferred that the MgO matrix is removed, using mineral acids, to reveal a nanoscaled nanostructure of the Si particles which are metallurgically bonded to the Ta support particles.

The resulting materials are tested for capacity over time, coulomb efficiency over time and differential capacity over cell voltage, and the results shown in FIGS. 4-6.

The resulting Si coated refractory material can be formed into useful LIB anodes via any standard manufacturing method, including, but not limited to: thin wet-lay methods deposited on a current collector, with or without conductive carbon additive; calendared fabrics; coins; etc. For example, referring to FIGS. 7 and 8, the coated mats are then assembled in a stack between separator sheets 36 to form positive (anode) and negative (cathode) electrodes 38, 40. The electrodes 38, 40 and separator sheets 36 are wound together in a jelly roll and inserted in the case 42 with a positive tab 44 and a negative tab 46 extending from the jelly roll in an assembly station 48. The tabs can then be welded to exposed portions of the electrode substrates, and the case filled with electrolyte and the case sealed. The result is a high capacity rechargeable battery in which the electrode material comprises extremely ductile fine metal composite filaments capable of repeated charging and draining without adverse effects. Other methods are also contemplated.

Various changes may be made in the above invention without departing from the spirit and scope thereof. For example, the invention has been described particularly in connection with silicon, other materials such as germanium advantageously may be employed. Still other changes may be made without departing from the spirit and scope of the invention.

Claims

1. An electrically active electrode material for use with a lithium ion cell, the electrochemically active electrode material comprising a substrate material consisting of individual filaments of a valve metal selected from the group consisting of tantalum, niobium, an alloy of tantalum, an alloy of niobium, and an alloy of hafnium, titanium and aluminum, not larger than about 10 microns across, which filaments are adhered together to form a mat or porous sheet and wherein the individual filaments of the mat or porous sheet are coated with a coating of crystalline silicon inside in a stabilizing magnesium oxide coating matrix, wherein the silicon is metallurgically bonded to the valve metal filaments.

2. The electrically active electrode material of claim 1, wherein the valve metal filaments have a thickness of less than 10 microns.

3. The electrically active electrode material of claim 1, wherein the valve metal filaments have a thickness below about 1 micron.

4. The electrically active electrode material of claim 1, formed into an anode.

5. A method of forming an electrode substrate useful for forming a lithium ion battery comprising the steps of:

(a) providing valve metal substrate material formed of individual filaments of a valve metal selected from the group consisting of tantalum, niobium, an alloy of tantalum, an alloy of niobium, and an alloy of hafnium, titanium and aluminum, not larger than about 10 microns across;
(b) forming the individual filaments of step (a) into a mat or porous sheet; and
(c) subjecting the mat or porous sheet of step (b) and silica to a simultaneous magnesiothermic co-reaction with magnesium to produce a coating of crystalline silicon inside in a stabilizing magnesium oxide coating matrix, wherein the silicon coating is metallurgically bonded to the individual valve metal filaments.

6. The method of claim 5, wherein the magnesiothermic co-reaction is conducted under vacuum or in an inert gas at elevated temperature of 800-1200° C.

7. The method of claim 6, wherein the elevated temperature is 900-1100° C.

8. The method of claim 6, wherein the magnesiothermic co-reaction is conducted for 2-10 hours.

9. The method of claim 5, wherein the filaments have at thickness of less than 10 microns.

10. The method of claim 5, wherein the filaments have a thickness below about 1 micron.

11. A lithium ion battery comprising a case 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.

12. The method of claim 6, wherein the elevated temperature is 950-1050° C.

13. The method of claim 6, wherein the magnesiothermic co-reaction is conducted for 4-8 hours.

14. The method of claim 6, wherein the magnesiotheimic co-reaction is conducted for 5-6 hours.

15. The electrically active electrode material of claim 1, wherein the valve metal filaments have a thickness of less than 5 microns.

