Please do not remove this page

Electrochemically self assembled batteries, U.S. Patent 9,331,357

Amatucci, Glenn G.; Plitz, Irene; Badway, Fadwa https://scholarship.libraries.rutgers.edu/discovery/delivery/01RUT_INST:ResearchRepository/12643416170004646?l#13643526190004646

Amatucci, G. G., Plitz, I., & Badway, F. (2016). Electrochemically self assembled batteries, U.S. Patent 9,331,357. Rutgers University. https://na04.alma.exlibrisgroup.com/discovery/delivery/01RUT_INST:01RUT/12643416170004646

This work is protected by copyright. You are free to use this resource, with proper attribution, for research and educational purposes. Other uses, such as reproduction or publication, may require the permission of the copyright holder. Downloaded On 2021/10/02 02:25:19 -0400 US009331357B2

(12) United States Patent (10) Patent No.: US 9,331,357 B2 Amatucci et al. (45) Date of Patent: May 3, 2016

(54) ELECTROCHEMICALLY SELFASSEMBLED (2013.01); H0IM 10/0565 (2013.01), HOLM BATTERIES 2/022 (2013.01), HOLM 4/582 (2013.01), HOLM 10/0472 (2013.01); HOIM 2300/002 (2013.01); (75) Inventors: Glenn G. Amatucci, Peapack, NJ (US); HOIM 2300/0082 (2013.01), HOIM 2300/0085 Irene Plitz, North Plainfield, NJ (US); (2013.01), HOLM 2300/0091 (2013.01) Fadwa Badway, Old Bridge, NJ (US) (58) Field of Classification Search None (73) Assignee: Rutgers, The State University of New See application file for complete search history. Jersey, New Brunswick, NJ (US) (56) References Cited (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 |U.S. PATENT DOCUMENTS U.S.C. 154(b) by 1623 days. 4,007,122 A * 2/1977 Owens et al...... 252/62.2 4,544,615 A * 10/1985 Shishikura et al...... 429/339 (21) Appl. No.: 11/813,309 (Continued)- (22) PCT Filed: Jan. 6, 2006 FOREIGN PATENT DOCUMENTS (86) PCT No.: PCT/US2006/000448 DE 3930304 A1 3/1991 § 371 (c)(1), EP 0.1494.21 * 7/1985 ...... H01M 4/60 (2), (4) Date: Jun. 19, 2008 (Continued) (87) PCT Pub. No.: WO2006/078472 OTHER PUBLICATIONS PCT Pub. Date: Jul. 27, 2006 International Search Report for International Application No. PCT/ US06/00448. (65) Prior Publication Data (Continued) |US 2009/0004560 A1 Jan. 1, 2009 Primary Examiner – Barbara Gilliam Related U.S. Application Data Assistant Examiner – Angela Martin (60) Provisional application No. 60/641,449, filed on Jan. (74) Attorney, Agent, or Firm – Greenberg Traurig, LLP 6, 2005, provisional application No. 60/727,471, filed (57) ABSTRACT on Oct. 17, 2005. The present invention- - relates to in- situ- formation- of a single- (51) Int. Cl. layered electrochemical cell comprising a full tri-layer bat H0 IM 6/22 (2006.01) tery structure containing a discrete positive electrode, solid H0 IM 6/18 (2006.01) state electrolyte, and negative electrode from self-assembled H0 IM 10/0565 (2010.01) nanocomposites. The single layered cell makes it possible to (Continued) fabricate cells in three dimensions resulting in a very high energy density power source within very small and/or com (52) U.S. CI. plex dimensions. CPC ...... H01M 10/0422 (2013.01), H01B 1/122 (2013.01); H0IM 6/18 (2013.01); H0IM 6/22 27 Claims, 12 Drawing Sheets

US 9,331,357 B2 Page 2

(51) Int. Cl. 6,517,974 B1 2/2003 Kobayashi et al. H0 IM 10/04 (2006.01) 2005/0003270 A1* 1/2005 Phillips ...... 429/223 H0 IB I/I 2 (2006.01) 2010/0323,098 A1* 12/2010 Kosuzu et al...... 427/77 % º FOREIGN PATENT DOCUMENTS e EP () 1494.21 A2 7/1985 (56) References Cited JP 08.1386.35 A 5/1996

|U.S. PATENT DOCUMENTS OTHER PUBLICATIONS 4,560,633 A * 12/1985 Kobayashi et al...... 429/213 5,360,686 A 11/1994 Peled et al. European Search Report dated Aug. 27, 2009. 5,792,574 A 8/1998 Mitate et al. 6,168,884 B1 1/2001 Neudecker et al. * cited by examiner U.S. Patent May 3, 2016 Sheet 1 of 12 US 9,331,357 B2

