US10916753

USO10916753B2
( 12 ) Visco
Unitedet al .
States Patent ( 10 ) Patent No .: US 10,916,753 B2
Feb. 9 , 2021
(45 ) Date of Patent :
( 54 ) LITHIUM METAL — SEAWATER BATTERY ( 58 ) Field of Classification Search

CELLS HAVING PROTECTED LITHIUM None
ELECTRODES See application file for complete search history .
( 71 ) Applicant: PolyPlus Battery Company, Berkeley , ( 56 ) References Cited
CA (US ) U.S. PATENT DOCUMENTS
(72) Inventors: Steven J. Visco , Berkeley , CA (US ) ; 3,343,988 A 9/1967 Friend
Bruce D. Katz , Moraga, CA (US ); 3,528,856 A 9/1970 Ovshinsky
Yevgeniy S. Nimon , Danville, CA ( Continued )
( US ) ; Lutgard C. De Jonghe,
Lafayette , CA (US ) FOREIGN PATENT DOCUMENTS
( 73 ) Assignee : PolyPlus Battery Company , Berkeley EP 111213 11/1983
EP 111214 11/1983
( * ) Notice: Subject to any disclaimer, the term of this (Continued )
patent is extended or adjusted under 35
U.S.C. 154 ( b ) by 0 days. OTHER PUBLICATIONS
( 21 ) Appl . No .: 16 /695,054 EP Application No. 03 809 186.4 , Decision to Refuse , dated Jul. 13 ,
2017 , 52 pages .
(22 ) Filed : Nov. 25 , 2019 (Continued )
( 65 ) Prior Publication Data Primary Examiner Tracy M Dove
( 74 ) Attorney, Agent, or Firm Weaver Austin
US 2020/0168876 A1 May 28 , 2020 Villeneuve & Sampson LLP
( 57 ) ABSTRACT
Related U.S. Application Data Active metal and active metal intercalation electrode struc
tures and battery cells having ionically conductive protective
( 60) Continuation of application No. 15 / 487,364 , filed on architecture including an active metal (e.g. , lithium ) con
Apr. 13 , 2017 , now Pat . No. 10,529,971 , which is a ductive impervious layer separated from the electrode (an
( Continued ) ode ) by a porous separator impregnated with a non - aqueous
electrolyte ( anolyte ). This protective architecture prevents
(51 ) Int. Ci. the active metal from deleterious reaction with the environ
HOIM 2/16 ( 2006.01 ) ment on the other ( cathode ) side of the impervious layer,
HOIM 6/34 ( 2006.01 ) which may include aqueous or non -aqueous liquid electro
(Continued ) lytes ( catholytes ) and/ or a variety electrochemically active
( 52) U.S. Ci . materials, including liquid , solid and gaseous oxidizers .
CPC HOIM 2/1673 (2013.01 ) ; HOIG 11/06 Safety additives and designs that facilitate manufacture are
( 2013.01 ) ; HONG 11/52 ( 2013.01 ) ; also provided .
( Continued ) 16 Claims , 6 Drawing Sheets
Potential- time curve for Li anode in cell having solid electrolyte membrane
separating non -aqueous anolyte from aqueous catholyte
-3.4
Anolyte : 1 M LIPF , PC
Catholyte: Seawater
-3.2
Discharge rate: 0.3 mA / cm2
OCP = 3.05 V
-3.0
Pvs.
SHE
o(
)tential
V
-2.8
-2.6
-2.4
0 2 4 6 8 10 12 14
Time (hrs )
US 10,916,753 B2
Page 2
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U.S. Patent Feb. 9 , 2021 Sheet 1 of 6 US 10,916,753 B2
110 104
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FIG . 1
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US 10,916,753 B2
1 2
LITHIUM METAL - SEAWATER BATTERY relates to an active metal ( e.g. , alkali metals , such as
CELLS HAVING PROTECTED LITHIUM lithium ), active metal intercalation (e.g. lithium -carbon,
ELECTRODES carbon ) and active metal alloys ( e.g. , lithium - tin ) alloys or
alloying metals (e.g. , tin) electrochemical ( e.g. , electrode)
CROSS - REFERENCE TO RELATED 5 structures and battery cells . The electrode structures have
APPLICATIONS ionically conductive protective architecture including an
active metal ( e.g. , lithium ) conductive impervious layer
This application is a continuation of U.S. patent applica separated from the electrode (anode ) by a porous separator
tion Ser. No. 15 /487,364 , filed Apr. 13 , 2017 , now allowed , impregnated with a non - aqueous electrolyte . This protective
which is a continuation of U.S. patent application Ser. No. 10 architecture prevents the active metal from deleterious reac
15 / 150,231 , filed May 9 , 2016 , now issued as U.S. Pat . No. tion with the environment on the other ( cathode) side of the
9,666,850 on May 30 , 2017 , which is a continuation of U.S. impervious layer, which may include aqueous, air or organic
patent application Ser. No. 14 / 156,267 , filed Jan. 15 , 2014 , liquid electrolytes and /or electrochemically active materials.
now issued as U.S. Pat . No. 9,368,775 on Jun . 14 , 2016 ,
which claims priority to U.S. Provisional Patent Application 15 2. Description of Related Art
No. 61 / 763,412 filed Feb. 11 , 2003 , titled PROTECTED LITHIUM
ELECTRODES HAVING A POROUS ELECTROLYTE INTERLAYER AND BAT- The low equivalent weight of alkali metals, such as
TERY CELLS THEREOF; and is a continuation - in -part of U.S. lithium , render them particularly attractive as a battery
patent application Ser. No. 13 / 929,653 , filed Jun . 27 , 2013 , electrode component. Lithium provides greater energy per
titled LITHIUM BATTERY HAVING A PROTECTED LITHIUM ELECTRODE 20 volume than the traditional battery standards, nickel and
AND AN IONIC LIQUID CATHOLYTE, now U.S. Pat. No. 8,828,580 ; cadmium . Unfortunately, no rechargeable lithium metal bat
which is a continuation of U.S. patent application Ser. No. teries have yet succeeded in the market place .
13 / 615,351 , filed Sep. 13 , 2012 , titled PROTECTED LITHIUM The failure of rechargeable lithium metal batteries is
ELECTRODES HAVING A POLYMER ELECTROLYTE INTERLAYER AND largely due to cell cycling problems. On repeated charge and
BATTERY CELLS THEREOF, now U.S. Pat. No. 8,501,339 ; which 25 discharge cycles , lithium “ dendrites” gradually grow out
is a continuation of U.S. patent application Ser. No. 12/888 , from the lithium metal electrode, through the electrolyte,
154 , filed Sep. 22 , 2010 , titled PROTECTED ACTIVE METAL and ultimately contact the positive electrode . This causes an
ELECTRODE AND BATTERY CELL WITH IONICALLY CONDUCTIVE PRO internal short circuit in the battery, rendering the battery
TECTIVE ARCHITECTURE, now U.S. Pat . No. 8,293,398 ; which is unusable after a relatively few cycles . While cycling, lithium
a continuation of U.S. patent application Ser. No. 11/824 , 30 electrodes may also grow “ mossy ” deposits that can dis
597 , filed Jun . 28 , 2007 , titled PROTECTED ACTIVE METAL lodge from the negative electrode and thereby reduce the
ELECTRODE AND BATTERY CELL STRUCTURES WITH NON -AQUEOUS battery's capacity.
INTERLAYER ARCHITECTURE, now U.S. Pat . No. 7,829,212 ; To address lithium's poor cycling behavior in liquid
which is a divisional of U.S. patent application Ser. No. electrolyte systems , some researchers have proposed coating
10/ 824,944 , filed Apr. 14 , 2004 , titled PROTECTED ACTIVE 35 the electrolyte facing side of the lithium negative electrode
METAL ELECTRODE AND BATTERY CELL STRUCTURES WITH NON- with a “ protective layer .” Such protective layer must con
AQUEOUS INTERLAYER ARCHITECTURE, now U.S. Pat . No. 7,282 , duct lithium ions , but at the same time prevent contact
295 ; which in turn claims priority to U.S. Provisional Patent between the lithium electrode surface and the bulk electro
Application No. 60 / 542,532 filed Feb. 6 , 2004 , titled PRO lyte . Many techniques for applying protective layers have
TECTED ACTIVE METAL ELECTRODE AND BATTERY CELL STRUCTURES 40 not succeeded .
WITH NON - AQUEOUS INTERLAYER ARCHITECTURE ; and U.S. Pro- Some contemplated lithium metal protective layers are
visional Patent Application No. 60/ 548,231 filed Feb. 27 , formed in situ by reaction between lithium metal and
2004 , titled VARIATIONS ON PROTECTED ACTIVE METAL ELECTRODE compounds in the cell's electrolyte that contact the lithium .
AND BATTERY CELL STRUCTURES WITH NON -AQUEOUS INTERLAYER Most of these in situ films are grown by a controlled
ARCHITECTURE. 45 chemical reaction after the battery is assembled . Generally,
Application Ser. No. 14/ 156,267 also claims the benefit of such films have a porous morphology allowing some elec
U.S. Provisional Patent Application No. 61 /763,412 filed trolyte to penetrate to the bare lithium metal surface. Thus,
Feb. 11 , 2013 , titled PROTECTED LITHIUM ELECTRODES HAVING A they fail to adequately protect the lithium electrode.
POROUS ELECTROLYTE INTERLAYER AND BATTERY CELLS THEREOF. Various pre - formed lithium protective layers have been
The disclosures of all these prior applications are incor- 50 contemplated . For example ,U.S. Pat. No. 5,314,765 (issued
porated herein by reference in their entirety and for all to Bates on May 24 , 1994 ) describes an ex situ technique for
purposes . fabricating a lithium electrode containing a thin layer of
sputtered lithium phosphorus oxynitride (“ LiPON ”) or
STATEMENT OF GOVERNMENT SUPPORT related material. LiPON is a glassy single ion conductor
55 ( conducts lithium ion ) that has been studied as a potential
This invention was made with Government support under electrolyte for solid state lithium microbatteries that are
Award No .: DE -AR0000349 awarded by the Advanced fabricated on silicon and used to power integrated circuits
Research Projects Agency -Energy (ARPA - E ), U.S. Depart- ( See U.S. Pat . Nos . 5,597,660 , 5,567,210 , 5,338,625 , and
ment of Energy. The Government has certain rights in this 5,512,147 , all issued to Bates et al . ) .
invention . 60 Work in the present applicants’ laboratories has devel
oped technology for the use of glassy or amorphous protec
BACKGROUND OF THE INVENTION tive layers , such as LiPON , in active metal battery elec
trodes . ( See , for example, U.S. Pat. No. 6,025,094 , issued
1. Field of the Invention Feb. 15 , 2000 , U.S. Pat . No. 6,402,795 , issued Jun . 11 , 2002 ,
65 U.S. Pat. No. 6,214,061 , issued Apr. 10 , 2001 and U.S. Pat.
The present invention relates generally to active metal No. 6,413,284 , issued Jul. 2 , 2002 , all assigned to PolyPlus
electrochemical devices. More particularly, this invention Battery Company ).
US 10,916,753 B2
3 4
Prior attempts to use lithium anodes in aqueous environ- soluble in water, for example dioxolane (Diox )/polydiox
ments relied either on the use of very basic conditions such aloane and the catholyte may include a polymerization
as use of concentrated aqueous KOH to slow down the initiator for the monomer , for example, a protonic acid .
corrosion of the Li electrode, or on the use of polymeric In addition, the structures and cells of the present inven
coatings on the Li electrode to impede the diffusion of water 5tion may take any suitable form . One advantageous form
to the Li electrode surface. In all cases however, there was that facilitates fabrication is a tubular form .
substantial reaction of the alkali metal electrode with water. In one aspect , the invention pertains to an electrochemical
In this regard, the prior art teaches that the use of aqueous cell structure . The structure includes an anode composed of
cathodes or electrolytes with Li -metal anodes is not possible an active metal, active metal - ion , active metal alloy, active
since the breakdown voltage for water is about 1.2 V and a 10 metal alloying metal or active metal intercalating material .