16. The method of claim 5, wherein the filaments have a thickness of less than 5 microns.

Referenced Cited
U.S. Patent Documents
2299667 January 1942 Waterman
2277687 March 1942 Brennan
2278161 March 1942 Brennan
2310932 February 1943 Brennan et al.
2616165 November 1952 Brennan
3141235 July 1964 Lenz
3277564 October 1966 Webber et al.
3379000 April 1968 Webber et al.
3394213 July 1968 Roberts et al.
3418106 December 1968 Pierret
3473915 October 1969 Pierret
3540114 November 1970 Peter et al.
3557795 January 1971 Hirsch
3567407 March 1971 Yoblin
3677795 July 1972 Bokros et al.
3698863 October 1972 Roberts et al.
3740834 June 1973 Douglass
3742369 June 1973 Douglass
3800414 April 1974 Shattes et al.
3817746 June 1974 Tsuei
4017302 April 12, 1977 Bates et al.
4149277 April 17, 1979 Bokros
4378330 March 29, 1983 Verhoeven et al.
4441927 April 10, 1984 Getz et al.
4502884 March 5, 1985 Fife
4534366 August 13, 1985 Soukup
4551220 November 5, 1985 Oda
4578738 March 25, 1986 Zoltan
4646197 February 24, 1987 Wong
4674009 June 16, 1987 Wong et al.
4699763 October 13, 1987 Sinharoy et al.
4722756 February 2, 1988 Hard et al.
4734827 March 29, 1988 Wong
4846834 July 11, 1989 von Recum et al.
4940490 July 10, 1990 Fife et al.
4945342 July 31, 1990 Steinemann
4983184 January 8, 1991 Steinemann
5030233 July 9, 1991 Ducheyne
5034857 July 23, 1991 Wong
5062025 October 29, 1991 Verhoeven et al.
5143089 September 1, 1992 Alt
5185218 February 9, 1993 Brokman
5211741 May 18, 1993 Fife
5217526 June 8, 1993 Fife
5231996 August 3, 1993 Bardy et al.
5245415 September 14, 1993 Mimura
5245514 September 14, 1993 Fife et al.
5282861 February 1, 1994 Kaplan
5284531 February 8, 1994 Fife
5306462 April 26, 1994 Fife
5324328 June 28, 1994 Li et al.
5448447 September 5, 1995 Chang et al.
5580367 December 3, 1996 Fife
5635151 June 3, 1997 Zhang et al.
5869196 February 9, 1999 Wong et al.
5894403 April 13, 1999 Shah et al.
5908715 June 1, 1999 Liu et al.
5910382 June 8, 1999 Goodenough et al.
5920455 July 6, 1999 Shah et al.
5926362 July 20, 1999 Muffoletto et al.
6007945 December 28, 1999 Jacobs et al.
6143448 November 7, 2000 Fauteux et al.
6224985 May 1, 2001 Shah et al.
6231993 May 15, 2001 Stephenson et al.
6316143 November 13, 2001 Foster et al.
6319459 November 20, 2001 Melody et al.
6334879 January 1, 2002 Muffoletto et al.
6468605 October 22, 2002 Shah et al.
6475673 November 5, 2002 Yamawaki et al.
6524749 February 25, 2003 Kaneda et al.
6648903 November 18, 2003 Pierson
6666961 December 23, 2003 Skoczylas
6687117 February 3, 2004 Liu et al.
6728579 April 27, 2004 Lindgren et al.
6780180 August 24, 2004 Goble
6792316 September 14, 2004 Sass
6859353 February 22, 2005 Elliott et al.
6965510 November 15, 2005 Liu et al.
6980865 December 27, 2005 Wang et al.
7012799 March 14, 2006 Muffoletto et al.
7020947 April 4, 2006 Bradley
7072171 July 4, 2006 Muffoletto et al.
7073559 July 11, 2006 O'Leary et al.
7092242 August 15, 2006 Gloss et al.
7094499 August 22, 2006 Hung
7116547 October 3, 2006 Seitz et al.
7146709 December 12, 2006 Wong
7158837 January 2, 2007 Osypka et al.
7235096 June 26, 2007 Tassel et al.
7271994 September 18, 2007 Stemen et al.
