USOO962O808B2

(12) United States Patent (10) Patent No.: US 9,620,808 B2

Aryanfar (45) Date of Patent: Apr. 11, 2017
(54) METHOD AND DEVICE FOR DENDRITE (58) Field of Classification Search
RESEARCH AND DISCOVERY IN CPC ............. H01M 10/0427; H01M 2/022; H01M
BATTERIES 10/0585; H01M 10/4285
See application file for complete search history.
(71) Applicant: Asghar Aryanfar, Pasadena, CA (US)
(72) Inventor: Asghar Aryanfar, Pasadena, CA (US) (56) References Cited
U.S. PATENT DOCUMENTS
(73) Assignee: California Institute of Technology,
Pasadena, CA (US) 6,749,648 B1* 6/2004 Kumar ................... B82Y 3O/OO
29/623.1
(*) Notice: Subject to any disclaimer, the term of this 2004/0146780 A1* 7/2004 Rubino ................. HO1M 2/O23
patent is extended or adjusted under 35 429,164
U.S.C. 154(b) by 434 days. 2009, O1971.71 A1* 8, 2009 Nakazato ............... HO1G 9,016
429,209
(21) Appl. No.: 14/201.979 2014/0093.052 A1* 4/2014 Chupas ............ GO1N 23, 20025
378,208
(22) Filed: Mar. 10, 2014 * cited by examiner
(65) Prior Publication Data
US 2014/0255763 A1 Sep. 11, 2014
Primary Examiner — Barbara Gilliam
Assistant Examiner —Nathanael Zemui
Related U.S. Application Data (74) Attorney, Agent, or Firm — Gavrilovich, Dodd &
Lindsey LLP; Joseph R. Baker, Jr.
(60) Provisional application No. 61/776,454, filed on Mar.
11, 2013.
(57) ABSTRACT
(51) Int. C.
An electrolytic coin cell that has been used to study the
HIM I/04 (2006.01) growth of lithium dendrites by optical observation is
HOLM 2/02 (2006.01)
HIM IO/0585 (2010.01) described. The cell makes possible observation of the
HIM ID/242 (2006.01) growth of the dendrites in response to various applied
conditions, such as applied electrical signals, chemical
(52) U.S. C.
effects, and temporal effects in a real coin cell geometry.
CPC ....... H0IM 10/0427 (2013.01); H0IM 2/022
(2013.01); H0IM 10/0585 (2013.01); H0IM
10/4285 (2013.01) 9 Claims, 6 Drawing Sheets

{Carnaiian: $;8cate 8xxixer

Sectices A
---
x
Acrylic separator x,
x
U.S. Patent Apr. 11, 2017 Sheet 1 of 6 US 9,620,808 B2