Li /water cell can have a voltage of about 3.0 V. Direct The anode has an ionically conductive protective architec
contact between lithium metal and aqueous solutions results ture on its surface. The architecture includes an active metal
in violent parasitic chemical reaction and corrosion of the ion conducting separator layer that has a non - aqueous
lithium electrode for no useful purpose . Thus, the focus of anolyte and is chemically compatible with the active metal
research in the lithium metal battery field has been squarely 15 and in contact with the anode, and a substantially impervious
on the development of effective non -aqueous (mostly ionically conductive layer chemically compatible with the
organic ) electrolyte systems . separator layer and aqueous environments and in contact
with the separator layer. The separator layer may be , a
SUMMARY OF THE INVENTION semi-permeable membrane impregnated with an organic
20 anolyte , for example , a micro - porous polymer impregnated
The present invention relates generally to active metal with a liquid or gel phase anolyte. Such an electrochemical
electrochemical devices. More particularly, this invention ( electrode) structure may be paired with a cathode system ,
relates to an active metal (e.g. , alkali metals , such as including an aqueous cathode system , to form battery cells
lithium ), active metal intercalation (e.g. lithium -carbon , in accordance with the present invention .
carbon) and active metal alloys ( e.g. , lithium - tin , lithium- 25 The structures and battery cells incorporating the struc
silicon) alloys or alloying metals (e.g. , tin , silicon) electro tures of the present invention may have various configura
chemical ( e.g. , electrode) structures and battery cells . The tions , including prismatic and cylindrical, and compositions,
electrochemical structures have ionically conductive protec- including active metal ion , alloy and intercalation anodes,
tive architecture including an active metal ( e.g. , lithium ) ion aqueous , water, air, metal hydride and metal oxide cathodes ,
conductive substantially impervious layer separated from 30 and aqueous, organic or ionic liquid catholytes; electrolyte
the electrode ( anode ) by a porous separator impregnated (anolyte and / or catholyte ) compositions to enhance the
with a non - aqueous electrolyte ( anolyte ). This protective safety and / or performance of the cells ; and fabrication
architecture prevents the active metal from deleterious reac- techniques.
tion with the environment on the other ( cathode) side of the These and other features of the invention are further
impervious layer, which may include aqueous, air or organic 35 described and exemplified in the detailed description below.
liquid electrolytes ( catholytes ) and / or electrochemically
active materials . BRIEF DESCRIPTION OF THE DRAWINGS
The separator layer of the protective architecture prevents
deleterious reaction between the active metal ( e.g. , lithium ) FIG . 1 is a schematic illustration of an electrochemical
of the anode and the active metal ion conductive substan- 40 structure cell incorporating an ionically conductive protec
tially impervious layer. Thus, the architecture effectively tive interlayer architecture in accordance with the present
isolates (de - couples ) the anode/anolyte from solvent, elec- invention .
trolyte processing and / or cathode environments, including FIG . 2 is a schematic illustration of a battery cell incor
such environments that are normally highly corrosive to Li porating an ionically conductive protective interlayer archi
or other active metals , and at the same time allows ion 45 tecture in accordance with the present invention .
transport in and out of these potentially corrosive environ- FIGS . 3A - C illustrate embodiments of battery cells in
ments . accordance with the present invention that use a tubular
Various embodiments of the cells and cell structures of the protected anode design .
present invention include active metal, active metal - ion, FIGS . 4-6 are plots of data illustrating the performance of
active metal alloying metal, and active metal intercalating 50 various cells incorporating anodes with ionically conductive
anode materials protected with an ionically conductive pro- protective interlayer architecture in accordance with the
tective architecture having a non - aqueous anolyte. These present invention .
anodes may be combined in battery cells with a variety of FIG . 7 illustrates a Li/water battery and hydrogen gen
possible cathode systems, including water, air, metal hydride erator for a fuel cell in accordance with one embodiment of
and metal oxide cathodes and associated catholyte systems, 55 the present invention .
in particular aqueous catholyte systems.
Safety additives may also be incorporated into the struc DETAILED DESCRIPTION OF SPECIFIC
tures and cells of the present invention for the case where the EMBODIMENTS
substantially impervious layer of the protective architecture
( e.g. , a glass or glass -ceramic membrane ) cracks or other- 60 Reference will now be made in detail to specific embodi
wise breaks down and allows the aggressive catholyte to ments of the invention . Examples of the specific embodi
enter and approach the lithium electrode. The non -aqueous ments are illustrated in the accompanying drawings. While
interlayer architecture can incorporate a gelling/polymeriz- the invention will be described in conjunction with these
ing agent that, when in contact with the reactive catholyte, specific embodiments, it will be understood that it is not
leads to the formation of an impervious polymer on the 65 intended to limit the invention to such specific embodi
lithium surface. For example , the anolyte may include a ments. On the contrary, it is intended to cover alternatives,
monomer for a polymer that is insoluble or minimally modifications, and equivalents as may be included within
US 10,916,753 B2
5 6
the spirit and scope of the invention as defined by the There are a variety of applications that could benefit from
appended claims . In the following description, numerous the use of aqueous solutions , including water and water
specific details are set forth in order to provide a thorough based electrolytes, air, and other materials reactive to lithium
understanding of the present invention . The present inven- and other active metals, including organic solvents /electro
tion may be practiced without some or all of these specific 5 lytes and ionic liquids, on the cathode side of the cell with
details. In other instances, well known process operations an active (e.g. , alkali , e.g. , lithium ) metal or active metal
intercalation ( e.g. , lithium alloy or lithium - ion ) anode in a
have not been described in detail so as to not unnecessarily battery
obscure the present invention . cell.
When used in combination with “ comprising , ” “ a method The use of lithium intercalation electrode materials like
comprising,” “ a device comprising” or similar language in 10 lithium -carbon
on Sn and andcombinations
Si ) , and lithium alloythereof
anodes, rather
(e.g., than
thoselithium
based
this specification and the appended claims , the singular metal , for the anode can also provide beneficial battery
forms “ a , " " an ,” and “ the” include plural reference unless characteristics
the context clearly dictates otherwise. Unless defined oth prolonged cycle. First of all , it allows the achievement of
life of the battery without risk of formation
erwise, all technical and scientific terms used herein have the 15 of lithium metal dendrites that can grow from the Li surface
same meaning as commonly understood to one of ordinary to the membrane surface causing the membrane's deterio
skill in the art to which this invention belongs . ration . Also , the use of lithium - carbon and lithium alloy
Introduction anodes in some embodiments of the present invention
Active metals are highly reactive in ambient conditions instead of lithium metal anode can significantly improve a
and can benefit from a barrier layer when used as electrodes. 20 battery's safety because it avoids formation of highly reac
They are generally alkali metals such (e.g. , lithium , sodium tive “ mossy ” lithium during cycling .
or potassium ), alkaline earth metals ( e.g. , calcium or mag- The present invention describes a protected active metal,
nesium) , and / or certain transitional metals (e.g. , zinc ) , and / alloy or intercalation electrode that enables very high energy
or alloys of two or more of these. The following active density lithium batteries such as those using aqueous elec
metals may be used : alkali metals (e.g. , Li , Na , K) , alkaline 25 trolytes or other electrolytes that would otherwise adversely
earth metals (e.g. , Ca , Mg , Ba ) , or binary or ternary alkali react with lithium metal, for example. Examples of such
metal alloys with Ca , Mg , Sn , Ag , Zn , Bi , Al , Cd , Ga , In . high energy battery couples are lithium - air, lithium -water
Preferred alloys include lithium aluminum alloys , lithium lithium -metal hydride, lithium -metal oxide , and the lithium
silicon alloys , lithium tin alloys , lithium silver alloys , and alloy and lithium - ion variants of these . The cells of the
sodium lead alloys (e.g. , Na4Pb ) . A preferred active metal 30 invention may incorporate additional components in their
electrode is composed of lithium . electrolytes ( anolytes and catholytes) to enhance cell safety,
The low equivalent weight of alkali metals, such as and may have a variety of configurations, including planar
lithium , render them particularly attractive as a battery and tubular /cylindrical.
electrode component. Lithium provides greater energy per Non -Aqueous Interlayer Architecture
volume than the traditional battery standards, nickel and 35 The non - aqueous interlayer architecture of the present
cadmium . However, lithium metal or compounds incorpo- invention is provided in an electrochemical cell structure ,
rating lithium with a potential near that (e.g. , within about a the structure having an anode composed of a material
volt) of lithium metal , such as lithium alloy and lithium - ion selected from the group consisting of active metal, active
( lithium intercalation ) anode materials, are highly reactive to metal - ion, active metal alloy, active metal alloying and
many potentially attractive electrolyte and cathode materi- 40 active metal intercalating material, and an ionically conduc
als . This invention describes the use of a non - aqueous tive protective architecture on a first surface of the anode.
electrolyte interlayer architecture to isolate an active metal The architecture is composed of an active metal ion con
( e.g. , alkali metal , such as lithium ), active metal alloy or ducting separator layer with a non -aqueous anolyte, the
active metal -ion electrode (usually the anode of a battery separator layer being chemically compatible with the active
cell ) from ambient and / or the cathode side of the cell . The 45 metal and in contact with the anode, and a substantially
architecture includes an active metal ion conducting sepa- impervious ionically conductive layer chemically compat
rator layer with a non - aqueous anolyte (i.e. , electrolyte about ible with the separator layer and aqueous environments and
the anode ), the separator layer being chemically compatible in contact with the separator layer. The separator layer may
with the active metal and in contact with the anode , and a include a semi-permeable membrane , for example, a micro
substantially impervious ionically conductive layer chemi- 50 porous polymer, such as are available from Celgard , Inc.
cally compatible with the separator layer and aqueous envi- Charlotte, N.C. , impregnated with an organic anolyte.
ronments and in contact with the separator layer. The In some embodiments , the porous separator layer is
non - aqueous electrolyte interlayer architecture effectively flexible . For instance the separator may be a porous poly
isolates (de - couples ) the anode from ambient and / or cath- meric material layer, such as a porous polyolefin ( e.g. ,
ode , including catholyte ( i.e. , electrolyte about the cathode) 55 polyethyelenes or polypropylenes ) , porous polytetraflouro
environments, including such environments that are nor- ethylene layer ( e.g. , expanded PTFE ), porous polyethylene
mally highly corrosive to Li or other active metals, and at the terepthalate (PET ) or some combination thereof such as a
same time allows ion transport in and out of these potentially polyolefin multi-layer ( e.g. , a tri -layer ) or a multi - layer of a
corrosive environments. In this way , a great degree of porous PET or PTFE layer combined (e.g. , by lamination to
flexibility is permitted the other components of an electro- 60 another layer or some other means of adhering the layers
chemical device , such as a battery cell , made with the such as using a porous adhesives or chemical dissolution
architecture . Isolation of the anode from other components bonding ) with a porous polyolefin layer to provide enhanced
of a battery cell or other electrochemical cell in this way chemical compatibility in contact with lithium metal ( e.g. , a
allows the use of virtually any solvent, electrolyte and /or bi - layer where the polyolefin layer contacts the lithium ) or
cathode material in conjunction with the anode . Also , opti- 65 the PTFE layer or PET layer may be sandwiched between
mization of electrolytes or cathode -side solvent systems may two different porous polymer layers (e.g. , between two
be done without impacting anode stability or performance . polyolefin layers ). The porous polymer layers may be pro
US 10,916,753 B2
7 8
cessed using dry or wet methods, as are known in the battery made including Li1 +xTi2 - A1- (PO4)3 and the like which are
separator arts. In the dry process, the film can be stretched known in the lithium battery arts .