7280875 October 9, 2007 Chitre et al.
7286336 October 23, 2007 Liu et al.
7342774 March 11, 2008 Hossick-Schott et al.
7410728 August 12, 2008 Fujimoto
7480978 January 27, 2009 Wong
7483260 January 27, 2009 Ziarniak et al.
7485256 February 3, 2009 Mariani
7490396 February 17, 2009 Bradley
7501579 March 10, 2009 Michael et al.
7666247 February 23, 2010 He et al.
7667954 February 23, 2010 Lessner et al.
7679885 March 16, 2010 Mizusaki et al.
7727372 June 1, 2010 Liu et al.
7813107 October 12, 2010 Druding et al.
7837743 November 23, 2010 Gaffney et al.
7879217 February 1, 2011 Goad et al.
7983022 July 19, 2011 O'Connor et al.
8081419 December 20, 2011 Monroe et al.
8194393 June 5, 2012 Inoue et al.
8224457 July 17, 2012 Strandberg et al.
8257866 September 4, 2012 Loveness et al.
8313621 November 20, 2012 Goad et al.
8435676 May 7, 2013 Zhamu et al.
8450012 May 28, 2013 Cui et al.
8460286 June 11, 2013 Stangenes et al.
8603683 December 10, 2013 Park et al.
8637185 January 28, 2014 Berdichevsky et al.
8673025 March 18, 2014 Wong
8722226 May 13, 2014 Chiang et al.
8722227 May 13, 2014 Chiang et al.
8858738 October 14, 2014 Wong
8906447 December 9, 2014 Zhamu
8993159 March 31, 2015 Chiang et al.
9065093 June 23, 2015 Chiang et al.
9155605 October 13, 2015 Wong
9178208 November 3, 2015 Park et al.
9312075 April 12, 2016 Liu et al.
9397338 July 19, 2016 Park et al.
9498316 November 22, 2016 Wong
9633796 April 25, 2017 Liu et al.
10090513 October 2, 2018 Canham et al.
20030183042 October 2, 2003 Oda et al.
20040121290 June 24, 2004 Minevski et al.
20040244185 December 9, 2004 Wong
20050159739 July 21, 2005 Paul
20060195188 August 31, 2006 O'Driscoll et al.
20060237697 October 26, 2006 Kosuzu et al.
20060279908 December 14, 2006 Omori et al.
20070020519 January 25, 2007 Kim et al.
20070031730 February 8, 2007 Kawakami et al.
20070093834 April 26, 2007 Stevens et al.
20070122701 May 31, 2007 Yamaguchi
20070148544 June 28, 2007 Le
20070167815 July 19, 2007 Jacobsen
20070214857 September 20, 2007 Wong et al.
20070244548 October 18, 2007 Myers et al.
20080072407 March 27, 2008 Wong
20080234752 September 25, 2008 Dahners
20090018643 January 15, 2009 Hashi et al.
20090044398 February 19, 2009 Wong
20090075863 March 19, 2009 O'Driscoll et al.
20090095130 April 16, 2009 Smokovich et al.
20090176159 July 9, 2009 Zhamu et al.
20090185329 July 23, 2009 Breznova et al.
20090187258 July 23, 2009 Ip et al.
20090228021 September 10, 2009 Leung
20090234384 September 17, 2009 Hadba
20090269677 October 29, 2009 Hirose
20100044076 February 25, 2010 Chastain et al.
20100047671 February 25, 2010 Chiang et al.
20100075168 March 25, 2010 Schaffer
20100134955 June 3, 2010 O'Connor et al.
20100211147 August 19, 2010 Schiefer et al.
20100239915 September 23, 2010 Hochgattrerer et al.
20100255376 October 7, 2010 Park et al.
20100280584 November 4, 2010 Johnson et al.
20100310941 December 9, 2010 Kumta
20110020701 January 27, 2011 Park et al.
20110082564 April 7, 2011 Liu et al.
20110086271 April 14, 2011 Lee
20110137419 June 9, 2011 Wong
20110177393 July 21, 2011 Park et al.
20110189510 August 4, 2011 Caracciolo et al.
20110189520 August 4, 2011 Carter et al.