FIG. 2

Etched or Ion Milled Metal Substrate Metal Substrate ~

- electrode U.S. Patent May 3, 2016 Sheet 2 of 12 US 9,331,357 B2

FIG. 3

LiI electrolyte

Li? based nanocomposite

7 assembly

Iodine based (+) U.S. Patent May 3, 2016 Sheet 3 of 12 US 9,331,357 B2

FIG. 4

Hair U.S. Patent May 3, 2016 Sheet 4 of 12 US 9,331,357 B2

FIG. 5

in-situ formation of anode, cathode, and electrolyte ^recharge/formation of micro cell (l) #b?) ->

discharge of micro cell

2^ initial single layer

0 20 40 60 80 100 Time/h

5 y i i —- i i T-I- | -T—r H H r—r— -- I J

4 | cell formation (3 layer) on oxidation l

3 H -

§ | I § - -

sº - -- 2 H ? - development of discharge capacity 1 H as function of formation

| OV 1 layer O 4— l 3. 3. — T l—l l—— O 20 40 60 80

U.S. Patent May 3, 2016 Sheet 6 of 12 US 9,331,357 B2

FIG. 8

5 0.02

4. -, * ~ * * ~ *- * * ~ ,- * ~ * * * * : * ~ * * * ------T 0.015

(i) cell : t recharge 0.01 Q 39 formation - * . and continued # 5 2 …" ... Discharge ------# * cell. ------j-... º E. -> : formation - 0.005 # 1 º -

0 –0V. ! - 0

-1 — -0.005 0 50 100 150 200 250 300 350 400 Time (h)

FIG. 9 Figure 9 refers to figure 8, it is just the second discharge result U.S. Patent May 3, 2016 Sheet 7 of 12 US 9,331,357 B2

FIG. 10

0.05

0.04 4 0.03 Q #Q H "E 0.02 E. > 2-y 2 ? 0.01 S

1 O

() -0.01 O 50 100 150 200 250 U.S. Patent May 3, 2016 Sheet 8 of 12 US 9,331,357 B2

FIG. 11

cres tº go o LiI - H2O

530 0

Hill520 ol y —ººl“"

Degrees Two-theta U.S. Patent May 3, 2016 Sheet 9 of 12 US 9,331,357 B2

FIG. 12

| -4 *~~~~| 7

13.0 16.0 19.0 22.0 25.0 28.0 31.0 34.0 37.0 40.0 43.0 46.0 49.0 52.0 55.0 Degrees Two-Theta U.S. Patent May 3, 2016 Sheet 10 of 12 US 9,331,357 B2

FIG. 13

0.42%,

0.40 0.38 0.36 0.34 0.32 0.30 0.28 0.26 0.24 0.22 0.20 0.18 0.16 0.14 O.12 0.10 0.08% 0.08% 0.04+ 0.02 4000" 3500 3000 2500 2000