to introduce micropores. The porous polymer layer may In various embodiments , the ceramic particle or porous
further be a nonwoven film or coating, which is processed ceramic film may be composed in whole or in part of lithium
from polymeric fibers into a film or coating . 5 ion conductive materials which are suitable for use herein as
The porous polymeric separator material layer is not the lithium ion conducting material of the substantially
limited to polyolefins, PTFE, or PET specifically but is impervious membrane layer, and which are described in
understood to include all types of polymers which can be more detail below in the section on the second material layer
fabricated into a porous material layer including polyvi- ( i.e. , the substantially impervious layer ). In other embodi
nylidene fluoride (PVDF ) , polycarbonates, cellulosics , poly- 10 ments the aforementioned porous ceramic film or coating
urethanes, polyesters , polyethers , polyacrylates, copolyether may be sandwiched between two porous polymeric layers.
esters , copolyether amides , polyethyelene ( PE) , polypropyl- While the porous separators described herein above are
ene (PP ) , polyacrylates, copolyether esters , copolyether generally flexible, for instance having an elastic modulus
amides , chitosn, and fluoropolymers generally . (i.e. , Young's modulus ) in the range of less than 10 GPa , the
Suitable fluoropolymers include expanded PTFE as 15 invention is not so limited, and it is contemplated that rigid
taught in U.S. Pat. No. 3,953,566 , which is hereby incor- porous material layers may also serve as an interlayer ( e.g. ,
porated by reference for the purpose of disclosing this those having an elastic modulus greater than 10 GPa such ).
composition and methods for its fabrication and use . For Such rigid layers include porous ceramic layers , porous
instance, and as described above , to stabilize the porous metal layers , porous carbon foam layers and porous glass
PTFE membrane for direct contact with lithium , the PTFE 20 layers and which optionally may serve as a layer on the
layer may be sandwiched on one or both sides by a polymer surface of a porous polymer layer, or porous polymer layer
layer of different composition, e.g. , a polyolefin . may be coated on the surface of the ceramic , metal or glass
In various embodiments, the porous separator serving as layer and thereon serve to provide some stability in contact
interlayer may be a porous polymer layer or multilayer with lithium metal (e.g. , the surface layer a polyolefin ), or
devoid of other material additives , or in other embodiments 25 the porous rigid layer (be it a polycrystalline metal oxide
the separator layer may be a composite of a polymer ( e.g. , (e.g. , a ceramic ) or glass , or metal , may be sandwiched
serving as the base material layer) and a second material between two porous polymer layers. For instance a porous
such as a ceramic , for example a metal oxide , ( e.g. , ceramic ceramic layer of alumina such as anodized alumina may be
metal oxide particles ) disposed in pores of the polymer layer used .
or a porous ceramic coating or thin porous ceramic film 30 In some embodiments, the ceramic particles are conduc
disposed on one or both polymer surface ( e.g. , sandwiching tive of alkali metal ions , or conductive of electrons or
the polymer layer) . For instance, a nano - porous ceramic film otherwise insulating or semiconducting. In some embodi
may be used . In some embodiments, the ceramic (be it a ments, the particles may be nano particles. In some embodi
particle or film ) is non - conductive to lithium ions and in ments, the ceramic particles or ceramic layers may be
other embodiments the ceramic is a lithium ion conductor. 35 reactive to lithium metal in contact, and thereby serve as a
Suitable ceramic materials which may be used as a ceramic getter for shorting dendrites which may grow as a result of
particle in the pores of a porous layer, typically a polymeric cell cycling . Suitable reactive ceramic layers include inter
layer, serving as the base layer of the separator include metal calation materials which may in contact with lithium metal
oxides generally , and in particular the following: alumina reduce and intercalate lithium ions . Such intercalation mate
(e.g. , A1,03), magnesia (e.g., MgO) , LiA102 , lithium oxide, 40 rials are known in the lithium ion battery art and include
titanium oxide , magnesium oxide , aluminum oxide, zirconia titanium , tungsten , cobalt , and manganese oxides and the
( i.e. , zirconium oxide ) , hafnium oxide , iron oxide, silica , like.
barium titanate , and yttrium oxide . Other ceramic materials In some embodiments , the porous separator layer has a
which are conductive of lithium ions and may be used as a polymeric base layer impregnated with a lithium ion con
ceramic particle or porous ceramic film include lithium 45 ductive ceramic component, typically in particle form .
titanium phosphates and the like as well as lithium ion In some embodiments , the separator layer may be a
conducting garnets , as described in more detail below . composite of a porous polymeric base layer having ceramic
Other particularly suitable materials as a ceramic particle filler particles disposed in pores of the base layer and further
or ceramic film or coating are lithium ion conducting oxides comprising a polymer capable of swelling or being gelled by
having a garnet like structures . These include 50 a liquid electrolyte and thus serving in the separator as a gel
LigBaLa Ta2012; Li LazZr2012, LisLazNb20129 material. Other materials which may be incorporated in the
LisLazM2012 ( M = Nb, Ta )Li7+ A Laz-/ Zr2012 where A may separator include ion exchange resin like materials, such as
be Zn . These materials and methods for making them are ion exchange polymeric materials , typically having func
described in U.S. Patent Application Pub . No .: 2007 / tional groups that provide ion exchange properties, such as
0148533 ( application Ser. No. 10 /591,714) and is hereby 55 carboxylic, sulfonic and phosphonic groups. Suitable gel
incorporated by reference for disclosure of these materials materials are known in the lithium battery art, and include
and methods for their making and use , and suitable garnet copolymers of vinylidene fluoride with hexafluoropropylene
like structures, described , for example, in International Pat- (PVDF - HFP ) , poly (methyl methacrylate ( PMMA ), poly
ent Application Pub . No .: W0/2009 /003695 , which is ( acrylonitrile) ( PAN ) and polyethyelene oxide ( PEO )
hereby incorporated by reference for disclosure of these 60 In the aforementioned embodiments, the separator layer
materials and methods for their making and use . Suitable may be further impregnated with a gelling agent, which is
ceramic active metal ion conductors are described, for typically a polymer material capable of being swelled by the
example, in U.S. Pat . No. 4,985,317 to Adachi et al . , liquid electrolyte which is incorporated therein .
incorporated by reference herein for disclosure of these Material layers suitable for use herein as an interlayer
materials and methods for their making and use . LiM2 65 component in the instant protected electrodes include those
( PO4 ) 3 where M may be Ti, Zr, Hf, Ge and related compo- described in U.S. Pub . No .: 2012/0169016 to Hisano et al . ,
sitions such as those into which certain ion substitutions are published Jul . 5 , 2012 ; U.S. Pat . No. 6,242,135 to Mushiake,
US 10,916,753 B2
9 10
U.S. Pat . Nos . 3,953,566 ; 4,187,390 ; 4,539,256 ; 4,429,000 ; ceramic materials are substantially gap - free, non- swellable
4,726,989 ; 4,100,238 ; 3,679,540 , all of which are hereby and are inherently ionically conductive . That is , they do not
incorporated by reference for disclosure of these materials, depend on the presence of a liquid electrolyte or other agent
as well as those manufactured by Celgard LLC (e.g. , PE , PP for their ionically conductive properties. They also have
and PP /PE / PP ), Asahi Kasei chemicals (e.g. , Hipore ); Entek 5 high ionic conductivity, at least 10-7 S /cm , generally at least
Membranes (e.g. , Separion ), ExxonMobil/ Tonen , SK 10-6S / cm , for example at least 10-5S /CM to 10-4 S /cm , and
Energy, Evonik , and DuPont ( e.g. , the Energain ). Other as high as 10-3 S/ cm or higher so that the overall ionic
suitable material layers which may serve herein as an
interlayer include those which are described by S. S. Zhang conductivity of the multi -layer protective structure is at least
10-7 S/ cm and as high as 10-3 S /cm or higher. The thickness
in164an(2007
article) 351-364
published. in the Journal of Power of Sources 10 of the layer is preferably about 0.1 to 1000 microns, or,
In yet other embodiments, the porous interlayer may where about
the ionic conductivity of the layer is about 10-7S/cm,
0.25 to 1 micron , or, where the ionic conductivity of
include or be composed of an inorganic matrix material such
as a porous layer composed of inorganic fibers, such as glass the layer is between about 10-4 about 10-3 S/ cm , about 10 to
and/or ceramic fibers; the layer being thin (e.g. , less than 50 15 more
1000 microns , preferably between 1 and 500 microns , and
preferably between 10 and 100 microns , for example
um) or thick . In embodiments wherein the glass or ceramic 20 microns .
fiber contacts the active metal anode , the composition of the Suitable examples of suitable substantially impervious
fiber should be chemically compatible with the active metal
anode; e.g. , for embodiments wherein the glass or ceramic lithium ion conducting layers include glassy or amorphous
fiber contacts the lithium metal anode layer. For instance, a 20 metal ion conductors, such as a phosphorus - based glass ,
glass or ceramic mat is contemplated for use herein as an oxide -based glass , phosphorus -oxynitride -based glass , sul
interlayer. Glass mats are known for their use as battery pher -based glass , oxide / sulfide based glass , selenide based
separators, especially for lead acid batteries (e.g. , an AGM glass , gallium based glass , germanium -based glass or
separator ). AGM stands for absorptive glass mat and it boracite glass ( such as are described D. P. Button et al . , Solid
generally a nonwoven fabric made with glass microfibers . 25 State Ionics, Vols. 9-10 , Part 1 , 585-592 (December 1983 ) ;
In addition to microporous separator layers, non - woven ceramic active metal ion conductors, such as lithium beta
fabric type separators may be used as an interlayer or alumina , sodium beta - alumina, Li superionic conductor
interlayer component herein , including those described in (LISICON) , Na superionic conductor (NASICON ), and the
U.S. Pat . No. 5,002,843 to Cieslak, which discloses aramid like ; or glass - ceramic active metal ion conductors . Specific
fibers in a non -woven mat format, and is hereby incorpo- 30 examples include LiPON , Li PO .Li,S.SIS
rated by reference . Other non - woven fabric type separators Li2S.GeS2.Ga2S3 , Li20.11A12O3 , Na20.11A1,03 , (Na,
may be composed of glass or other inorganic or organic Li) 1 + x Ti2 -xA1_ (PO4)3 ( 0.6sxs0.9 ) and crystallographically
( e.g. , polymeric fiber ) fiber like materials . For instance , this related structures, Na Zr Si PO123 LizZr_Si_PO123
may include non - woven polyesters and the like . In various NazZrP , 012, NazTiP2012, NazFe , P2012 , Na NbP , 012 ,
embodiments the interlayer is a solid polymer electrolyte 35 LigZrP2012, Li TiP2012,LizFe,P2012 and Li_NbP2012, and
such as polyethylene oxide ( PEO ) and derivatives and combinations thereof, optionally sintered or melted . Suitable
blends thereof having a lithium salt ( e.g. , Li - TFSI ) dissolved ceramic ion active metal ion conductors are described , for
therein . These include blends such as block co -polymers of example, in U.S. Pat . No. 4,985,317 to Adachi et al . ,
e.g. , polystyrene (PS ) -block -polyethylene oxide -block- incorporated by reference herein in its entirety and for all
polystyrene copolymers. Polymers based on block copoly- 40 purposes.
mers of PS and PEO are disclosed in U.S. patent application A particularly suitable glass -ceramic material for the
Ser. No. 12/ 225,934 and other useful compositions are substantially impervious layer of the protective architecture
disclosed in US Patent Publication No .: 20130066025 , US is a lithium ion conductive glass -ceramic having the follow
Patent Publication No .: 20110318648 and US Patent Publi- ing composition :
cation No .: 20130273419. Suitable lithium salts for the solid 45
polymer anolyte interlayer, which are also suitable for
anolytes based on various nonaqueous liquid solvents, Composition mol %
include lithium trifluoromethansulfonate (LiCF3SO3), P205 26-55 %
lithium bis ( trifluoromethanesulfonimidate ) (Li ( CF2SO2 ) 2 SiO2 0-15 %
N) ; lithium bis (trifluoromethanesulfonimide) (Li 50 GeO2 + TiO2 25-50 %
( C2F5S02 ) 2 N , lithium perchlorate (LiC104) , and lithium in which Ge020-50 %
0-50 %
bis ( oxalato )borate ( LiB ( C204 ) 2 ) . The solid polymer electro TiO2
ZrO2 0-10 %
lyte may be modified by adding a plasticizer such as M203 0-10 %
succinonitrile, polysquarate , EC , PC or some combination Al2O3 0-15 %
thereof, which reduces crystallization and thus generally 55 Ga203
Li20
0-15 %
3-25 %
increases conductivity, especially near room temperature.