20110200848 August 18, 2011 Chiang et al.
20110229761 September 22, 2011 Cui et al.
20110274948 November 10, 2011 Duduta et al.
20110311888 December 22, 2011 Garsuch
20120081840 April 5, 2012 Matsuoka et al.
20120094192 April 19, 2012 Qu et al.
20120164499 June 28, 2012 Chiang et al.
20120219860 August 30, 2012 Wang et al.
20120239162 September 20, 2012 Liu
20130019468 January 24, 2013 Ramasubramanian et al.
20130055559 March 7, 2013 Slocum et al.
20130065122 March 14, 2013 Chiang
20130149605 June 13, 2013 Kakehata et al.
20130282088 October 24, 2013 Bondhus
20130314844 November 28, 2013 Chen et al.
20130323581 December 5, 2013 Singh et al.
20130337319 December 19, 2013 Doherty et al.
20130344367 December 26, 2013 Chiang et al.
20140004437 January 2, 2014 Slocum et al.
20140030605 January 30, 2014 Kim et al.
20140030623 January 30, 2014 Chiang et al.
20140057171 February 27, 2014 Sohn et al.
20140065322 March 6, 2014 Park et al.
20140154546 June 5, 2014 Carter et al.
20140170498 June 19, 2014 Park
20140170524 June 19, 2014 Chiang et al.
20140234699 August 21, 2014 Ling et al.
20140248521 September 4, 2014 Chiang et al.
20140255774 September 11, 2014 Singh et al.
20140266066 September 18, 2014 Turon Teixidor et al.
20140287311 September 25, 2014 Wang
20140315097 October 23, 2014 Tan et al.
20140322595 October 30, 2014 Zhang et al.
20141315097 October 2014 Tan et al.
20150028263 January 29, 2015 Wang et al.
20150044553 February 12, 2015 Chen
20150099185 April 9, 2015 Joo et al.
20150104705 April 16, 2015 Canham
20150129081 May 14, 2015 Chiang et al.
20160190599 June 30, 2016 Kim et al.
20160225533 August 4, 2016 Liu et al.
20170125177 May 4, 2017 Perez et al.
20170125178 May 4, 2017 Perez et al.
20170148576 May 25, 2017 Hahl et al.
20170232509 August 17, 2017 Yang et al.
Foreign Patent Documents
1809904 July 2006 CN
1816401 August 2006 CN
103779534 June 2013 CN
104040764 September 2014 CN
3163593 May 2017 EP
3166117 May 2017 EP
3171378 May 2017 EP
1267699 March 1972 GB
H11288849 October 1999 JP
2009230952 October 2009 JP
2012-109224 June 2012 JP
2014-116318 June 2014 JP
2015525189 September 2015 JP
20120114117 October 2012 KR
20130033251 April 2013 KR
2014-0097967 August 2014 KR
20150000032 January 2015 KR
189157 May 2013 SG
WO 98/28129 July 1998 WO
WO 2008/039707 April 2008 WO
WO 2008/063526 May 2008 WO
WO 2009/082631 July 2009 WO
WO 2012/027702 May 2012 WO
WO 2012/138302 October 2012 WO
WO 2014/093876 June 2014 WO
WO2014147885 September 2014 WO
WO 2014/208996 December 2014 WO
WO 2015/038076 March 2015 WO
WO2016/026092 February 2016 WO
WO 2016/187143 November 2016 WO
Other references
  • Chinese Office Action (w/machine translation) issued in application No. 201780057333.X, dated Apr. 2, 2020 (13 pgs).
  • Japanese Office Action (w/translation) issued in application No. 2019-511852, dated Mar. 2, 2020 (8 pgs).
  • Japanese Office Action (w/translation) issued in application No. 2019-559509, dated Feb. 19, 2020 (8 pgs).
  • Chinese Office Action (w/machine translation) issued in application No. 201680028157.2, dated Apr. 1, 2020 (15 pgs).
  • European Office Action issued in application No. 17847651.1, dated Mar. 9, 2020 (8 pgs).