US 9,331,357 B2 1 2 ELECTROCHEMICALLY SELF ASSEMBLED meric electrolytes (W. H. Meyer, Adv. Mater, 10:439 (1998), BATTERIES J. Y. Song, Y.Y. Wang and C. C. Wan, J. Power Sources, 77: 183 (1999)) include gel electrolytes formed by polymers CROSS-REFERENCE TO RELATED swollen by solutions and solid polymer electro APPLICATIONS 5 lytes (SPEs) (I. C. Murata, S. Isuchi and Y. Yoshihisa, Elec trochem. Acta 45: 1501 (2000)). The overall thickness of this This application claims priority to U.S. provisional appli type of flat batteries, including packaging, lies in the 0.3-3 cation No. 60/641,449, filed Jan. 6, 2005, and 60/727,471. mm range. The size, packaging and electrochemical perfor filed Oct. 17, 2005. The contents of each of these applications mance of such cells make then unsuitable for direct applica are incorporated by reference herein in their entirety. 10 tion to small electronic circuitry as would be commonplace in sensors and MEMS. GOVERNMENT SUPPORT b. Thin Film Batteries An alternative to further decrease the overall thickness of This work is supported at least in part by grants to Dr. flat batteries by an order of magnitude to approximately 10 Amatucci. The government may have certain rights in this 15 pum lay in the use of microelectronic fabrication techniques, invention. such as sputtering and vacuum evaporation, to fabricate all solid state thin film batteries. This battery technology is based FIELD OF THE INVENTION on thin glassy oxide and sulfide electrolytes. These liquid free electrolytes suppressed the risk of liquid leakage, a criti The present invention relates to a new concept in the devel- 20 cal issue due to the proximity of the power source to the opment of an electrochemically self assembled battery. Par electronic components. Their low ionic conductivity is ticularly, the self assembled chemistry relates to an ideal way counter-balanced by low diffusion lengths as a result of to fabricate microbatteries. More particularly, this chemistry reduced film thickness allowed by the microelectronic fabri can be applied to the development of a micro battery rod, cation techniques. Furthermore, these fabrication techniques which allows unprecedented application as a power platform 25 allow the deposition of the battery components directly on the for micro sensors and as power and structural members for microsystem substrate to achieve small footprint and sub micromachines. strate localization to the operating device. Eveready Battery Company (S. D. Jones and J. R. Akridge BACKGROUND OF THE INVENTION Solid State Ionics, 86–88: 1291 (1996)) and Hydromecanique 30 Et Frottements (HEF), in collaboration with the University of The size of microelectronic and microelectromechanical Bordeaux (J. P. Terra, M. Martin, A. Levasseur, G. Meunier systems continues to decrease as a result of improved inte and P. Vinatier, Tech. Mg., Genie Blear. D., 3342: 1 (1998)), gration and microprocessing techniques. However, the mac have manufactured rechargeable all state thin film lithium roscopic power systems currently employed to power these batteries less than 10 pum thick. While the latter based its microdevices are much larger than the devices themselves 35 battery technology on amorphous titanic or molybdenum and require complex circuitry. Although the search for oxysulfide cathodes, the former utilized TiS, cathodes. In micropower sources has recently raised an increasing amount both cases, the lithium anodes were obtained by vacuum of interest, the demand for suitable small-scale power system evaporation while the cathodes and electrolytes were depos that meet microsystem power and energy requirements has ited by sputtering. The use of a hydrophobic polymer protec yet to be fulfilled. In most applications, power supply minia- 40 tive packaging increased the overall thickness of the batteries turization advanced to the microdevice scale would provide to about 100 pum. more control over the power delivery to each component of The most successful thin film battery technology has been the microsystem and would also simplify electronic circuitry. demonstrated by Oak Ridge National Laboratory (J. B. Bates, The incorporation of a micropower source directly into N. J. Dudney, B. Neudecker, A. Ueda and C. D. Evans, Solid microsystems that also integrate communication and signal- 45 State Ionics 135: 33 (2000)). This group has developed processing components would offer the advantage of com rechargeable lithium batteries using RF magnetron sputtering plete autonomy, a critical feature in many applications such as (lithium transition metal oxide cathode and UPON electro microsensors. (J. Long, B. Dunn, D. Holism and H. White, lyte) and thermal evaporation (Li anode). These batteries, Chem. Rev. 104: 4463 (2004)). One crucial issue related to sealed with a protective hermetic multilayer coating of micro-power sources is to provide enough energy and power 50 parylene and titanium, presented the advantage of retaining to all the components for the remote microsystem to function an overall thickness of less than 15 pum. This battery design while minimizing the size of the power system. As constituent was further improved to be compatible with the integrated materials and fabrication techniques often restrict battery circuit (IC) assembly solder reflow process performed at 250 thickness, system optimization usually consists in minimiz 260° C. The low melting lithium metal anode (180°C.) was ing footprint occupancy while meeting the energy and power 55 replaced by high melting inorganic anodes in Li-ion batteries requirements. This challenge opens opportunities for the and by in-situ lithium platted copper anodes in initially development of fabrication technologies for materials in the lithium-free batteries. micro and nano scale. Although these very thin batteries offer long cycle and Existing Energy Storage Solutions shelf life, they are unable to satisfy the area energy require a. Thick Film Polymer Batteries 60 ments for microsystem applications. Sputtering techniques High-energy density primary and secondary batteries of prevent the addition of carbon to enhance the electronic con relatively thin dimensions are currently commercially avail ductivity of the semi-conducting cathode, limiting its thick able. (J. L. Souquet and M. Duclot, Solid State Ionics, 148: ness and therefore its capacity per area. Sequential sputtering 375 (2002)). These thick-film batteries are constructed with of complete electrochemical cells to build on thickness does polymer electrolyte films laminated to the positive and nega- 65 not afford a solution, as multiple current collectors must be tive electrodes and packaged with polylaminate aluminum/ utilized thereby limiting columetric energy density. In addi polyethylene heats sealable packaging material. Major poly tion, sputtering and vacuum evaporation fabrication methods US 9,331,357 B2 3 4 are costly and time consuming due to low film deposition position comprises a fluoride ion. According to another rates in the order of nm to pum/h. Therefore there is a critical embodiment, the metal halide composite of the composition need to establish technology with the small footprint of thin comprises an iodide ion. film batteries but with thicker electrodes in the range of According to another embodiment, a compound compris 25-100 microns to deliver the required energy. 