F.G. 1A F.G. 1B

FIG 1C F.G. 1D

FG. 2C FG. 2D
U.S. Patent Apr. 11, 2017 Sheet 2 of 6 US 9,620,808 B2

FIG. 3C FIG. 3D

FIG. 4B FIG. 4C
U.S. Patent Apr. 11, 2017 Sheet 3 of 6 US 9,620,808 B2

FIG 5A

F.G. 6C F.G. 6D
U.S. Patent Apr. 11, 2017 Sheet 4 of 6 US 9,620,808 B2

FIG. 7

FIG. 8
U.S. Patent Apr. 11, 2017 Sheet S of 6 US 9,620,808 B2

upu?a
se

ue,
U.S. Patent Apr. 11, 2017 Sheet 6 of 6 US 9,620,808 B2

FIG. 12
 US 9,620,808 B2
1. 2
METHOD AND DEVICE FOR DENDRITE Society, 2008. 155 (11): p. A806-A811; Howlett, P. C., D. R.
RESEARCH AND DISCOVERY IN MacFarlane, and A. F. Hollenkamp. A sealed optical cell for
BATTERIES the study of lithium-electrode electrolyte interfaces. Journal
of Power Sources, 2003. 114 (2): p. 277-284; Schweikert,
CROSS-REFERENCE TO RELATED N., et al., Suppressed lithium dendrite growth in lithium
APPLICATIONS batteries using ionic liquid electrolytes. Investigation by
electrochemical impedance spectroscopy, scanning electron
This application claims priority to and the benefit of microscopy, and in situ Li nuclear magnetic resonance
co-pending U.S. provisional patent application Ser. No. spectroscopy. Journal of Power Sources, 2013. 228 (0): p.
61/776,454, filed Mar. 11, 2013, which application is incor 10 237-243) and electrolyte concentration (see Brissot, C., et
porated herein by reference in its entirety. al. In situ concentration cartography in the neighborhood of
dendrites growing in lithium/polymer-electrolyte/lithium
FIELD OF THE INVENTION cells. Journal of the Electrochemical Society, 1999. 146
(12): p. 4393-4400; Brissot, C., et al., Concentration mea
The invention relates to apparatus used in research in 15 surements in lithium/polymer-electrolyte/lithium cells dur
general and particularly to apparatus that allows in situ ing cycling. Journal of Power Sources, 2001. 94 (2): p.
experimental visualization. 212-218) on dendrite formation.
Methods that have been developed to slow down dendrite
BACKGROUND OF THE INVENTION formation include the use of powdered electrodes (see Kim,
W. S. and W. Y. Yoon, Observation of dendritic growth on
Rechargeable batteries are known to fail unexpectedly via Li powder anode using optical cell. Electrochimica Acta,
short-circuiting through metallic dendrites that grow 2004. 50 (2-3): p. 541-545), the application of successive
between electrodes upon recharging. This phenomenon trig bipolar charge pulses (see Chen, L. L., Xue Li Zhao, Qiang
gers a series of events that begin with overheating, eventu Cai, Wen Bin Jiang, ZhiYu Bipolar Pulse current method for
ally followed by the thermal decomposition and ultimately 25 inhibiting the formation and lithium dendrites. Acta Phys.
the ignition of the organic Solvents used in Such devices. Chim. Sin, 2006. 22 (9): p. 1155-1158), and covering lithium
This flaw has become a major safety issue in the operation electrodes with adhesive lamellar block copolymers (see
of the recently introduced larger passenger aircraft. Stone, G. M., et al., Resolution of the Modulus versus
Many efforts have focused on exploring the effects of Adhesion Dilemma in Solid Polymer Electrolytes for
chemical composition and morphology of various electrode 30 Rechargeable Lithium Metal Batteries. Journal of the Elec
materials (see J. M Tarascon, M. A., Issues and challenges trochemical Society, 2012. 159 (3): p. A222-A227).
facing rechargeable lithium batteries. Nature, 2001 414: p. The dynamics of dendrite growth also has been charac
359-367: Armand, M. and J. M. Tarascon, Building better terized to some extent. Studies gave considered evolution
batteries. Nature, 2008. 451 (7179): p. 652-657) and the time (see Rosso, M., et al., Onset of dendritic growth in
nature of Solvents and electrolytes (see Xu, K. Nonaqueous 35 lithium/polymer cells. Journal of Power Sources, 2001.97-8:
liquid electrolytes for lithium-based rechargeable batteries. p. 804-806), growth rate (see Brissot, C., et al. In situ study
Chem Rev, 2004. 104 (10): p. 4303-417) on the energy of dendritic growth in lithium/PEO-salt/lithium cells. Elec
density and lifetime of batteries. However, ultimate battery trochimica Acta, 1998. 43 (10-11): p. 1569-1574) and elec
performance is still limited by capacity decay and failure trolyte convection see Fleury, V., J. N. Chazalviel, and M.
due to short-circuiting via dendrite formation. Lithium is 40 Rosso, Theory and Experimental-Evidence of Electrocon
used in lithium battery electrodes, whose energy density vection around Electrochemical Deposits. Physical Review
(38.62 mAh/g) is more than 10 times larger than graphite Letters, 1992. 68 (16): p. 2492-2495).
(372 mAh/g). On the other hand, lithium is more prone to On the theoretical side, the few idealistic schemes have
grow dendrites relative to graphite, since lithium deposition been developed to account for lithium dendrite growth have
is dominant over lithium intercalation (see Daniel, C., Mate 45 multiple deficiencies, such as dendrite shape and one dimen