The protective architecture of this invention incorporates
a substantially impervious layer of an active metal ion and containing a predominant crystalline phase composed of
conducting glass or glass -ceramic (e.g. , a lithium ion con- Lii + (M ,A1,Ga ), (Ge-, Ti, )2- (PO4)3 where Xs0.8 and
ductive glass -ceramic (LIC - GC)) that has high active metal 60 OsYsl.0 , and where M is an element selected from the
ion conductivity and stability to aggressive electrolytes that group consisting of Nd , Sm , Eu, Gd , Tb , Dy, Ho , Er, Tm and
vigorously react with lithium metal , for example) such as Yb, and / or Lil + x +yl.Ti2- XSi, P3-012 where 0 < X50.4 and
aqueous electrolytes. Suitable materials are substantially O < Y 50.6 , and where Q is Al or Ga . The glass - ceramics are
impervious, ionically conductive and chemically compatible obtained by melting raw materials to a melt , casting the melt
with aqueous electrolytes or other electrolyte ( catholyte) 65 to a glass and subjecting the glass to a heat treatment. Such
and / or cathode materials that would otherwise adversely materials are available from OHARA Corporation, Japan
react with lithium metal , for example. Such glass or glass- and are further described in U.S. Pat . Nos . 5,702,995 ,
US 10,916,753 B2
11 12
6,030,909 , 6,315,881 and 6,485,622 , incorporated herein by Particularly suitable solid - state electrolyte materials
reference for disclosure of these materials and methods of include the following:
making them . (i ) garnet like compounds as described in PCT Patent
Such lithium ion conductive substantially impervious Application WO 2013/010692 having Robert Bosch GMBH
layers and techniques for their fabrication and incorporations as applicant and inventors Eisele, Koehler, Hinderberger,
in battery calls are described in U.S. Provisional Patent Logeat, and Kozinsky and which is herein incorporated by
Application No. 60/418,899 , filed Oct. 15 , 2002 , titled reference :
IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ANODES Li,[A3-a -2 A2, A " " ][B 2-666 %B6,B " ][CC
AND ELECTROLYTES, its corresponding U.S. patent application 10
C " ]012 wherein
Ser. No. 10/ 686,189 ( Attorney Docket No. PLUSPO27 ) , A represents at least one element selected from the group
filed Oct. 14 , 2003 , and titled IONICALLY CONDUCTIVE COMPOS- consisting of La , Y, Pr, Nd , Sm , Eu , Gd , Tb , Dy, Ho , Er,
ITES FOR PROTECTION OF ACTIVE METAL ANODES, U.S. patent Tm and Yb ;
application Ser. No. 10/731,771 ( Attorney Docket No. A' represents at least one element selected from the group
PLUSPO27X1 ) , filed Dec. 5 , 2003 , and titled IONICALLY 15 consisting of Ca , Sr, and Ba ;
CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL A " represents at least one element selected from the group
ANODES, and U.S. patent application Ser. No. 10/ 772,228 consisting of Na and K ;
( Attorney Docket No. PLUSP039 ) , filed Feb. 3 , 2004 , and with Osa' <2 and Osa " < 1
titled IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF B represents at least one element selected from the group
ACTIVE METAL ANODES AND BATTERY CELLS. These applications 20 consisting of Zr, Hf , and Sn ;
are incorporated by reference herein in their entirety for all B ' represents at least one element selected from the group
purposes. consisting of Ta, Nb , Sb , and Bi ;
Another particularly suitable material for the second layer B " represents at least one element selected from the group
of the protective composite is a lithium ion conducting oxide consisting of Te , W , and Mo
having a garnet like structure . These include 25 with Osb's2 and Osb " s2;
LigBaLa Ta2012; Li LazZr2012 LisLazNb 0123 C ' represents at least one element selected from the group
LisLazM20,2 ; 12
be Zn . These materials and methods for making them are
consisting of Al and Ga ;
C " represents at least one element selected from the group
described in U.S. Patent Application Pub . No .: 2007 / consisting of Si and Ge ;
0148533 ( Appl. Ser. No. 10/ 591,714 ) and is hereby incor- 30 with Osc's0.5 and Osc " 50.4
porated by reference , and suitable garnet like structures, are and n = 7 + a '+ 2a " -b ' - 2b " -3c - 4c" and 5.5sns6.875 ( or
described in International Patent Application Pub . No .: 5sns7 ) .
WO/ 2009 /003695 which is hereby incorporated by refer- Particular examples include but are not limited to :
ence . Li6.875LazTa..125Zr1.875012; Li6.75LazTao.25Zr1,75012;
A critical limitation in the use of these highly conductive 35 Lio sLa TaosZr1.5012 ; Li6.25La Tao.75Zr1.25012 ;
glasses and glass -ceramics in lithium ( or other active metal LicLazTaZr012 ; Lis.Laz Ta1.5Zr0.5012;
or active metal intercalation ) batteries is their reactivity to Alo . Lis. La, Zr2O2 A10.17L16.49LazZr2012 ;
lithium metal or compounds incorporating lithium with a A10.23L16.31LazZr2012 ; A10.29L16.13LazZr2012 ;
potential near that (e.g. , within about a volt ) of lithium A10.35Li5.95LazZr2012 ; Al, Lis.85Sro.25
metal . The non -aqueous electrolyte interlayer of the present 40 La2.75Nbo5Zr1.5012; Sio 2Lis 2La Zr2012
invention isolates the lithium ( for example ) electrode from (ii ) garnet like compounds as described in U.S. Patent
reacting with the glass or glass -ceramic membrane . The Application Pub .No .: 2011/0244337 having Kabushiki Kai
non - aqueous interlayer may have a semi-permeable mem- sha Toyota Chuo Kenkyusho as assignee and inventors Ohta ,
brane , such as a Celgard micro -porous separator, to prevent Kobayashi, Asaoka , Asai , and which is herein incorporated
mechanical contact of the lithium electrode to the glass or 45 by reference :
glass -ceramic membrane. The membrane is impregnated List Laz( Zrx,A2-x )012 wherein
with organic liquid electrolyte ( anolyte ) with solvents such A is at least one selected from the group consisting of Sc ,
as ethylene carbonate ( EC ) , propylene carbonate (PC ) , 1,2- Ti, V, Y , Nb , Hf, Ta, Al , Si , Ga , Ge , and Sn and X
dimethoxy ethane (DME ) , 1,3 -dioxolane ( DIOX ) , or various satisfies the inequality 1.45X <2 ; or
ethers, glymes , lactones, sulfones, sulfolane, or mixtures 50 A is one obtained by substituting an element having an
thereof. It may also or alternatively have a polymer elec ionic radius different from that of Zr for Zr sites in a
trolyte , a gel - type electrolyte, or a combination of these . The garnet type lithium ion conducting oxide represented
important criteria are that the lithium electrode is stable in by the formula Li,LazZr2012
the non -aqueous anolyte, the non -aqueous anolyte is suffi- (iii ) garnet like compounds as described in U.S. Pat . No.
ciently conductive to Li * ions , the lithium electrode does not 55 8,092,941 having Werner Weppner as assignee and inventors
directly contact the glass or glass - ceramic membrane, and Weppner and Thangadurai, and which is herein incorporated
the entire assembly allows lithium ions to pass through the by reference:
glass or glass -ceramic membrane . ListA ,G,,M2012 wherein
In various embodiments the liquid impermeable solid A is in each case independently a monovalent, divalent,
electrolyte membrane ( i.e. , the substantially impervious 60 trivalent, or tetravalent cation (e.g. A is an alkaline
layer ) may be a glass , glass -ceramic or ceramic membrane earth metal or transition metal such as Ca , Sr, Ba , Mg
composed in whole or in part of an active metal ion and /or Zn ;
conducting solid - state electrolyte material. For instance, the G is in each case independently a monovalent, divalent,
membrane fabricated by sintering a pellet or tape cast layer trivalent, or tetravalent cation ( e.g. La ) ;
of said solid - state electrolyte material , including sintering of 65 Mis in each case independently a trivalent, tetravalent, or
a tape cast glass material that in the process of densification pentavalent cation ; with 0 < xs3, O<ys3 , and 0 <zs3
during sintering crystallizes to a highly conductive phase . (e.g. a transition metal such as Nb, Ta, Sb and V) ; and
US 10,916,753 B2
13 14
O can be partially or completely replaced by divalent -continued
and / or trivalent anions such as e.g. N3- ; and further Composition
more, Mol %
within a structure of this formal composition L , A , G and 5 Ga203 0 - 15 %
M can each be the same or different. Li20 3 - 25 %
For example, ListA ,G3. M ,012 ( such as
Li ALa M2012, e.g. , LiGALa, Ta2012 ( A = Sr, Ba ) ] And in particular lithium ion conductive compounds having
( iv ) garnet like compounds as described in U.S. Patent Pub . the following general formula :
No .: 2011/0053002 having NGK Insulators, Ltd. , as 10 Lii + (M , A ,G ),(Ge Ti,)2- (PO4)3 where xs0.8 and
assignee and inventors Yamamura, Hattori, Yoshida, Honda, Osxs1.0 and where M is an element selected from the group
and Sato , and which is herein incorporated by reference , for consisting of Nd , Sm , Eu , Gd , Tb , Dy, Ho , Er, Tm and Yb
instance a ceramic material containing: and /or Lil +x+yQxTi2-2Si,P3-y, 012 where 0 < x < 0.4 and
O < y > 0.6 and where Q is Al or Ga . For example Li ( 1 + x )
(a ) Li , La , Zr, Nb , O ; or (b ) Li , La , Zr, Ta , O ; or (c ) Li , Al Ti2-- (PO4)3 where X is 0 to 0.8 as described in U.S. Pat.