5 ing an oxidized iodate ion forms at the positive electrode upon Three Dimensional Batteries application of a charging potential to the metal halide com As discussed, existing thick film technology and thin film posite of the composition. According to another embodiment, battery technology offer poor solutions to the majority of an oxidized compound comprising a polyiodide ion forms at micropower applications. Having identified this problem, a the positive electrode upon application of a charging potential 10 to the metal halide composite of the composition. According number of researchers have instituted studies related to the to another embodiment, an oxidized compound comprising a development of three dimensional battery microstructures. metal iodide forms at the positive electrode upon application The advantage of such microstructures is that they consume of a charging potential to the metal halide composite of the small amount of surface area on the electronic component and composition. According to another embodiment, the metal allow the development of energy by building the energy stor 15 halide composite of the composition is a nanocomposite. age device in the z or third direction perpendicular from the According to another embodiment, the metal halide com substrate. However, due to the intrinsic complexity of the posite of the composition further comprises an organic com lithium battery technology, it is very difficult to assemble ponent. According to another embodiment, the organic com such batteries in a reliable manner that enables such struc ponent is an organic material that forms compounds with tures to be incorporated. To date, no one has identified a 20 . According to another embodiment, the organic mate means to do so and demonstrated a working cell. The lithium rial that forms compounds with iodine is poly(vinylpyrroli battery technology consists of a negative electrode (Limetal), done). According to another embodiment, the organic com an electrolyte/separator (solid state lithium ion conductor) ponent is a conductive compound. According to another and positive electrode material. Successively deposited or embodiment, the conductive compound is a compound self assembled architectures are very difficult to achieve in 3 25 selected from the group consisting of poly(2 vinylpyridine), dimensions and have poor prospects for robustness once polyethylene oxide, polyvinyldene fluoride, polythiophene, assembled. The latter point is due to the tendency to form polyfluorothiophene, polypyrrole, polyaniline, and their electronic shorts through the electrolyte/separator. respective monomers. The common theme of all the above techniques is the use of According to another embodiment, the composition fur traditional lithium-ion or lithium metal related battery con 30 ther comprises a nanostructured inorganic component. figurations to address a very complex and unique problem. It According to another embodiment, the nanostructured inor is readily apparent that a new approach is needed, and that is ganic component is at least one compound selected from the the subject of this invention. group consisting of silicon oxide, aluminum oxide, barium titanate, and silicon nitride. According to another embodi SUMMARY OF THE INVENTION 35 ment, the metal halide composite of the composition further comprises at least one subgroup selected from the group The present invention provides a single-layered electro consisting of water and hydroxyl ions. chemical cell comprising a full tri-layer battery structure According to another embodiment, the negative electrode containing a discrete positive electrode, solid state electro further comprises a metal current collector. According to lyte, and negative electrode formed in situ from self-as 40 another embodiment, the metal current collector of the nega sembled composites or nanocomposites. According to one tive electrode is formed of a metal selected from the group embodiment of the present invention, an ionically conducting consisting of stainless steel, silicon, nickel, aluminum, tin, composition comprises a metal halide composite to which an gold, silver, platinum, and copper. According to another electrical potential is applied to form a negative electrode embodiment, the oxidized halide ion forms a complex with comprising a reduced form of a metal cation and a positive 45 the metal current collector of the positive electrode. Accord electrode comprising an oxidized halide anion, wherein the ing to another embodiment, the positive electrode comprises negative electrode and positive electrode are formed in situ. a metal current collector. According to another embodiment, According to another embodiment, the metal halide compos the metal current collector of the positive electrode is formed ite of the composition comprises a compound selected from of a metal selected from the group consisting of stainless the group consisting of an halide, an alkaline 50 steel, copper, nickel, aluminum, gold, silver, and platinum. earth metal halide, and a rare earth metal halide. According to According to another embodiment, the composition is another embodiment, the alkali metal halide composite of the deposited in a thickness of less than about 100 microns. composition comprises an alkali metal selected from the According to another embodiment, the composition is depos group consisting of lithium, , , , ited by a direct write technology. and cesium. According to another embodiment, the alkali 55 According to yet another embodiment, an electrochemical metal halide composite of the composition comprises lithium cell of the present invention comprises a tube having dimen iodide. According to another embodiment, the alkaline earth sions of length, width and depth, wherein in cross-section, the metalhalide composite of the composition comprises an alka tube has a shape selected from the group consisting of a circle, line earth metal selected from the group consisting of mag an oblong, a square and a rectangle, wherein the axial ratio is nesium, calcium, strontium, and barium. According to 60 >1, and wherein the thickness of the tube in 2 of the 3 dimen another embodiment, the rare earth metal halide composite of sions is less than 1 mm. According to another embodiment, the composition comprises a rare earth metal selected from the electrochemical cell further comprises a conducting wire the group consisting of yttrium and lanthanum. According to located approximately centered in the cross section of the another embodiment, the metal halide composite of the com tube, wherein the conducting wire continues down the length position comprises a halide selected from the group consist 65 of the cell. According to another embodiment, the electro ing of , , iodine and . According to chemical cell is a cylinder less than about 1 mm in diameter. another embodiment, the metal halide composite of the com According to another embodiment, the outside