rials and Processing for Lithium-Ion Batteries. JOM, 2008. sional cell geometry (see Chazalviel, J. N., Electrochemical
60). Aspects of the Generation of Ramified Metallic Electrode
Researchers have tried to prevent the growth of dendritic posits. Physical Review A, 1990. 42 (12): p. 7355-7367:
microstructures using various techniques, which are still Monroe, C. and J. Newman, Dendrite growth in lithium/
unsuccessful. On the experimental side, several studies have 50 polymer systems—A propagation model for liquid electro
tracked the influence of control parameters such as current lytes undergalvanostatic conditions. Journal of the Electro
density (see F. Orsini, A.D.P. B. Beaudoin, J. M. Tarascon, chemical Society, 2003. 150 (10): p. A1377-A1384). This
M. Trentin, N. Langenhuisen, E. D. Beer, P. Notten. In Situ has been confirmed by experimental studies on electro
Scanning Electron Microscopy (SEM) observation of inter chemical deposition of Zinc and copper (see Sagues, F., M.
faces with plastic lithium batteries. Journal of power 55 Q. Lopez-Salvans, and J. Claret, Growth and forms in
sources, 1998. 76: p. 19-29; Graciela Gonzalez, M. R., and quasi-two-dimensional electrocrystallization. Physics
Elisabeth Chassaing, Transition between two dendritic Reports-Review Section of Physics Letters, 2000. 337 (1-2):
growth mechanisms in electrodeposition. Physical Review p.97-115). Nonetheless, the dendrite morphology evolution
E, 2008. 78 (011601)), geometry (see Monroe, C. and J. mechanism is not yet understood. The microstructure study
Newman, The effect of interfacial deformation on electrode 60 is experimentally hard and the SEM imaging of dendrites is
position kinetics. Journal of the Electrochemical Society, not usually practical since the dendrites are very fragile and
2004. 151 (6): p. A880-A886; Liu, X. H., et al., Lithium fiber disassembling the cell and exposure of lithium metal to open
growth on the anode in a nanowire lithium ion battery atmosphere will not provide accurate results, for example
during charging. Applied Physics Letters, 2011. 98 (18)), because lithium reacts with oxygen and water vapor in the
Solvent and electrolyte chemical composition (see Crowther, 65 atmosphere.
O. and A. C. West, Effect of electrolyte composition on Other experimental approaches for observing dendrites
lithium dendrite growth. Journal of the Electrochemical have been unsuccessful as well (see Brissot, C., et al.,
 US 9,620,808 B2
3 4
Dendritic growth mechanisms in lithium/polymer cells. Jour the principles of the invention. In the drawings, like numer
nal of Power Sources, 1999.81: p. 925-929). als are used to indicate like parts throughout the various
There is a need for systems and methods that allow more views.
accurate observation of dendrite formation dynamics in FIG. 1A is a plan view of an anode current collector for
more realistic device similar to current batteries. 5 use in the coin cell.
FIG. 1B is a cross section view from one side of the anode
SUMMARY OF THE INVENTION current collector.
FIG. 1C is a cross section view of the anode current
collector from a direction 90 degrees away from the view of
According to one aspect, the invention features a coin FIG. 1B.
10
cell. The coin cell comprises a pair of current collectors, one FIG. 1D is a perspective view of the anode current
of the pair of current collectors having defined therein a collector.
sealable aperture, each current collector having a flat face, FIG. 2A is a plan view of a cathode current collector for
each current collector having an electrical contact accessible use in the coin cell.
on an exterior Surface of the coin cell; a non-conductive FIG. 2B is a cross section view from one side of the
15 cathode current collector.
separator having a transparent region, the non-conductive FIG. 2C is a cross section view of the cathode current
separator having a central cavity defined therein so as to collector from a direction 90 degrees away from the view of
space the respective flat faces of the pair of current collectors FIG. 2B.
apart by a predefined distance; a plurality of gaskets, each FIG. 2D is a perspective view of the cathode current
gasket forming an hermetic Seal between the non-conductive collector.
separator and one of the pair of current collectors when FIG. 3A is a plan view of a transparent separator for use
assembled; a seal for the additional sealable aperture of one in the coin cell.
of the pair of current collectors; and a plurality of non FIG. 3B is a cross section view from one side of the
conductive clamps that hold the pair of current collectors, transparent separator.
the non-conductive separator and the plurality of gaskets in 25 FIG. 3C is a cross section view of the transparent sepa
registry when assembled. rator from a direction 90 degrees away from the view of FIG.
3B.
In one embodiment, each of the pair of current collectors FIG. 3D is a perspective view of the transparent separator.