  • European Office Action issued in application No. 17840375.4, dated Mar. 26, 2020 (15 pgs).
  • U.S. Appl. No. 15/694,575, filed Sep. 1, 2017.
  • Chinese Office Action (w/machine translation) issued in application No. 201780057333.X, dated Jul. 15, 2020 (16 pgs).
  • Japanese Decision of Allowance (w/translation) issued in application No. 2019-511852, dated Aug. 3, 2020 (4 pgs).
  • Bobyn et al., “Characteristics of bone ingrowth and interface mechanics of a new porous tantalum biomaterial,” The Journal of Bone & Joint Surgery (Br), Vo. 81-B, No. 5, Sep. 1999 (8 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).
  • “Comparison of battery types” Wikipedia article https://en.wikipedia.prg/wiki/Comparison_of_battery_type, Jul. 8, 2015 (1 pg).
  • “Design of Highly Integrated Structures with Additive Manufacturing and Composites” pdlz Product Development Group Zurich, accessed Sep. 18, 2015 (2 pgs).
  • Electrochemistry at the Nanoscale, edited by Patrik Schmuki, Sannakaisa Virtanen, Google Books print out, accessed Aug. 7, 2015 (1 pg).
  • European Search Report for corresponding EP Application Serial No. 16797109.2, dated Jan. 4, 2019 (9 pages).
  • 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).
  • Grifantini, K., “Nervy Repair Job,” Technology Review, Jan./Feb. 2010, pp. 80-82 (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).
  • “Lithium-ion battery” Wikipedia page https://wikipedia.org/wiki/Lithium-ion_battery#Materials_of_commercial_cells, Jul. 7, 2015 (27 pgs).
  • Office Action issued in U.S. Appl. No. 15/675,557, dated Aug. 24, 2018 (14 pgs).
  • Office Action issued in related U.S. Appl. No. 15/694,575, dated Apr. 2, 2018 (24 pgs).
  • Office Action issued in related U.S. Appl. No. 15/694,575, dated Aug. 30, 2018 (16 pgs).
  • Office Action issued in related U.S. Appl. No. 15/574,121, dated Apr. 11, 2019 (8 pgs).
  • Office Action issued in related U.S. Appl. No. 15/574,121, dated Feb. 20, 2019 (8 pgs).
  • Office Action issued in related U.S. Appl. No. 15/574,121, dated Nov. 13, 2018 (10 pgs).
  • Office Action issued in related U.S. Appl. No. 15/574,121, dated Aug. 27, 2018 (13 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).
  • “Ultra-fast charging batteries that can be 70% recharges in just two minutes” Nanyang Tehcnological University, dated Oct. 13, 2014 (3 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).
  • Chinese Office Action (w/machine translation) issued in application No. 201780050465.X, dated Jan. 8, 2020 (6 pgs).
  • Chinese Office Action (w/translation) issued in application No. 201780057333.X, dated Oct. 25, 2019 (13 pgs).
  • Japanese Office Action (w/translation) issued in application No. 2019-511852, dated Nov. 19, 2019 (8 pgs).
  • Korean Office Action (w/translation) issued in application No. 10-2019-7009289, dated Nov. 22, 2019 (16 pgs).
  • Notice of Allowance issued in U.S. Appl. No. 15/694,575, dated Dec. 20, 2018 (16 pgs).
  • Notice of Allowance issued in U.S. Appl. No. 15/694,575, dated Feb. 5, 2019 (11 pgs).
  • Office Action issued in U.S. Appl. No. 15/675,557, dated May 4, 2018 (50 pgs).