surface of the US 9,331,357 B2 5 6 tube is an outside current collector and the conducting wire is the electrochemical cell is extended to a second longer length an inside current collector. According to another embodi dimension, and a group comprising sensing, wireless com ment, the outside current collector is a positive electrode and munications, and energy harvesting electronics is contained the inside current collector is a negative electrode. According within the second longer length dimension of the electro to another embodiment, the positive electrode is made of at chemical cell. least one material selected from the group consisting of stain less steel, silicon, tungsten, chromium, and aluminum. BRIEF DESCRIPTION OF THE FIGURES According to another embodiment, the negative electrode is made of at least one material selected from the group consist FIG. 1 depicts the in-situ formation of a full tri-layer (posi ing of stainless steel, silicon, tungsten, magnesium, chro 10 tive electrode, electrolyte, negative electrode) battery struc mium, and aluminum. ture from a single layer according to the present invention. According to another embodiment, the electrochemical FIG. 2 shows a 3D battery cell fabricated according to the cell is formed in situ by a composite comprising a compound, present invention. wherein the composite is placed between two electrodes and FIG. 3 shows a micropower rod fabricated according to the the cell forms by application of an electrical potential to the 15 composite. According to another embodiment, the composite present invention. further comprises at least one subgroup selected from the FIG. 4 illustrates the scalability of the micropower rod group consisting of water and hydroxyl ions. According to configuration fabricated according to the present invention. another embodiment, a compound comprising an oxidized FIG. 5 is a graph depicting the in situ formation of an iodine ion forms at the positive electrode of the cell upon 20 electrochemical cell from a composite formed from Lil and application of a charging potential. According to another poly(vinylpyrrolidone) reagents. embodiment, an oxidized compound comprising at least one FIG. 6 is a graph depicting the in situ formation of an ion selected from the group consisting of an iodide ion and a electrochemical cell from a composite of Lil and polyethyl polyiodide ion forms at the positive electrode of the cell upon ene oxide reagents. application of a charging potential. According to another 25 FIG. 7 is a bar graph showing the ionic conductivity of embodiment, an oxidized compound comprising a metal various samples formed from a composite of Lil and poly iodide forms at the positive electrode of the cell upon appli (vinylpyrrolidone) reagents. cation of a charging potential. FIG. 8 is a graph depicting the formation, first discharge According to another embodiment, the compound com curve and energy density calculations for Example 5 from prises a metal halide. According to another embodiment, the 30 Table 1. metal halide is selected from the group consisting of an alkali FIG. 9 is a graph depicting the reformation, second dis metal halide, an alkaline earth metal halide, and a rare earth charge curve, and energy density calculations for Example 5 metal halide. According to another embodiment, the alkali from Table I. metal halide comprises an alkali metal selected from the FIG. 10 is a graph depicting the formation, first discharge group consisting of lithium, sodium, potassium, rubidium, 35 curve, and energy density calculations for two cells fabricated and cesium. According to another embodiment, the alkali from the composition of Example 11 from Table I. metal halide comprises lithium. According to another FIG. 11 shows X-ray diffraction data of LiI nanocompos embodiment, the alkali metal halide is . ites fabricated in the presence of different amounts of acetone. According to another embodiment, the alkaline earth metal FIG. 12 shows X-ray diffraction patterns of various useful halide comprises an alkaline earth metal selected from the 40 composites and nanocomposites prepared in accordance with group consisting of magnesium, calcium, strontium, and examples 7-12 in table I. barium. According to another embodiment, the rare earth FIG. 13 shows an FTIR spectrum of a composition from metal halide comprises a rare earth metal selected from the Table I example 3 that was removed from the cell after cycling group consisting of yttrium and lanthanum. According to for six cycles. anotherembodiment, the metalhalide compound comprises a 45 FIG. 14 shows a Raman spectrum of the positive electrode halide selected from the group consisting of fluorine, bro of a composition from Table I that was removed from the cell mine, iodine and chlorine. after cycling for a number of cycles. According to another embodiment, the composite of the FIG. 15 shows the voltage profile of a lithium iodide-PVP electrochemical cell further comprises an organic compo based composite fabricated with the addition of 5 wt.%20mm ment. According to another embodiment, the organic compo 50 particle size fumed silicon oxide. ment is an organic material that forms compounds withiodine. According to another embodiment, the organic material that DETAILED DESCRIPTION OF THE INVENTION forms compounds with iodine is poly(vinylpyrrolidone). According to another embodiment, the organic component is The present invention enables the fabrication of small and/ a conductive compound. According to another embodiment, 55 or complex three dimensional energy storage electrochemical wherein the conductive compound is selected from the group cells. Within the present invention, compounds have been consisting of poly(2 vinylypyridine), polyethylene oxide, identified, which, when processed in the correct fashion, can polyvinyldene fluoride, polypyrrole, polythiophene, poly be deposited or absorbed into a complex shape as a single fluorothiophene, polyaniline, and their respective monomers. layer material. Through the application of a voltage to this According to another embodiment, the composition further 60 single layer material, a full tri-layer battery structure contain comprises a nanostructured inorganic component. According ing a discrete positive electrode, solid state electrolyte, and to another embodiment, the nanostructured inorganic com negative electrode is formed in-situ. This is a challenge and ponent is at least one compound selected from the group concept that has not been met or addressed to date. The single consisting of silicon oxide, aluminum oxide, barium titanate, layered cell enables the unparalleled capability to fabricate and silicon nitride. According to another embodiment, the 65 cells in three dimensions resulting in a very high energy composite of the electrochemical cell is a nanocomposite. density power source within very small and/or complex According to another embodiment, the length dimension of dimensions. US 9,331,357 B2 7 8 It has previously been shown that nanostructured metal such IT oxidation in presence of a small amount of oxygen fluorides can be converted to and metal (See supplied by water or an