having a plurality of apertures defined therein, the plurality FIG. 4A is a perspective view of a screw used to hold the
of apertures of one of the pair of current collectors defined coin cell together when assembled.
so as to be in registry with the plurality of apertures of the 30
FIG. 4B is an end view of a screw used to hold the coin
other of the pair of current collectors when assembled, and cell together when assembled.
the non-conductive separator having a plurality of apertures FIG.4C is a side view of a screw used to hold the coin cell
defined therein so as to be in registry with the plurality of together when assembled.
apertures of each of the pair of current collectors when FIG. 5A is a perspective view of a nut used to hold the
assembled. 35 coin cell together when assembled.
In another embodiment, the plurality of non-conductive FIG. 5B is an end view of a nut used to hold the coin cell
clamps are nuts and screws. together when assembled.
In yet another embodiment, the screws are fabricated from FIG. 5C is a side view of a nut used to hold the coin cell
a non-conductive material. together when assembled.
In still another embodiment, the screws are fabricated 40 FIG. 6A is a plan view of a gasket for use in the coin cell.
from a conductive material and Screw insulators fabricated FIG. 6B is a cross section view from one side of the
from a non-conductive material are provided to electrically gasket.
separate the screws from at least one of the pair of current FIG. 6C is a cross section view of the gasket from a
collectors. direction 90 degrees away from the view of FIG. 6B.
In a further embodiment, the coin cell further comprises 45 FIG. 6D is a perspective view of the gasket used to
a foil made of an electrically conductive material that is hermetically seal the cell.
compatible with an electrolyte that is to be inserted into the FIG. 7 is a perspective view of a screw insulator used to
coin cell, the foil positioned in electrical contact with and electrically insulate the screws that hold the coin cell
covering the flat face of one of the pair of current collectors. together from at least one of the anode current collector and
In yet a further embodiment, the coin cell further com 50 the cathode current collector.
prises a pressure washer that makes electrical contact FIG. 8 is a schematic diagram showing a coin cell in
between the foil and the one of the pair of current collectors. partially assembled configuration and an eye of a viewer
In another embodiment, the electrically conductive mate looking across the coin cell from one side.
rial and the electrolyte comprise a metal. FIG. 9 is an exploded view of one embodiment of a coin
In yet another embodiment, the metal is lithium. 55 cell according to principles of the invention.
In an additional embodiment, the coin cell has cylindrical FIG. 10 is an image of an assembled coin cell held in a
symmetry. hand to show relative scale.
The foregoing and other objects, aspects, features, and FIG. 11 is a schematic diagram of a system in which
advantages of the invention will become more apparent from experiments have been performed using the electrolytic coin
the following description and from the claims. 60 cell according to principles of the invention.
FIG. 12 is an image of dendrites observed in situ using a
BRIEF DESCRIPTION OF THE DRAWINGS cell that operates according to principles of the invention.
The objects and features of the invention can be better DETAILED DESCRIPTION
understood with reference to the drawings described below, 65
and the claims. The drawings are not necessarily to scale, More direct techniques for monitoring dendrite formation
emphasis instead generally being placed upon illustrating with better time and spatial resolution seem essential to
 US 9,620,808 B2
5 6
advance our understanding of the phenomenon of dendrite Table 1 lists the dimensions used in one embodiment of
growth (see Bhattacharyya, R., et al. In situ NMR observa the coin cell, which dimensions are indicated in the various
tion of the formation of metallic lithium microstructures in drawings. The angle C. is 120 degrees in a preferred embodi
lithium batteries. Nature Materials, 2010.9 (6): p. 504-510). ment, but any convenient angle and any convenient number
We now describe a coin cell that provides direct visual N greater than or equal to two of Screws and corresponding
observation of dendrite growth and morphology in situ and nuts can be used.
offers more accurate information for understanding the
behavior of lithium batteries. TABLE 1.
The coin cell is constructed of components that are
separable. In operation, the coin cell can be sealed to prevent 10 Dimension Size (inches)
reaction with undesired chemical species, such as water D1 1.OO
vapor and oxygen in room air. The components of the coin D2 O.625
cell are as follows: D3 O.12
Current collectors are made of brass, copper or any R1
T1
O4O625
0.1875