Lawherein
, Zr, Nb , Ta, o . theFortotalexample
M represents number, Liof moles
La,Zr,MOof Nb 15 No. 5,702,995 having Kabushiki Kaisha Ohara as assignee
and Ta, the molar ratios of the constitutive metal and inventor Jie Fu , and which is herein incorporated by
reference.
elements containing Nb and Ta can be set to be a : b : X + Other suitable materials include glassy or amorphous
y : y =7 : 3 : 2 : 0.1 or greater to 0.6 or lower. In addition the metal ion conductors, such as a phosphorus -based glass ,
ceramic material may contain Al ( e.g. , Li,La , Zr, M ,OC 20 oxide - based glass , phosphorus -oxynitride-based glass , sul
ZAl (wherein M represents the total number of moles of pher -based glass , oxide/sulfide based glass , selenide based
Nb and Ta and the molar ratios of the constitutive metal glass , gallium based glass , germanium -based glass , Nasi
elements can be set to be a : b : x + y : z =7 : 3 : 2 : 0.025 or glass ; ceramic active metal ion conductors , such as lithium
greater to 0.35 or lower. beta - alumina, sodium beta - alumina , Li superionic conductor
(v) garnet like compounds as described in U.S. Patent Pub . 25 (LISICON) , Na superionic conductor (NASICON ), and the
No .: 2010/0203383 having BASF SE , as assignee and like; or glass-ceramic active metal ion conductors . Specific
inventor Werner Weppner, and which is herein incorporated examples include LiPON , Li3PO4.Li S.SiS2,
by reference , for instance a compound having the general Li S.GeS2.Ga S3, Li_0.11A1,03, Na 0.11A1,03,
formula : (Na ,Li) Tiz A1, (PO4), (0.1sx50.9) and crystallographi
Li7+ 463. Zr2012 wherein 30 cally related structures, Lil+xHf2 - AL (PO4)3 (0.1sx50.9 ) ,
A is in each case independently a divalent cation (or NazZr2Si PO12, LizZr2Si_P012 , NazZrP2012, NasTiP 2012,
combination of such cations , preferably divalent metal NazFe2P2012 , Na NbP3012, Na -Silicates, Lio.3LaosTiO3,
cations such as alkaline earth metal ions such as Ca , Sr, Na MSi_012 ( M : rare earth such as Nd , Gd , Dy )
Ba , and / or Mg and also divalent cations such as Zn) ; LizZrP , 0,2, LizTiP , 012, LizFe , P , 012 and Li NbP3012, and
G is in each case independently a trivalent cation (or 35 combinations thereof, optionally sintered or melted . Suitable
combination of such cations, with preference given to ceramic ion active metal ion conductors are described, for
La ); example, in U.S. Pat . No. 4,985,317 to Adachi et al . ,
with Osxs3 ( and preference is given to Osxs2 and in incorporated by reference herein in its entirety and for all
particular Osxsl ) ; and purposes.
O can be partly or completely replaced by divalent or 40 A particularly suitable glass -ceramic material is a lithium
trivalent anions such as N3 ion conductive glass - ceramic having the following compo
(vi ) nasicon like compounds as described in U.S. Pat. No. sition :
4,985,317 having Japan Synthetic Rubber Co. , Ltd. as
assignee and inventors Adachi, Imanaka, Aono , Sugimoto ,
Sadaoka, Yasuda, Hara, Nagata , and which is herein incor- 45 Composition mol %
porated by reference , for instance a compound ( sometimes P205 26-55 %
referred to as LTP ) having the general formula : SiO2 0-15 %
( a ) Lii +xM . Tiz . (PO ) wherein GeO2 + TiO2
in which Ge02
25-50 %
0-50 %
M is at least one element selected from the group con TiO2 0-50 %
sisting of Fe , Al and rare earth elements and x is a 50 ZrO2 0-10 %
number from 0.1 to 1.9 ; or M203 0-10 %
( b ) Li1+ , Ti, Si, P3,012 wherein y is a number from 0.1 to Al2O3 0-15 %
2.9 ; or Ga203 0-15 %
(c ) or some combination of (a ) and (b ) Li20 3-25 %
(vii ) lithium ion conductive compounds having the follow- 55
ing composition : and /or such a material containing a predominant crystalline
phase composed of Li1+z(M ,A1,Ga), (Ge ., Ti,)2.x (PO4)3
where X =0.8 and O = Y = 1.0, and where M is an element
Composition Mol % selected from the group consisting of Nd, Sm, Eu , Gd, Tb ,
P?O , 26 - 55 % 60 Dy, Ho , Er, Tm and Yb and / or Li1 + x+yQ.Ti2 -xSi, P3-1012
SiO2 0 - 15 % where O < X = 0.4 and 0 < Y = 0.6 , and where Q is Alor Ga . The
GeO2 and TiO2 25 - 50 % glass - ceramics are obtained by melting raw materials to a
in which TiO2 0- 50 % melt , casting the melt to a glass and subjecting the glass to
in which GeO2 0 - 50 %
a heat treatment. Such materials are available from OHARA
ZrO2 0- 10 %
M203 0< 10 % 65 Corporation , Japan and are further described in U.S. Pat .
Al2O3 0 - 15 % Nos . 5,702,995 , 6,030,909 , 6,315,881 and 6,485,622 , incor
porated herein by reference.
US 10,916,753 B2
15 16
Suitable solid - state ion conductor materials for the mem- inorganic solvents such as those described above, as well as
brane include LiBaLa Ta2012; Li,La,Zr, 0,23 ionic liquid solvents. For instance the chemically compatible
LisLazNb2012, LizLazM2012 ( M = Nb, Ta )Li7 + A Laz-x anolyte may be composed of an ionic liquid in combination
Zr2012 where A may be Zn or another transition metal . with non - aqueous organic liquid solvent (s ) and an optional
These materials and methods for making them are described 5 salt . When the anolyte is in the gel phase , gelling agents such
in U.S. Patent Application Pub. No .: 2007/0148533 (appli- as polyvinylidine fluoride (PVdF ) compounds, hexafluro
cation Ser. No. 10/ 591,714 ) and is hereby incorporated by propylene -vinylidene fluoride copolymers (PVdf-HFP ),
reference in its entirety and suitable garnet like structures, polyacrylonitrile compounds, cross - linked polyether com
are described in International Patent Application Pub . No .: pounds , polyalkylene oxide compounds, polyethylene oxide
WO/ 2009 /003695 , herein incorporated by reference for all 10 compounds, and combinations and the like may be added to
that it contains. gel the solvents. Suitable anolytes will also , of course , also
The garnet structure can be modified by doping different include active metal salts , such as , in the case of lithium , for
elements so enhance performance such as chemical com- example , LiPF , LiBF4, LiAsF , LISO , CF ; or LiN
patibility, ease of fabrication , reducing cost , and increasing ( SO , C2F5 ) 2 . One example of a suitable separator layer is 1
conductivity. Particularly suitable substantially impervious 15 M LIPF . dissolved in propylene carbonate and impregnated
garnet like layers include modified garnet like layers having in a Celgard microporous polymer membrane.
compositions of about LigSrLa Ta2012, Li BaLa Ta2012, When the anolyte is in the gel phase it may be used as a
Li Cala Nb2012 Li SrLa Nb2012 Li BaLa Nb2012 , freestanding layer or otherwise as a coating on the lithium
LisLazBi2012 , Li SrLa Bi_012, LisLa Nb ..Y..012, metal or on the substantially impervious layer. Both organic
Li–LazHf,012, Li6.55LazHf 55T20.45012 , LigNdzSb2012, 20 solvent- and ionic liquid -based gels as well as combinations
Li ,LazSn , 012 Li La Zr2012, Li6.75La Zr1.75N60.250129 thereof are contemplated for use herein as an interlayer.
Li6.25LazZr Ga0.25012 , Li LazZr2012 (LLZO ) doped with As described in U.S. Pat. No. 8,332,028 , other anolyte
Ge , Si , In , Al or some combination thereof solvents including ionic liquids , and especially non - aqueous
Referring to FIG . 1 , a specific embodiment of the present organic ionic liquids, as well as inorganic ionic liquids
invention is illustrated and described . FIG . 1 shows an 25 which are sufficiently compatible in contact with the lithium
unscaled depiction of an electrochemical cell structure 100 anode layer ( e.g. , lithium metal or lithium intercalation
having an active metal, active metal - ion, active metal alloy- material, such as carbon ) may be used as anolyte herein .
ing metal , or active metal intercalating material anode 102 Ionic liquids are a subclass of non - aqueous solvents and are
and an ionically conductive protective architecture 104. The generally known in the battery art for their use as an
protective architecture 104 has an active metal ion conduct- 30 electrolyte component. Ionic liquids generally suitable for
ing separator layer 106 with a non -aqueous anolyte (some- use herein are preferably liquids at room temperature,
times also referred to as a transfer electrolyte) on a surface although the invention is not limited as such , and organic
of the anode 102 and a substantially impervious ionically salts having melting points below 100 ° C. are generally
conductive layer 108 in contact with the separator layer 106 . contemplated. Ionic liquids are known in the art, including
The separator layer 106 is chemically compatible with the 35 liquids
active metal and the substantially impervious layer 108 is
those based on imidazolium and pyrrolidinium . The ionic
will generally contain a lithium salt , such as those
chemically compatible with the separator layer 106 and having a TFSI anion .
aqueous environments . The structure 100 may optionally As a particular type of non -aqueous electrolyte, ionic
include a current collector 110 , composed of a suitable liquid based electrolytes may be impregnated in a porous
conductive metal that does not alloy with or intercalate the 40 membrane (e.g. , a microporous membrane) or caused to
active metal . When the active metal is lithium , a suitable swell or gel a polymeric separator material. Typically , the
current collector material is copper. The current collector ionic liquid will further comprise a lithium salt dissociated
110 can also serve to seal the anode from ambient to prevent therein to provide charge carriers . In some instances the
deleterious reaction of the active metal with ambient air or ionic liquid may be caused to polymerize, and in such
moisture . 45 instances, the polymeric ionic liquid may itself serve as the
In various embodiments the separator layer 106 is com- lithium ion conducting separator layer. Ionic liquid based
posed of a porous membrane impregnated with a non- electrolytes , including those which are caused to swell or gel
aqueous anolyte . For example, the membrane may be a a polymeric separator layer (e.g. , polyvinylidene fluoride
micro - porous polymer, such as are available from Celgard , [ PVdF ] or poly - ethylene oxide [ PEO ] ) are suitable for use
Inc. The non - aqueous anolyte may be in the liquid or gel 50 herein and are known in the art . Ionic liquids may be
phase . For example, the anolyte may include a solvent classified according to their cation and anion compositions.
selected from the group consisting of organic carbonates, For example ionic liquid cations which are known in the art
ethers, lactones, sulfones , etc , and combinations thereof, include those of the Pyrrolidinium type (e.g. , N -methyl-N
such as EC , PC , DEC , DMC , EMC , 1,2 - DME or higher propylpyrrolidinium , N - propyl-N -methylpyrrolidinium
glymes , THF, 2MeTHF, sulfolane, ionic liquids ( as are 55 [ PYR13 + ] , 1 -butyl- 1 -methylpyrrolidinium [ PYR14 + ] , Imi
known in the art) and combinations thereof. 1,3 -dioxolane dazolium ( e.g. , 1 - ethyl - 3 -methylimidazolium [ EMI + ] ) . For
may also be used as an anolyte solvent, particularly but not example ionic liquid anions which are known in the art
necessarily when used to enhance the safety of a cell include those of the type bis ( trifluoromethanesulfonyl ) imide
incorporating the structure , as described further below. Gen- and bis (fluorosulfonyl)imide. A particularly suitable lithium
erally the anolyte should be chemically compatible in con- 60 salt is that of the type lithium bis( trifluoromethanesulfonyl)
tact with the active metal anode , and in this regard may imide . For example, N -Butyl-N -methylpyrrolidinium bis
include compatible liquid solvents (i.e. , those which are ( trifluoromethanesulfonyl) imide [ PYR14TFSI] and
solely compatible) as well as those solvents which are not N -Butyl- N -methylpyrrolidinium bis (fluorosulfonyl ) imide
compatible by themselves but in combination with a suitable [ PYR14FSI ] impregnated in a porous separator or caused to
electrolytic salt and / or additional solvent ( s) leads to a 65 gel or swell a suitable polymer such as PEO or PVDF, and
chemically compatible anolyte. Such liquid solvents ( solely having dissolved therein the lithium salt LiTFSI . It should be
chemically compatible or otherwise) may include organic or understand to one of skill in the art that the search for new
US 10,916,753 B2
17 18
and improved ionic liquid based electrolytes (or electrolytes For instance, the integrated structure may be fabricated by
comprising ionic liquids) for use in lithium batteries is an tape casting of a multi -layer ( e.g. , a dual layer ) wherein at
ongoing worldwide effort, and thus it is contemplated herein least one of the layers is substantially impervious and the
that novel and hitherto unknown ionic liquids suitable for layer opposing the anode ( e.g. , in direct contact) is porous .