  • Bobyn et al., “Characteristics of bone ingrowth and interface mechnics of a new porous tantalum biomaterial,” The Journal of Bone & Joint Surgery (Br), Vo. 81-B, No. 5, Sep. 1999 (8 pgs).
  • Extended European Search Report issued in related application No. 10835252.7, dated May 12, 2014 (7 pgs).
  • Grifantini, K., “Nervey Repair Job,” Technology Review, Jan./Feb. 2010, pp. 80-82 (3 pgs).
  • International Preliminary Report on Patentability issued in application No. PCT/US2013/060702, dated Apr. 2, 2015 (8 pgs).
  • International Preliminary Report on Patentability issued in application No. PCT/US2013/063915, dated Apr. 23, 2015 (7 pgs).
  • International Preliminary Report on Patentability issued in PCT/US2010/059124 dated Jun. 14, 2012 (6 pgs).
  • International Preliminary Report on Patentability, issued in application No. PCT/US2014/061385, dated May 12, 2016 (8 pgs).
  • International Search Report and Written Opinion issued in application PCT/US14/61385, dated Mar. 17, 2015 (11 pgs).
  • International Search Report and Written Opinion issued in PCT/US2010/059124, dated Feb. 15, 2011 (9 pgs).
  • Journal article by Yarlagadda et al. entitled “Recent Advances and Current Developments in Tissue Scaffolding” published in Bio-Medical Materials and Engineering 2005 15(3), pp. 159-177 (26 pgs).
  • Li et al., “Ti6Ta4Sn Alloy and Subsequent Scaffolding for Bone Tissue Engineering,” Tissue Engineering: Part A, vol. 15, No. 10, 2009, pp. 3151-3159 (9 pgs).
  • Lu, N., “Soft, flexible electronics bond to skin and even organs for better health monitoring,” Technology Review, Sep./Oct. 2012 (4 pgs).
  • Markaki et al., “Magneto-mechanical stimulation of bone growth in a bonded array of ferromagnetic fibres,” Biomaterials 25, 2004, pp. 4805-4815 (11 pgs).
  • Meier et al., “Cardiologist Issues Alert On St. Jude Heart Device,” The New York Times, Business Day section, Aug. 22, 2012, pp. B1-B2, (2 pgs).
  • Notice of Allowance issued in U.S. Appl. No. 14/857,614, dated May 26, 2016 (9 pgs).
  • Office Action issued in U.S. Appl. No. 14/517,312, dated Oct. 8, 2015 (8 pgs).
  • Office Action issued in U.S. Appl. No. 14/696,130, dated Nov. 3, 2015 (24 pgs).
  • Office Action issued in U.S. Appl. No. 14/707,944, dated Jan. 29, 2016 (13 pgs).
  • Office Action issued in U.S. Appl. No. 14/857,614, dated Dec. 3, 2015 (24 pgs).
  • Office Action issued in U.S. Appl. No. 14/857,614, dated Feb. 26, 2016 (15 pgs).
  • Office Action issued in U.S. Appl. No. 14/871,677, dated May 13, 2016 (15 pgs).
  • Office Action issued in related U.S. Appl. No. 12/961,209, dated Jul. 5, 2012 (12 pgs).
  • Office Action issued in related U.S. Appl. No. 13/713,885, dated May 10, 2013 (12 pgs).
  • Office Action issued in related U.S. Appl. No. 13/713,885, dated Aug. 8, 2013 (7 pgs).
  • Office Action issued in related U.S. Appl. No. 13/713,885, dated Oct. 30, 2013 (11 pgs).
  • Office Action issued in related U.S. Appl. No. 14/030,840, dated Jul. 17, 2014 (13 pgs).
  • Office Action issued in related U.S. Appl. No. 14/030,840, dated Apr. 9, 2014 (13 pgs).
  • Office Action issued in related U.S. Appl. No. 14/030,840, dated Dec. 13, 2013 (9 pgs).
  • Office Action issued in related U.S. Appl. No. 14/174,628, dated Jun. 10, 2014 (19 pgs).