organic can lead to the formation of PCT/US2005/35625, entitled “Bismuth Fluoride Based high energy iodates (IOS) or periodates (IOA) . This in effect Nanocomposites as Electrode Materials” and U.S. patent forms the positive electrode. Normally, such a reaction would application Ser. No. 11/177,729, entitled “Copper Fluoride be difficult to control. Based nanocomposites as Electrode Materials; the contents In certain embodiments, the ionically conducting compo of each of these applications is incorporated by reference sition of the invention further comprises a nanostructured herein). This technology has enabled the reversible conver inorganic component. The nanostructured inorganic compo sion reaction of these nanostructured metal fluorides for use ment is at least one compound selected from the group con as very high energy density electrodes for traditional lithium 10 sisting of silicon oxide, aluminum oxide, barium titanate, and batteries. According to a preferred embodiment of the present silicon nitride or a mixture thereof. invention, that concept has been extended in reverse by start If the in-situ cell formation reaction is brought to comple ing the single layer battery with a nanostructured lithium tion, the electronically conducting Li metal negative elec halide and then applying charge. trode would eventually contact the iodine containing and According to the present invention, it is preferred that such 15 conductive positive electrode resulting in an electrically a cell is based on lithium metal anodes due to the intrinsic shorted cell. Shorting is a major problem in small cells as the high voltage of lithium metal. Alternatively, certain alkaline separation distances between the negative and positive elec earth metals, preferably magnesium or its alloys, may be trodes are extremely small and subject to compromise. This utilized to enhance volumetric energy. In order to form a failure is further aggravated by repeated volume changes lithium metal electrode and a counter electrode that has a 20 occurring at the positive and negative electrodes during large voltage difference according to the present invention, cycling. Non-electrochemical reasons for cell failure due to alkali metal halides, alkaline earth metal halides, or rare earth shorting can be induced by thermal cycling of the cell and metal halides are used. Of the lithium or alkaline earth mechanical abuse as one would expect in many sensoror drug halides, the iodides are most preferred, due to their high delivery applications. However, according to the present mobility, but bromides, chlorides, or fluorides may be utilized 25 invention, this is not the case as iodine when contacting Li for the higher voltage they impart to the electrochemical cell. will reform the Lil electrolyte thermodynamically and stabi The very basic lithium (Li) metal vs iodine (I2) cells have lize the cell. Likewise, this would be expected to occur for the been utilized in cardiac pacemakers for many years because alternative metal halide combinations of the present inven of their intrinsically high volumetric energy density which tion. As a result of this behavior, it would be very difficult for exceeds that of existing lithium ion approaches discussed 30 this cell to internally short, as the passivating, ionically con above by a great factor. Most importantly, lithium iodine ducting Lil layer always forms. chemistry is very difficult to short: when the two electrodes Li After polarization and in-situ formation of the cell accord and I2 are brought in contact, they form a LiI conversion ing to the present invention, a modified version of a high product, which acts as a solid state electrolyte, thereby grant volumetric energy density rechargeable lithium/iodine cell is ing self healing attributes and incredible robustness to the 35 essentially formed in-situ. The self assembled chemistry of technology. The cell reaction for the lithium iodine chemistry the present invention allows unprecedented ease of fabricat 1S. ing thin cells in all three dimensions, which will enable exceptional utilization of valuable sensor surface area, easy tuning of the cell voltage by changing parallel vs. series After Lil is formed, the cell is discharged and dead. How 40 configuration, high reliability, low cost, and easy hermetic ever, the focus of the present invention is to utilize a compos sealing. ite or nanocomposite form of the inactive discharge product In certain embodiments, the present invention is used to LiI as the starting component and to reverse the reaction, power sensor and sensor arrays in an on-chip configuration demonstrated by the following simplistic representation: where sensor electronics, communications and powering 45 exist on a common platform. For such applications, incorpo Lil 4-> Lili, ration of the power source directly on or in the substrate is It will be shown later that although the cell formed in-situ vital to preserving small format. Such on-chip incorporation is similar to a simple Li-I2 chemistry, it has a positive elec will allow production of sensors in larger numbers for smart trode which differentiates itself from such chemistries. node array deployment that will be beneficial for applications According to the present invention, as shown in the sim 50 such as infrastructure monitoring and in-vivo biomedical plified schematic of FIG. 1, a highly ionically conductive, applications. Because it is desirable to preserve the surface electrically insulative nanocomposite based on Lil and a area of the sensor, the fabrication of such power sources is binder is placed between two current collectors. Upon the focused in the third dimension or “Z” direction. application of potential, lithium ions (Li") diffuse towards the In other embodiments, the present invention is used to form negative electrode and the iodide anions (IT) diffuse towards 55 three dimensional (3D) batteries. FIG. 2 depicts a 3D cell the positive electrode. At the negative electrode, the lithium fabricated according to the present invention where parallel ions reduce and plate at the negative electrode in the form of plates of the battery are formed directly in the depth of the lithium metal, thereby forming in-situ the lithium metal nega sensor substrate. This configuration enables the utilization of tive electrode. At the positive electrode, the IT oxidizes either the silicon substrate in a multifunctional way. As shown in to form elemental iodine (I2), polyiodides (I,) form a complex 60 FIG. 2, the cell is fabricated by etching orion milling parallel with the metal current collector, such as Ni to form NiI2, or, plates of a metal collector into the metal substrate. Parallel even more preferably, the IT reacts with a complexing organic plates having a separation distance of approximately 25-50 component, such as polyvinylpyrrolidone or conducting con microns are formed through micro wire EDM or laser micro jugated polymers such as poly(2-vinylpyridine), or other con machining. In other embodiments, the plates are micromilled jugated conducting polymers such as those based on 65 to enable varying degrees of parallel and series connectivity. thiophenes