use herein as an anolyte will be discovered , and especially 5 In some embodiments, the integrated structure may be
those having improved stability against electroactive lithium further paired with an additional porous interlayer which
materials such as lithium metal , and thus will provide separates the integrated layer from the anode and by this
particular benefit, and by this expedient such ionic liquids expedient allows for the use of an anode incompatible
are contemplated herein for use as an anolyte of the instant integrated structure into the protective architecture .
protected anode. 10 In other embodiments, it is contemplated that the sub
Another suitable anolyte includes a solution of a non- stantially impervious layer may be formed on or in conjunc
aqueous solvent ( s) combined with a very high concentration tion with an electronically insulating and ionically insulating
of a lithium salt (e.g. , about an equimolar complex of liquid porous substrate as a support layer. The substantially imper
solvent with lithium salts ) ; for example , an about equimolar vious layer may be fabricated as a coating or film on the
complex of a glyme ( e.g. , tri -glyme or tetra -glyme) and a 15 porous support ( e.g. , the porous support composed of a rigid
lithium salt of lithium bis ( trifluoromethanesulfonyl)amide glass or polycrystalline ceramic or glass -ceramic ), or it may
[ LiTFSA] or other such as lithium bis (trifluoromethane- be fabricated using multilayer tape casting wherein one or
sulfonyl)imide LiTFSI or lithium bis ( fluorosulfonyl) imide. more layers are lithium ion conductors and one or more
This anolyte may behave like a concentrated solution or an other layers provide a porous , non -conducting support.
ionic liquid . In some embodiments, fumed silica or other 20 In addition, porous metal support layer embodiments are
high surface area particles may be added to the solution to also contemplated . Generally when a porous metal support
enhance solution properties and in some instances for mak- is used it may be positioned on the surface that opposes the
ing the solution behave like a semi - solid . external environment about the protected anode (e.g. , that
In various embodiments the anolyte may be in the gel side which opposes the cathode ). However, this embodiment
phase or the anolyte may be a liquid anolyte swelled in or by 25 is not limited as such and the porous metal support may
a polymer layer. Such embodiments contemplate gel phase oppose the anode, but in such embodiments an insulating
anolytes of non - aqueous organic or ionic liquid solvents generally porous polymeric separator may be incorporated
typically in combination with a salt , or combinations thereof between the porous metal layer and the lithium layer, for the
of a gel phase anolyte comprising both a non - aqueous purpose of providing electronic isolation therebetween .
organic liquid solvent and a suitable ionic liquid solvent as 30 In yet a further embodiment, the interlayer may effec
described above . tively be provided by a gap ( i.e. , a space ) which contains a
There are a number of advantages of a protective archi- liquid phase anolyte but no material interlayer. The gap may
tecture in accordance with the present invention. In particu- be incorporated in the anode structure using any number of
lar, cell structures incorporating such an architecture may be suitable constructions, including wherein the substantially
relatively easily manufactured . In one example , lithium 35 impervious membrane is attached to a frame ( e.g. , provided
metal is simply placed against a micro -porous separator by the battery casing ) at a spaced apart distance from the
impregnated with organic liquid or gel electrolyte and with lithium metal layer, and the gap subsequently created there
the separator adjacent to a glass /glass ceramic active metal between the layers filled with liquid anolyte. In other words
ion conductor. a liquid anolyte interlayer devoid of a porous solid material
An additional advantage of the non -aqueous interlayer is 40 layer is contemplated herein .
realized when glass - ceramics are used . When amorphous Battery Cells
glasses of the type described by the OHARÀ Corp. patents The non -aqueous interlayer architecture is usefully
cited above are heat- treated , the glass devitrifies, leading to
adopted in battery cells . For example, the electrochemical
the formation of a glass -ceramic. However, this heat treat- structure 100 of FIG . 1 can be paired with a cathode system
ment can lead to the formation of surface roughness which 45 120 to form a cell 200 , as depicted in FIG . 2. The cathode
may be difficult to coat using vapor phase deposition of an system 120 includes an electronically conductive compo
inorganic protective interlayer such as LiPON , Cu2N , etc. nent, an ionically conductive component, and an electro
The use of a liquid (or gel ) , non -aqueous electrolyte inter- chemically active component. The cathode system 120 may
layer would easily cover such a rough surface by normal have any desired composition and, due to the isolation
liquid flow , thereby eliminating the need for surface polish- 50 provided by the protective architecture, is not limited by the
ing , etc. In this sense, techniques such as " draw - down” (as anode or anolyte composition. In particular, the cathode
described by Sony Corporation and Shott Glass ( T. Kessler, system may incorporate components which would otherwise
H. Wegener, T. Togawa, M. Hayashi, and T. Kakizaki, be highly reactive with the anode active metal , such as
“ Large Microsheet Glass for 40 - in . Class PALC Displays," aqueous materials, including water, aqueous catholytes and
1997 , FMC2-3 , incorporated herein by reference ) could be 55 air, metal hydride electrodes and metal oxide electrodes .
used to form thin glass layers (20 to 100 microns ) , and these In one embodiment, a Celgard separator would be placed
glasses heat treated to form glass -ceramics. against one side of the thin glass -ceramic, followed by a
In yet other embodiments, the interlayer may be inte- non - aqueous liquid or gel electrolyte, and then a lithium
grated with the second material layer (i.e. , the substantially electrode . On the other side of the glass ceramic membrane,
impervious layer ). For instance, the second material layer 60 an aggressive solvent could be used , such as an aqueous
may be a sintered layer of a glass , ceramic or glass ceramic electrolyte . In such a way, an inexpensive Li/water or Li/ air
and the porous interlayer integrated therewith . For example , cell , for example, could be built .
the porous interlayer composed of a substantially similar Cathode Systems
composition and / or crystal structure as that of the second As noted above , the cathode system 120 of a battery cell
material layer ( e.g. , an anode compatible LTP composition 65 in accordance with the present invention may have any
or Garnet like material) except that the integrated interlayer desired composition and, due to the isolation provided by the
is porous and therefore accepting of a liquid phase anolyte. protective architecture, is not limited by the anode or anolyte
US 10,916,753 B2
19 20
composition . In particular, the cathode system may incor- cathode material gets reduced . In a Li/water cell , the cata
porate components which would otherwise be highly reac- lytic electronically conductive support facilitates the redox
tive with the anode active metal , such as aqueous materials , reaction . As noted above , while not so limited , in a Li /water
including water, aqueous solutions and air, metal hydride cell , the cell reaction is believed to be :
electrodes and metal oxide electrodes. 5
Battery cells of the present invention may include, with Li+ H2O = LiOH + 1/2H2.
out limitation, water, aqueous solutions, air electrodes and The half -cell reactions at the anode and cathode are believed
metal hydride electrodes, such as are described in co to be :
pending application Ser. No. 10 /772,157 titled ACTIVE
METAL /AQUEOUS ELECTROCHEMICAL CELLS AND 10 Li= Litte Anode :
SYSTEMS , now U.S. Pat . No. 7,645,543 , incorporated
herein by reference in its entirety and for all purposes , and € + H2O = OH + AH2 Cathode:
metal oxide electrodes, as used, for example , in conven
tional Li - ion cells . Accordingly, the catalyst for the Li/water cathode pro
The effective isolation between anode and cathode 15 motes electron transfer to water, generating hydrogen and
achieved by the protective interlayer architecture of the hydroxide ion . A common , inexpensive catalyst for this
present invention also enables a great degree of flexibility in reaction is nickel metal ; precious metals like Pt , Pd, Ru, Au ,
the choice of catholyte systems, in particular aqueous sys etc. will also work but are more expensive.
tems , but also non - aqueous systems . Since the protected Also considered to be within the scope of Li ( or other
anode is completely decoupled from the catholyte, so that 20 active metal )/water batteries of this invention are batteries
catholyte compatibility with the anode is no longer an issue, with a protected Li anode and an aqueous electrolyte com
solvents and salts which are not kinetically stable to Li can posed of gaseous and / or solid oxidants soluble in water that
be used . can be used as active cathode materials ( electrochemically
For cells using water as an electrochemically active active component ). Use of water soluble compounds, which
cathode material, a porous electronically conductive support 25 are stronger oxidizers than water, can significantly increase
structure can provide the electronically conductive compo- battery energy in some applications compared to the lithium /
nent of the cathode system . An aqueous electrolyte (catho- water battery, where during the cell discharge reaction ,
lyte ) provides ion carriers for transport ( conductivity ) of Li electrochemical hydrogen evolution takes place at the cath
ions and anions that combine with Li . The electrochemically ode surface. Examples of such gaseous oxidants are 02 , SO2
active component (water) and the ionically conductive com- 30 and NO2 . Also , metal nitrites, in particular NaNO2 and
ponent ( aqueous catholyte ) will be intermixed as a single KNO2 and metal sulfites such as Na2SO3 and K2SO3 are
solution , although they are conceptually separate elements stronger oxidants than water and can be easily dissolved in
of the battery cell . Suitable catholytes for the Li/water large concentrations. Another class of inorganic oxidants
battery cell of the invention include any aqueous electrolyte soluble in water are peroxides of lithium , sodium and
with suitable ionic conductivity. Suitable electrolytes may 35 potassium , as well as hydrogen peroxide H,02 .
be acidic, for example, strong acids like HCI , H2SO4 , H3PO4 The use of hydrogen peroxide as an oxidant can be
or weak acids like acetic acid /Li acetate ; basic , for example, especially beneficial. There are at least two ways of utilizing
LiOH ; neutral, for example, sea water, LiCl , LiBr, Lil ; or hydrogen peroxide in a battery cell in accordance with the
amphoteric, for example, NH_C1 , NH_Br, etc present invention . First of all , chemical decomposition of
The suitability of sea water as an electrolyte enables a 40 hydrogen peroxide on the cathode surface leads to produc
battery cell for marine applications with very high energy tion of oxygen gas , which can be used as active cathode
density. Prior to use , the cell structure is composed of the material. The second , perhaps more effective way, is based
protected anode and a porous electronically conductive on the direct electroreduction of hydrogen peroxide on the
support structure ( electronically conductive component of cathode surface . In principal, hydrogen peroxide can be
the cathode ). When needed , the cell is completed by immers- 45 reduced from either basic or acidic solutions . The highest
ing it in sea water which provides the electrochemically energy density can be achieved for a battery utilizing hydro
active and ionically conductive components. Since the latter gen peroxide reduction from acidic solutions . In this case a
components are provided by the sea water in the environ- cell with Li anode yields Eº =4.82 V ( for standard condi
ment, they need not transported as part of the battery cell tions ) compared to Eº =3.05 V for Li /Water couple. How
prior to it use ( and thus need not be included in the cell's 50 ever, because of very high reactivity of both acids and
energy density calculation ). Such a cell is referred to as an hydrogen peroxide to unprotected Li , such cell can be
" open " cell since the reaction products on the cathode side practically realized only for protected Li anode such as in
are not contained . Such a cell is , therefore, a primary cell . accordance with the present invention .
Secondary Li /water cells are also possible in accordance For cells using air as an electrochemically active cathode
with the invention . As noted above , such cells are referred to 55 material, the air electrochemically active component of
as " closed" cells since the reaction products on the cathode these cells includes moisture to provide water for the elec
side are contained on the cathode side of the cell to be trochemical reaction . The cells have an electronically con
available to recharge the anode by moving the Li ions back ductive support structure electrically connected with the
across the protective membrane when the appropriate anode to allow electron transfer to reduce the air cathode
recharging potential is applied to the cell . 60 active material . The electronically conductive support struc
As noted above and described further below, in another ture is generally porous to allow fluid ( air) flow and either
embodiment of the invention , ionomers coated on the porous catalytic or treated with a catalyst to catalyze the reduction
catalytic electronically conductive support reduce or elimi- of the cathode active material. An aqueous electrolyte with
nate the need for ionic conductivity in the electrochemically suitable ionic conductivity or ionomer is also in contact with
active material. 65 the electronically conductive support structure to allow ion
The electrochemical reaction that occurs in a Li /water cell transport within the electronically conductive support struc
is a redox reaction in which the electrochemically active ture to complete the redox reaction .