  • Office Action issued in related U.S. Appl. No. 14/328,567, dated Feb. 25, 2015 (24 pgs).
  • Office Action issued in related U.S. Appl. No. 14/328,567, dated Apr. 1, 2015 (11 pgs).
  • Office Action issued in related U.S. Appl. No. 14/328,567, dated May 28, 2015 (19 pgs).
  • Office Action issued in related U.S. Appl. No. 14/494,940, dated Nov. 18, 2014 (14 pgs).
  • Office Action issued in related U.S. Appl. No. 14/517,312, dated Jun. 23, 2015 (40 pgs).
  • Office Action issued in related U.S. Appl. No. 14/517,312, dated May 29, 2015 (6 pgs).
  • PCT International Search Report and Written Opinion issued in corresponding application No. PCT/US13/60702, dated Dec. 5, 2013 (9 pgs).
  • Ryan et al., “Fabrication methods of porous metals for use in orthopaedic applications,” Biomaterials 27, 2006, pp. 2651-2670 (20 pgs).
  • Wang et al., “Biomimetic Modification of Porous TiNbZr Alloy Scaffold for Bone Tissue Engineering,” Tissue Engineering: Part A, vol. 00, No. 00, 2009, pp. 1-8, (8 pgs).
  • Wang, M., “Composite Scaffolds for Bone Tissue Engineering,” American Journal of Biochemistry and Biotechnology 2 (2), 2006, pp. 80-83 (4 pgs).
  • U.S. Appl. No. 12/961,209, filed Dec. 6, 2010.
  • U.S. Appl. No. 13/713,885, filed Dec. 13, 2012.
  • U.S. Appl. No. 14/030,840, filed Sep. 18, 2013.
  • U.S. Appl. No. 14/174,628, filed Feb. 6, 2014.
  • U.S. Appl. No. 14/328,567, filed Jul. 10, 2014.
  • U.S. Appl. No. 14/494,940, filed Sep. 24, 2014.
  • U.S. Appl. No. 14/517,312, filed Oct. 17, 2014.
  • U.S. Appl. No. 14/696,130, filed Apr. 24, 2015.
  • U.S. Appl. No. 14/707,944, filed May 8, 2015.
  • U.S. Appl. No. 14/857,614, filed Sep. 17, 2015.
  • U.S. Appl. No. 15/675,557, filed Aug. 11, 2017.
  • International Search Report and Written Opinion issued in application No. PCT/US2017/046619, dated Dec. 11, 2017 (12 pgs).
  • Invitation to Pay Additional Fees issued in application No. PCT/US2017/046619, dated Sep. 15, 2017 (2 pgs).
  • Issue Fee Transmittal for U.S. Appl. No. 14/479,689, filed Feb. 29, 2016 (1 pg).
  • Notice of Allowance issued in U.S. Appl. No. 14/479,689, dated Dec. 1, 2015 (8 pgs).
  • Office Action issued in U.S. Appl. No. 14/479,689, dated Nov. 13, 2015 (7 pgs).
  • Office Action issued in U.S. Appl. No. 15/675,557, dated Mar. 8, 2018 (7 pgs).
  • PCT International Search Report for related PCT International Patent Application Serial No. PCT/US17/49950, dated Nov. 16, 2017, 9 pgs.
  • Petition for Inter Partes Review of U.S. Pat. No. 9,312,075, dated May 15, 2017 (138 pgs).
  • Tantalum capacitor description from Wikipedia, downloaded on Jul. 25, 2016 (24 pgs).
Patent History
Patent number: RE49419
Type: Grant
Filed: Sep 23, 2019
Date of Patent: Feb 14, 2023
Assignee: COMPOSITE MATERIALS TECHNOLOGY, INC. (Shrewsbury, MA)
Inventors: James Wong (Shrewsbury, MA), David Frost (Shrewsbury, MA)
Primary Examiner: Sean E Vincent
Application Number: 16/579,586
Classifications
Current U.S. Class: 29/182
International Classification: H01M 4/62 (20060101); H01M 4/134 (20100101); H01M 4/36 (20060101); H01M 4/38 (20060101); H01M 10/0525 (20100101); H01M 4/02 (20060101);