and anilines, and their respective monomers, Afterwards, the single layer nanocomposite composition of which form a conducting composites with iodine. Finally the present invention is deposited by direct write technology US 9,331,357 B2 10 between the parallel plates followed by a top layer coating of tion. In addition, complete current collector structures com a hermetic barrier based on inorganic or inorganic/organic prising an inner current collector and an outer current collec hybrids containing an inorganic component including but not tor made according to the present invention can be micro limited to aluminum oxides, metals, silicon oxides, titanium machined from a metal monolithe. As envisioned, the MPRs oxides, silicon nitrides, and the like. The full cell then is could extend to long continuous dimensions or be intercon fabricated by electrochemical polarization. nected, both allowing large increases in stored energy. In other embodiments, micromachining capabilities, such as microwire electrodischarge machining (EDM) and laser EXAMPLES micromachining can be used to form discrete 3 dimensional The following examples are put forth so as to provide those micro power cubes (“MPC’s) smaller than 1 mm in dimen 10 of ordinary skill in the art with a complete disclosure and sion. MPCs prepared according to the present invention are description of how to make and use the present invention, and incorporated into electronics and handled very much like are not intended to limit the scope of what the inventors regard micro multilayered capacitors in implementation. as their invention nor are they intended to represent that the In certain embodiments, the present invention takes the experiments below are all or the only experiments performed. form of a micro power rod (“MPR”). As shown in FIG. 3, a 15 cylindrical sheathis formed of a hermetic conducting metal or Example 1 Si. The counter current collector wire at the center of the cylinder is formed of at least one metal selected from the Formation of Electrochemical Cells In Situ from a group of stainless steel, magnesium, chromium, tungsten and Nanocomposite of Lil and Poly(vinylpyrrolidone) aluminum. It is preferred that the current collector wire is 20 (PVP) formed of a stiff conducting metal, such as tungsten. The nanocomposite of the present invention is backfilled between LiI and poly(vinylpyrrolidone) (PVP) were dissolved in the two current collectors and polarized to form the three methanol and dried in a glass Petri dish at 150° C. under air. layers of the battery (anode, electrolyte, and cathode) in-situ. Afterwards, the material was ground and dried under vacuum. The resulting material was reground and placed inside of an The ends are sealed with a low melting point hermetic inor 25 electrochemical test cell of Swagelok construction. The cell ganic or inorganic/organic hybrid compound. The rod con was compressed such that the powderformed a densified disk figuration possesses multifold advantages. The metallic of approximately 200 micron thickness. The cell was placed sheath of the power rod acts a current collector and an excep on a computer-controlled galvanostat and the cell was tional hermetic barrier. In addition the rod configuration charged at a constant current of 10 pla. allows the energy storage chemistry of the present invention 30 As shown in the charge-discharge curve in FIG. 5, the to be an integral structural member which can be utilized to initial voltage of the cell was zero volts, consistent with the build the framework of micromachines and of micro air fact that only the LiI based composite but no electrochemical vehicles and, additionally, to give power. It is envisioned that cell existed. During the charge, a long plateau develops at a micro power rod made according to the present invention approximately 3.5V. At this point, a 3-layer cell is formed in can act as an antennae for communication applications. It is 35 situ. During charge, lithium metal is deposited at the negative further envisioned that the structural framework, antennae, current collector to form the anode and an iodine-PVP com actuator wing, and integral sensor of the micro air vehicle posite is formed by the oxidation of IT to an iodine species made according to the present invention comprise containing polyiodide. Intermediate in the charging process, micropower rods. the cell is placed on discharge to confirm the existence of the Another configuration of the present invention relates to 40 electrochemical couple. Surprisingly, a discharge plateau is smart needles. In such embodiments, a tube having three developed during discharge between 2-2.5 V. This confirms dimensions (length, width, and depth) that is circular, square, the in-situ formation of a useable electrochemical cell and oblong, or rectangular in cross section is extended in at least deliverance of useful electrochemical energy. one dimension to incorporate sensor, communications and Example 2 energy harvesting electronics technology within the tube. In a 45 preferred embodiment, the thickness of the tube in 2 of the 3 Formation of Electrochemical Cells In Situ from a dimensions is less than 1 mm, and the axial ratio is >1. The Nanocomposite of Lil and Polyethylene Oxide term “axial ratio” as used herein refers to ratio of the length of the tube to the diameter of the tube: LiI and polyethylene oxide (PEO) were dissolved and cast 50 Axial ratio (P)=length/diameter in a solvent of acetonitrile. The fabricated free-standing film was cut out and placed in an electrochemical cell and tested This smart needle configuration has the advantages of ease electrochemically as described in Example 1. Here, a tem of deployment and lower cross sectional profile. For pharma perature of 80°C. was utilized to improve kinetics. As shown ceutical or biomedical applications, a needle sensor made in the charge-discharge curve in FIG. 6, the cell showed no according to the present invention can be injected into the 55 initial voltage. However, after application of current, a three body of a patient to provide in-vivo sensor and localized drug layer cell was formed in-situ. The capacity of the cell could be delivery. FIG. 4 shows the scalability of the smart needle recovered on subsequent discharges. The length of the dis configuration: power rods of the present invention can be charge corresponds directly with the length of the formation formed from diameters larger than a pin (100s micron), and of the charge. from diameters between that of a pin and a hair (10s micron). 60 Present day state of the art stainless tube construction allows Example 3 a range from a small 450/338 pum outer diameter/inner diam eter (“OD/ID") down to a very fine 125/50 pm OD/ID for Fabrication and Electrochemistry of Lil/10% PVP stainless having a 25 pum tungsteninner core electrode. Newly Nanocomposites adopted micromachining techniques in silicon and stainless 65 allow an OD of about 30-50 pum with a 5-10 pum inner core Table 1 summarizes the fabrication conditions and result current collector, the limit of practicality for this configura ing electrochemical data of a number of examples of the