US 10,916,753 B2
21 22
The air cathode system includes an electronically con- DIOX ) or organic carbonates like dimethylcarbonate
ductive component ( for example , a porous electronic con- ( DMC ) , ethylmethylcarbonate (EMC ), diethylcarbonate
ductor ), an ionically conductive component with at least an (DEC ) , or their mixtures . Also , super low viscosity ester
aqueous constituent, and air as an electrochemically active solvents or co - solvents such as methyl formate and methyl
component. It may be any suitable air electrode, including 5 acetate , which are very reactive to unprotected Li , can be
those conventionally used in metal ( e.g. , Zn )/ air batteries or used . As is known to those skilled in the art, ionic conduc
low temperature (e.g. , PEM) fuel cells . Air cathodes used in tivity and diffusion rates are inversely proportional to vis
metal/ air batteries, in particular in Zn / air batteries, are cosity such that all other things being equal, battery perfor
described in many sources including “ Handbook of Batter- mance improves as the viscosity of the solvent decreases .
ies ” ( Linden and T. B. Reddy, McGraw -Hill, NY, Third 10 The use of such catholyte solvent systems significantly
Edition ) and are usually composed of several layers includ- improves battery performance , in particular discharge and
ing an air diffusion membrane , a hydrophobic Teflon layer, charge characteristics at low temperatures.
a catalyst layer, and a metal electronically conductive com- Ionic liquids may also be used in catholytes of the present
ponent/current collector, such as a Ni screen . The catalyst invention . Ionic liquids are organic salts with melting points
layer also includes an ionically conductive component/ 15 under 100 degrees, often even lower than room temperature .
electrolyte that may be aqueous and / or ionomeric . A typical The most common ionic liquids are imidazolium and pyri
aqueous electrolyte is composed of KOH dissolved in water. dinium derivatives , but also phosphonium or tetralkylam
A typical ionomeric electrolyte is composed of a hydrated monium compounds are also known . Ionic liquids have the
( water) Li ion conductive polymer such as a per-fluoro- desirable attributes of high ionic conductivity, high thermal
sulfonic acid polymer film ( e.g. , du Pont NAFION ). The air 20 stability, no measurable vapor pressure , and non -flamma
diffusion membrane adjusts the air ( oxygen ) flow . The bility. Representative ionic liquids are 1 -Ethyl- 3-methylimi
hydrophobic layer prevents penetration of the cell's electro- dazolium tosylate ( EMIM - Ts ), 1 -Butyl-3 -methylimidazo
lyte into the air - diffusion membrane . This layer usually lium octyl sulfate ( BMIM - OctS04 ) , 1 - Ethyl -3
contains carbon and Teflon particles. The catalyst layer methylimidazolium hexafluorophosphate, and 1-Hexyl-3
usually contains a high surface area carbon and a catalyst for 25 methylimidazolium tetrafluoroborate . Although there has
acceleration of reduction of oxygen gas . Metal oxides , for been substantial interest in ionic liquids for electrochemical
example MnO2, are used as the catalysts for oxygen reduc- applications such as capacitors and batteries, they are
tion in most of the commercial cathodes . Alternative cata- unstable to metallic lithium and lithiated carbon . However,
lysts include metal macrocycles such as cobalt phthalocya- protected lithium anodes as described in this invention are
nine , and highly dispersed precious metals such at platinum 30 isolated from direct chemical reaction , and consequently
and platinum /ruthenium alloys . Since the air electrode struc- lithium metal batteries using ionic liquids are possible as an
ture is chemically isolated from the active metal electrode, embodiment of the present invention. Such batteries should
the chemical composition of the air electrode is not con- be particularly stable at elevated temperatures.
strained by potential reactivity with the anode active mate- Safety Additives
rial . This can allow for the design of higher performance air 35 As a safety measure , the non -aqueous interlayer architec
electrodes using materials that would normally attack unpro- ture can incorporate a gelling /polymerizing agent that, when
tected metal electrodes. in contact with the reactive electrolyte ( for example water ),
Another type of active metal/aqueous battery cell incor- leads to the formation of an impervious polymer on the
porating a protected anode and a cathode system with an anode (e.g. , lithium ) surface . This safety measure is used for
aqueous component in accordance with the present inven- 40 the case where the substantially impervious layer of the
tion is a lithium (or other active metal ) /metal hydride protective architecture ( e.g. , a glass or glass - ceramic mem
battery. For example, lithium anodes protected with a non- brane ) cracks or otherwise breaks down and allows the
aqueous interlayer architecture as described herein can be aggressive catholyte to enter and approach the lithium
discharged and charged in aqueous solutions suitable as electrode raising the possibility of a violent reaction between
electrolytes in a lithium /metal hydride battery. Suitable 45 the Li anode and aqueous catholyte.
electrolytes provide a source or protons. Examples include Such a reaction can be prevented by providing in the
aqueous solutions of halide acids or acidic salts , including anolyte a monomer for a polymer that is insoluble or
chloride or bromide acids or salts , for example HCI , HBr, minimally soluble in water, for example dioxolane ( Diox )
NH C1 or NH Br. ( for example , in an amount of about 5-20 % by volume ) and
In addition to the aqueous , air, etc., systems noted above, 50 in the catholyte a polymerization initiator for the monomer,
improved performance can be obtained with cathode sys- for example, a protonic acid . A Diox based anolyte may be
tems incorporating conventional Li - ion battery cathodes and composed of organic carbonates (EC , PC , DEC , DMC ,
electrolytes, such as metal oxide cathodes (e.g. , Li,C002 , EMC ) , ethers ( 1 , 2 - DME , THF, 2MeTHF, 1,3 - dioxolane and
Li NiO2, Li,Mn , 04 and LiFePO ) and the binary, ternary or others) and their mixtures . Anolyte comprising dioxolane as
multicomponent mixtures of alkyl carbonates or their mix- 55 a main solvent (e.g. , 50-100% by volume) and Li salt , in
tures with ethers as solvents for a Li metal salt ( e.g. , LiPF69 particular, LiAsF . , LiBF4, LISO , CF3, LiN ( SO , C2Fs ) , is
LiAsFo or LiBF % ) ; or Li metal battery cathodes ( e.g. , especially attractive. Diox is a good passivating agent for Li
elemental sulfur or polysulfides ) and electrolytes composed surface, and good cycling data for Li metal has been
of organic carbonates, ethers, glymes , lactones, sulfones, achieved in the Diox based electrolytes ( see , e.g. , U.S. Pat.
sulfolane, and combinations thereof, such as EC , PC , DEC , 60 No. 5,506,068 ) . In addition to its compatibility with Li
DMC , EMC , 1,2 - DME , THF, 2 MeTHF, and combinations metal , Diox in combination with above -mentioned ionic
thereof, as described , for example , in U.S. Pat . No. 6,376 , salts forms highly conductive electrolytes. A corresponding
123 , incorporated herein by reference. aqueous catholyte contains a polymerization initiator for
Moreover, the catholyte solution can be composed of only Diox that produces a Diox polymerization product (polydi
low viscosity solvents, such as ethers like 1,2 -dimethoxy 65 oxolane) that is not or is only minimally soluble in water .
ethane ( DME ) , tetrahydrofuran ( THF ) , 2 -methyltetrahydro- If the membrane breaks down , the catholyte containing
furan , 1,3 -dioxolane (DIOX ) , 4 -methyldioxolane (4 -Me- the dissolved initiator comes in direct contact with the Diox
US 10,916,753 B2
23 24
based anolyte , and polymerization of Diox occurs next to the or cells ( anode, interlayer, cathode, etc. ) according to known
Li anode surface. Polydioxolane, which is a product of Diox battery cell fabrication techniques that are readily adaptable
polymerization , has high resistance, so the cell shuts down. to the present invention given the description of the structure
In addition , the Polydioxolane layer formed serves as a or cell components provided herein . These stacked layers
barrier preventing reaction between the Li surface and the 5 may be configured as prismatic structures or cells .
aqueous catholyte . Diox can be polymerized with protonic Alternatively, the use of tubular glass or glass - ceramic
acids dissolved in the catholyte. Also , the water soluble electrolytes with a non -aqueous interlayer architecture
Lewis acids , in particular benbenzoyl cation, can serve this allows for the construction of high surface area anodes with
purpose . low seal area . As opposed to flat -plate design where the seal
Thus, improvement in cyclability and safety is achieved 10 length increases with cell surface area , tubular construction
by the use of a dioxolane (Diox ) based anolyte and a utilizes an end seal where the length of the tube can be
catholyte containing a polymerization initiator for Diox . increased to boost surface area while the seal area is invari
Active Metal Ion and Alloy Anodes ant. This allows for the construction of high surface area
The invention pertains to batteries and other electro- Li /water and Li/ air cells that should have correspondingly
chemical structures having anodes composed of active met- 15 high power density.
als , as described above . A preferred active metal electrode is The use of a non -aqueous interlayer architecture in accor
composed of lithium (Li ) . Suitable anolytes for these struc dance with the present invention facilitates construction . An
tures and cells are described above . open -ended (with a seal ) or close - ended glass or glass
The invention also pertains to electrochemical structures ceramic ( i.e. , substantially impervious active metal ion con
having active metal ion ( e.g. , lithium -carbon ) or active metal 20 ductive solid electrolyte ) tube is partially filled with a
alloy ( e.g. , Li -Sn) anodes . Some structures may initially non - aqueous organic electrolyte ( anolyte or transfer electro
have uncharged active metal ion intercalation materials lyte ) as described above, for example such as is typically
( e.g. , carbon ) or alloying metals (e.g. , tin (Sn )) that are used in lithium primary batteries A lithium metal rod sur
subsequently charged with active metal or active metal ions . rounded by some type of physical separator ( e.g. , a semi
While the invention may be applicable to a variety of active 25 permeable polymer film such as Celgard , Tonin , polypro
metals , it is described herein primarily with reference to pylene mesh, etc.) having a current collector is inserted into
lithium , as an example. the tube . A simple epoxy seal , glass -to - metal seal , or other
Carbon materials commonly used in conventional Li - ion appropriate seal is used to physically isolate the lithium from
cells , in particular petroleum coke and mesocarbon micro- the environment.
bead carbons, can be used as anode materials in Li - ion 30
aqueous battery cells . Lithium alloys comprising one or airThe protected anode can then be inserted in a cylindrical
electrode to make a cylindrical cell , as shown in FIG . 3A .
several of the metals selected from the group including Ca , Or an array of anodes might be inserted into a prismatic air
Mg , Sn , Ag , Zn , Bi , Al , Cd , Ga , In and Sb , preferably Al , Sn electrode, as shown in FIG . 3B .
or Si , can also be used as anode materials for such a battery. This technology can also be used to build Li/water,
In one particular embodiment the anode comprises Li , Cu 35 Li/metal hydride or Li/metal oxide cells by substituting the
and Sn . air electrode with suitable aqueous, metal hydride or metal
Anolyte for such structures can incorporate supporting oxide cathode systems, as described herein above .
salts , for example, LiAsF . , LiC104 , LISO2CF3 , LiN In addition to the use of lithium metal rods or wires (in
(CF SO2)2 or LiN (SO , C2F5 ) 2 dissolved in binary or ternary capillary tubes ), this invention can also be used to isolate a
mixtures of non -aqueous solvents, for example, EC , PC , 40 rechargeable Licz anode from aqueous or otherwise corro
DEC , DMC , EMC , MA, MF, commonly used in conven- sive environments . In this case , appropriate anolyte ( transfer
tional Li - ion cells . Gel -polymer electrolytes, for instance electrolyte ) solvents are used in the tubular anode to form a
electrolytes comprising one of the above mentioned salts , a passive film on the lithiated carbon electrode. This would
polymeric binder, such as PVDF, PVDF - HFP copolymer, allow the construction of high surface area Li - ion type cells
PAN or PEO , and a plasticizer ( solvent) such as EC , PC , 45 using a number of exotic cathodes such as air, water, metal
DEC , DMC , EMC , THF, 2MeTHF, 1,2 - DME and their hydrides or metal oxides , for example, as shown in FIG . 3C .
mixtures, also can be used.