convenient conductive metal. They can be placed in elec 15
T2 0.1875
trical communication with electrodes to transfer current. D4 0.4
FIG. 1D is a perspective view of a first current collector, D5 O.08
which is circular with indentation and holes. FIG. 2D is a D2 - 6 O627
T 0.375
perspective view of a second current collector, which has the
same construction as the first current collector with the
exception that there is a threaded aperture defined in it (for FIG. 8 is a schematic diagram showing a coin cell in
example, a 1/71 treaded hole located in the middle of it) to partially assembled configuration and an eye of a viewer
provide a path for electrolyte injection into the coin cell. looking across the coin cell from one side.
FIG. 3D is a perspective view of a transparent separator FIG. 9 is an exploded view of one embodiment of a coin
is provided which determines the inter-electrode distance. 25
cell according to principles of the invention. In FIG. 9 two
The transparent separator can be made of acrylic (which is structures indicated as “electrodes' (one of which has an
easy to machine), or in alternative embodiments, from any aperture that is aligned with the filling hole in the electrode
transparent non-reactive material that is convenient. The shown in FIG. 2D) and two structures indicated as “wave
transparent separator needs to be transparent at a location disk springs' are illustrated. The electrodes can be thin
where one will observe the events that occur within the 30
volume of the coin cell that contains an electrolyte, but sheets of a metal (in one embodiment lithium metal) that is
otherwise could equally well be opaque elsewhere. The compatible with the dendrites that are intended to be studied.
separator should be an insulator, rather than conductive. The “wave disk springs are pressure washers analogous to
FIG. 4A is a perspective view of a screw used to hold the lock washers, Belleville washers (cupped spring washers or
coin cell together when assembled. In one embodiment, the 35 conical washers) or spring washers and are provided to make
screws are made of 1-71 stainless steel and are 1" long. a positive electrical contact between the respective electrode
However, it will be understood that the screws can be made and the corresponding current collector, so that electrical
of any convenient material that is strong enough to hold the continuity can be assured between the two parts. In some
assembled cell together when operating, can be any conve embodiments, the pressure washers cam be omitted if the
nient length that is sufficient to hold the assembled cell 40 pressure applied by the clamps is sufficient to assure elec
together, and can have any convenient thread. It will further trical contact between the foil and the current collector.
be understood that if the screws are made of a non-conduc As illustrated in FIG. 9, the coin cell comprises two Li'
tive material such as nylon, the screw insulators will be foil disc electrodes (1.59 cm diameter) separated 0.32 cm by
redundant and may be omitted. a transparent acrylic ring. The cell was filled with 1 M
FIG. 5A is a perspective view of a nut used to hold the 45 LiClO in propylene carbonate (PC) as electrolyte. All
coin cell together when assembled. In one embodiment, the operations were conducted in an argon-filled (H2O, O.<0.5
nuts are 1771 nuts made of stainless steel. However, it will ppm) glovebox. Arrays of multiple Such cells were simul
be understood that the nuts can be made of any convenient taneously electrolyzed under galvanostatic conditions with 2
material that is strong enough to hold the assembled cell mA cm pulses generated by a programmable multichannel
together when operating, and can have any thread that will 50 charger. After 48 mAh (173 Coulombs) have circulated
mate with the screws used to hold the assembled cell through the cells, the lengths of 45 dendrites around the cell
together. perimeter were measured through the acrylic separator using
FIG. 6D is a perspective view of a gasket used to a Leica M205FA optical microscope.
hermetically seal the cell. In one embodiment, the gasket is FIG. 10 is an image of an assembled coil cell held in a
made of compliant silicone rubber. In other embodiments, 55 hand to show relative scale.
other compliant materials that can be used as gaskets may be FIG. 11 is a schematic diagram of a system in which
employed. experiments have been performed using the electrolytic coin
FIG. 7 is a perspective view of a screw insulator used to cell according to principles of the invention.
electrically insulate the screws that hold the coin cell We have performed experiments in the electrolytic coin
together from at least one of the anode current collector and 60 cell that provides for in situ observation of the dendrites
the cathode current collector. grown on the perimeter of the disc electrodes at any stage
In alternative embodiments, the assembled coin cell can using a microscope as illustrated schematically in FIG. 11.