US 9,331,357 B2 15 16 by one of ordinary skill in the art to which this invention 2. The method according to claim 1, wherein the metal belongs. Although any methods and materials similar or halide nanocomposite is selected from the group consisting of equivalent to those described herein can also be used in the an alkali metal halide nanocomposite, an alkaline earth metal practice or testing of the present invention, the preferred halide nanocomposite, and a rare earth metal halide nano methods and materials are now described. All publications composite. mentioned herein are incorporated herein by reference to 3. The method according to claim 2, wherein the alkali disclose and describe the methods and/or materials in con metal halide nanocomposite comprises an alkali metal cation nection with which the publications are cited. selected from the group consisting of a lithium cation, a It must be noted that as used herein and in the appended sodium cation, a potassium cation, a rubidium cation, and a claims, the singular forms “a”, “and”, and “the include plural 10 cesium cation. references unless the context clearly dictates otherwise. All technical and scientific terms used herein have the same 4. The method according to claim 3, wherein the alkali meaning. Efforts have been made to ensure accuracy with metal halide nanocomposite is a lithium iodide nanocompos respect to numbers used (e.g. amounts, temperature, etc.) but ite comprising a lithium cation and an iodide anion. some experimental errors and deviations should be accounted 15 5. The method according to claim 2, wherein the alkaline for. Unless indicated otherwise, parts are parts by weight, earth metal halide nanocomposite comprises an alkaline earth molecular weight is weight average molecular weight, tem metal cation selected from the group consisting of a magne perature is in degrees Centigrade, and pressure is at or near sium cation, a calcium cation, a strontium cation, and a atmospheric. barium cation. Where a range of values is provided, it is understood that 20 6. The method according to claim 2, wherein the rare earth each intervening value, to the tenth of the unit of the lower metal halide nanocomposite comprises a rare earth metal limit unless the context clearly dictates otherwise, between cation selected from the group consisting of a yttrium cation the upper and lower limit of that range and any other stated or and a lanthanum cation. intervening value in that stated range is encompassed within 7. The method according to claim 1, wherein the metal the invention. The upper and lower limits of these smaller 25 halide nanocomposite comprises ahalide anion selected from ranges which may independently be included in the smaller the group consisting of a fluoride anion, a bromide anion, an ranges is also encompassed within the invention, subject to iodide anion and a chloride anion. any specifically excluded limit in the stated range. Where the 8. The method according to claim 1, wherein the metal stated range includes one or both of the limits, ranges exclud halide nanocomposite comprises a fluoride anion. ing either both of those included limits are also included in the 30 9. The method according to claim 1, wherein the metal invention. halide nanocomposite comprises an iodide anion. The publications discussed herein are provided solely for 10. The method according to claim 9, wherein the forming their disclosure prior to the filing date of the present applica in situ further comprises forming a compound comprising an tion. Nothing herein is to be construed as an admission that oxidized iodate ion at the positive electrode upon application the present invention is not entitled to antedate such publica 35 of the potential. tion by virtue of prior invention. Further, the dates of publi 11. The method according to claim 9, wherein the forming cation provided may be different from the actual publication in situ further comprises forming an oxidized compound dates which may need to be independently confirmed. comprising a polyiodide ion at the positive electrode upon The invention has been described with reference to the application of the potential. preferred embodiment to illustrate the principles of the inven 40 12. The method according to claim 9, wherein the forming tion and not to limit the invention to the particular embodi in situ further comprises forming an oxidized compound ment illustrated. Modifications and alterations may occur to comprising a metal iodide at the positive electrode upon others upon reading and understanding the preceding detailed application of the potential. description. It is intended that the scope of the invention be 13. The method according to claim 1, wherein the metal construed as including all modifications and alterations that 45 halide nanocomposite further comprises an organic compo may occur to others upon reading and understanding the nent. preceding detailed description insofaras they come within the 14. The method according to claim 13, wherein the organic scope of the following claims or equivalents thereof. component is an organic material that forms compounds with What is claimed is: iodine. 1. A method for forming an electrochemical cell in situ 50 15. The method according to claim 13, wherein the organic from a nanocomposite which enables self-assembly of a tri component is poly(vinylpyrrolidone). layer electrochemical cell, comprising the steps of: 16. The method according to claim 13, wherein the organic supplying an ionically conductive, electrically insulative component is a conductive compound. single-layer nanocomposite between two current collec 17. The method according to claim 13, wherein the organic tors at an initial voltage of 0 V, wherein the nanocom 55 component is a conductive compound selected from the posite has an ionic conductivity greater than 0.0001 group consisting of vinylpyridine, poly(2 vinylpyridine), eth mS/cm and includes a binder and a metal halide having ylene oxide, polyethylene oxide, vinyldene fluoride, polyvi a metal cation and a halide anion; and nyldene fluoride, thiophene, polythiophene, fluorothiophene, applying a potential across the nanocomposite by way of polyfluorothiophene, pyrrole, polypyrrole, aniline, and the two current collectors, thereby forming in situ the 60 polyaniline. tri-layer electrochemical cell comprising: 18. The method according to claim 1, wherein the metal (i) a negative electrode comprising an elemental metal halide nanocomposite further comprises a nanostructured formed by reducing the metal cation; inorganic component. (ii) a positive electrode comprising an oxidized form of the 19. The method according to claim 18, wherein the nano halide anion; and 65 structured inorganic component is at least one compound (iii) a thermodynamically stable electrolyte comprising the selected from the group consisting of siliconoxide, aluminum metal halide. oxide, barium titanate, and silicon nitride. US 9,331,357 B2 17 18 20. The method according to claim 1, wherein the metal halide nanocomposite further comprises at least one sub group selected from the group consisting of water and hydroxyl ions. 21. The method according to claim 1, wherein the negative electrode further comprises a metal current collector. 22. The method according to claim 21, wherein the metal current collector of the negative electrode is formed of a metal selected from the group consisting of stainless steel, silicon, nickel, aluminum, tin, gold, silver, platinum, and copper. 10 23. The method according to claim 21, wherein the oxi dized halide ion forms a complex with the metal current collector of the positive electrode. 24. The method according to claim 1, wherein the positive electrode comprises a metal current collector. 15 25. The method according to claim 24, wherein the metal current collector of the positive electrode is formed of a metal selected from the group consisting of stainless steel, copper, nickel, aluminum, gold, silver, and platinum. 26. The method according to claim 1, wherein the metal 20 halide nanocomposite is deposited in a thickness of less than 100 microns. 27. The method according to claim 1, wherein the metal halide nanocomposite is deposited by a direct write technol Ogy. 25