be held together by clamps, such as “C” clamps applied to FIG. 12 is an image of dendrites observed in situ using a
the opposite external (free) surfaces of the current collectors, cell that operates according to principles of the invention.
and the apertures that provide space for the screws to pass 65 The cell has capability for complete sealing for several
through the various layers of components, the screws them months and is also detachable from an electrical source for
selves, the nuts, and the screw insulators all can be omitted. further studies of dendrites.
 US 9,620,808 B2
7 8
Definitions ment with said plurality of apertures of the other of said
Unless otherwise explicitly recited herein, any reference pair of current collectors when assembled;
to an electronic signal or an electromagnetic signal (or their a non-conductive separator having a transparent region,
equivalents) is to be understood as referring to a non said non-conductive separator having a central cavity
transitory electronic signal or a non-transitory electromag defined therein so as to space said respective flat faces
netic signal. of said pair of current collectors apart by a predefined
Theoretical Discussion distance, wherein the non-conductive separator has a
Although the theoretical description given herein is plurality of apertures defined therein so as to be in
thought to be correct, the operation of the devices described alignment with said plurality of apertures of each of
and claimed herein does not depend upon the accuracy or 10
said pair of current collectors when assembled;
validity of the theoretical description. That is, later theoreti a plurality of gaskets, each gasket forming a hermetic seal
cal developments that may explain the observed results on a between said non-conductive separator and one of said
basis different from the theory presented herein will not pair of current collectors when assembled;
detract from the inventions described herein.
Any patent, patent application, patent application publi 15 a seal for said sealable aperture of one of said pair of
cation, journal article, book, published paper, or other pub current collectors; and
licly available material identified in the specification is a plurality of non-conductive clamps that hold said pair of
hereby incorporated by reference herein in its entirety. Any current collectors, said non-conductive separator and
material, orportion thereof, that is said to be incorporated by said plurality of gaskets in alignment when assembled.
reference herein, but which conflicts with existing defini 2. The coin cell of claim 1, wherein said plurality of
tions, statements, or other disclosure material explicitly set non-conductive clamps are nuts and screws.
forth herein is only incorporated to the extent that no conflict 3. The coin cell of claim 2, wherein said screws are
arises between that incorporated material and the present fabricated from a non-conductive material.
disclosure material. In the event of a conflict, the conflict is 4. The coin cell of claim 2, wherein said screws are
fabricated from a conductive material and screw insulators
to be resolved in favor of the present disclosure as the 25
fabricated from a non-conductive material are provided to
preferred disclosure.
While the present invention has been particularly shown electrically separate said screws from at least one of said pair
of current collectors.
and described with reference to the preferred mode as 5. The coin cell of claim 1, further comprising a foil made
illustrated in the drawing, it will be understood by one of an electrically conductive material that is compatible with
skilled in the art that various changes in detail may be 30
an electrolyte that is to be inserted into said coin cell, said
affected therein without departing from the spirit and scope foil positioned in electrical contact with and covering said
of the invention as defined by the claims. flat face of one of said pair of current collectors.
What is claimed is:
1. A coin cell, comprising: 6. The coin cell of claim 5, wherein said electrically
a pair of current collectors, one of the pair of current 35 conductive material and said electrolyte comprise a metal.
collectors having defined therein a sealable aperture, 7. The coin cell of claim 6, wherein said metal is lithium.
each current collector having a flat face, each current 8. The coin cell of claim 5, further comprising a pressure
washer that makes electrical contact between said foil and
collector having an electrical contact accessible on an said one of said pair of current collectors.
exterior surface of said coin cell, wherein each of said 9. The coin cell of claim 1, wherein said coin cell has
pair of current collectors has a plurality of apertures 40
cylindrical symmetry.
defined therein, said plurality of apertures of one of said
pair of current collectors defined so as to be in align