For batteries using these anodes , a suitable cathode struc EXAMPLES
ture may be added to the electrochemical structure on the
other side of the protective architecture . The architecture 50 The following examples provide details illustrating
enables Li - ion type cells using a number of exotic cathodes advantageous properties of Li metal and Li - ion aqueous
such as air, water, metal hydrides or metal oxides . For Li - ion battery cells in accordance with the present invention . These
aqueous battery cells , for example, aqueous catholyte can be examples are provided to exemplify and more clearly illus
basic , acidic or neutral and contains Li cations. One example trate aspects of the present invention and in no way intended
of a suitable aqueous catholyte is 2 M LiCl , 1 M HCl . 55 to be limiting.
During the first charge of the battery with lithium - carbon
lithium alloy anode , Li cations are transported from the Example 1 : Li/ Seawater Cell
catholyte through the protective architecture ( including the
anolyte) to the anode surface where the intercalation process A series of experiments was performed in which the
takes place as in conventional Li - ion cells . In one embodi- 60 commercial ionically conductive glass -ceramic from
ment, the anode is chemically or electrochemically lithiated OHARA Corporation was used as a membrane separating
ex - situ before cell assembly. aqueous catholyte and non - aqueous anolyte. The cell struc
Cell Designs ture was Li/non -aqueous electrolyte / glass -ceramic /aqueous
Electrochemical structures and battery cells in accordance electrolyte /Pt. A lithium foil from Chemetall Foote Corpo
with the present invention may have any suitable geometry. 65 ration with thickness of 125 microns was used as the anode .
For example, planar geometries may be achieved by stack- The GLASS -CERAMIC plates were in the range of 0.3 to
ing planar layers of the various components of the structures 0.48 mm in thickness . The GLASS - CERAMIC plate was
US 10,916,753 B2
25 26
fitted into an electrochemical cell by use of two o -rings such microporous Celgard separator placed on the other side of
that the GLASS - CERAMIC plate was exposed to an aque- the glass -ceramic were filled with non - aqueous electrolyte
ous environment from one side and a non - aqueous environ- comprised of 1 M LiPF dissolved in the mixture of ethylene
ment from the other side. In this case , the aqueous electro- carbonate and dimethyl carbonate ( 1 : 1 by volume). A
lyte comprised an artificial seawater prepared with 35 ppt of 5 layers
lithium ofwire reference
Celgard electrode
separator in orderwasto placed
control between two
the potential
“ Instant Ocean ” from Aquarium Systems , Inc. The conduc
tivity of the seawater was determined to be 4.5 10-2 S /cm . of the carbon anode during cycling. A platinum mesh
A microporous Celgard separator placed on the other side of completely immersed in the 2 M LiCl , 1 M HCl solution was
the GLASS - CERAMIC was filled with non - aqueous elec used as the cell cathode. An Ag /AgCl reference electrode
trolyte comprised of 1 M LiPF6 dissolved in propylene 10 placed in the aqueous electrolyte was used to control poten
carbonate. The loading volume of the nonaqueous electro tial of the carbon electrode and voltage drop across the
lyte was 0.25 ml per 1 cm² of Li electrode surface . A GLASS -CERAMIC plate , as well as potential of the Pt
platinum counter electrode completely immersed in the sea cathode during cycling . An open circuit voltage ( OCV)
water catholyte was used to facilitate hydrogen reduction around 1 volt was observed for this cell . The voltage
when the battery circuit was completed. An Ag/ AgCl refer- 15 Ag difference of 3.2 volts between Li reference electrode and
/AgCl reference electrode closely corresponding to the
ence electrode was used to control potential of the Li anode
in the cell . Measured values were recalculated into potentials thermodynamical value was observed . The cell was charged
in the Standard Hydrogen Electrode ( SHE ) scale . An open at 0.1 mA / cm² until the carbon electrode potential reached 5
circuit potential (OCP ) of 3.05 volts corresponding closely mV vs. Li reference electrode, and then at 0.05 mA /cm²
to the thermodynamic potential difference between Li /Li + 20 using the same cutoff potential . The discharge rate was 0.1
and H2 /H + in water was observed ( FIG . 4 ) . When the circuit mA / cm², and discharge cutoff potential for the carbon anode
was closed, hydrogen evolution was seen immediately at the was 1.8 V vs. Li reference electrode . The data in FIG . 6 show
Pt electrode , which was indicative of the anode and cathode that the cell with intercalation carbon anode and aqueous
electrode reactions in the cell , 2Li =2Li + 2e- and 2H + + electrolyte containing Li cations can work reversibly. This is
2e =H2. The potential- time curve for Li anodic dissolution 25 the first known example where aqueous solution has been
at a discharge rate of 0.3 mA / cm² is presented in FIG . 2.The used in Li - ion cell instead of solid lithiated oxide cathode as
results indicate an operational cell with a stable discharge a source of Li ions for charging of the carbon anode .
voltage . It should be emphasized that in all experiments
using a Li anode in direct contact with seawater utilization 30 Alternative Embodiment - Li /Water Battery and
of Li was very poor, and such batteries could not be used at Hydrogen Generator for Fuel Cell
all at low and moderate current densities similar to those
used in this example due to the extremely high rate of Li The use of protective architecture on active metal elec
corrosion in seawater ( over 19 A /cm²). trodes in accordance with the present invention allows the
construction of active metal/water batteries that have neg
Example 2 : Li/Air Cell 35 ligible corrosion currents, described above . The Li /water
battery has a very high theoretical energy density of 8450
The cell structure was similar to that in the previous Wh /kg. The cell reaction is Li+ H2O = LiOH + 1 /2 H2 . Although
example, but instead of a Pt electrode completely immersed the hydrogen produced by the cell reaction is typically lost ,
in the electrolyte, this experimental cell had an air electrode in this embodiment of the present invention it is used to
made for commercial Zn / Air batteries. An aqueous electro- 40 provide fuel for an ambient temperature fuel cell . The
lyte used was 1 M LiOH . A Li anode and a non -aqueous hydrogen produced can be either fed directly into the fuel
electrolyte were the same as described in the previous cell or it can be used to recharge a metal hydride alloy for
example. later use in a fuel cell . At least one company, Millenium Cell ,
An open circuit potential of 3.2 V was observed for this makes use of the reaction of sodium borohydride with water
cell . FIG . 5 shows discharge voltage -time curve at discharge 45 to produce hydrogen . However, this reaction requires the use
rate of 0.3 mA /cm2. The cell exhibited discharge voltage of of a catalyst , and the energy produced from the chemical
2.8-2.9 V. for more than 14 hrs. This result shows that good reaction of NaBH4 and water is lost as heat .
performance can be achieved for Li /air cells with solid NaBH4+ 2H20-4H2 +NaBO2
electrolyte membrane separating aqueous catholyte and non 50
aqueous anolyte. When combined with the fuel cell reaction , H2 + 02 =H20 ,
the full cell reaction is believed to be :
Example 3 : Li -Ion Cell NaBH4+ 202 > 2H2O + NaBO2
In these experiments the commercial ionically conductive The energy density for this system can be calculated from
glass -ceramic from OHARA Corporation was used as a
membrane separating aqueous catholyte and non - aqueous
55 grams
the equivalent weight of the NaBH4 reactant ( 38/ 4 = 9.5
/ equiv . ). The gravimetric capacity of NaBH , is 2820
anolyte. The cell structure was carbon /non -aqueous electro- mAh / g; since the voltage of the cell is about 1 , the specific
lyte / glass - ceramic plate /aqueous electrolyte / Pt. A commer- energy of this system is 2820 Wh /kg. If one calculates the
cial carbon electrode on copper substrate comprising a energy density based on the end product NaBO2 , the energy
synthetic graphite similar to carbon electrodes commonly 60 density is lower, about 1620 Wh/kg .
used in lithium - ion batteries was used as the anode. The In the case of the Li/water cell , the hydrogen generation
thickness of the glass -ceramic plate was 0.3 mm . The proceeds by an electrochemical reaction believed described
glass - ceramic plate was fitted into an electrochemical cell by by :
use of two o - rings such that the glass -ceramic plate was Li + H2O =LiOH + AH2
exposed to an aqueous environment from one side and a 65
non - aqueous environment from the other side. The aqueous In this case , the energy of the chemical reaction is
electrolyte comprised 2 M LiCl and 1 M HCl . Two layers of converted to electrical energy in a 3 volt cell , followed by
US 10,916,753 B2
27 28
conversion of the hydrogen to water in a fuel cell , giving an What is claimed is :
overall cell reaction believed described by : 1. A battery cell comprising:
a cathode comprising seawater ; and
Li + 1/2H2O + 1/402 = LiOH a protected lithium metal electrode comprising a lithium
5 anode and a protective architecture, the protective
where all the chemical energy is theoretically converted to architecture comprising a first lithium ion conducting
electrical energy . The energy density based on the lithium separator layer and a second lithium ion conducting
anode is 3830 mAh / g at a cell potential of about 3 volts layer;
which is 11,500 Wh /kg (4 times higher than NaBH4) . If one wherein the first layer further comprises a lithium ion
includes the weight of water needed for the reaction , the 10 conducting anolyte, and the second layer is a substan
energy density is then 5030 Wh /kg. If the energy density is tially impervious layer that prevents the lithium anode
based on the weight of the discharge product, LiOH , it is from deleterious reaction in direct contact with the
seawater of the cathode .
then 3500 Wh /kg, or twice the energy density of the NaBO2 2. The battery cell of claim 1 wherein the lithium anode
system . This can be compared to previous concepts where is lithium metal .
the reaction of lithium metal with water to produce hydrogen 15 3. The battery cell of claim 1 wherein the lithium anode
has also been considered . In that scenario the energy density comprises intercalating carbon.
is lowered by a factor of three, since the majority of the 4. The battery cell of claim 1 wherein the lithium anode
energy in the Li /H20 reaction is wasted as heat, and the comprises a lithium alloying material.
energy density is based on a cell potential for the H2/ 02 5. The battery cell of claim 4 wherein the lithium alloying
couple (as opposed to 3 for Li/H20) which in practice is less 20 material is silicon or tin.
6. The battery cell of claim 1 wherein the anolyte is a
than one . In this embodiment of the present invention , liquid electrolyte.
illustrated in FIG . 7 , the production of hydrogen can also be
carefully controlled by load across the Li /water battery, the electrolytebattery
7. The .
cell of claim 1 wherein the anolyte is a gel
Li/ water battery has a long shelf life due to the protective 8. Theelectrolyte
battery cell. of claim 1 wherein the anolyte is a
membrane, and the hydrogen leaving the cell is already 25 polymer
humidified for use in the Hz/ air fuel cell . 9. The battery cell of claim 1 wherein the first separator
layer further comprises glass or ceramic particles.
CONCLUSION 10. The battery cell of claim 9 wherein the glass or
ceramic particles getter shorting dendrites.
Although the foregoing invention has been described in 30 11. The battery cell of claim 1 wherein the lithium ion
some detail for purposes of clarity of understanding, it will conducting
contacts the
substantially impervious second layer directly
seawater of the cathode .
be apparent that certain changes and modifications may be 12. The battery cell of claim 1 wherein the substantially
practiced within the scope of the invention . In particular, impervious second material layer is a tape cast layer.
while the invention is primarily described with reference to 35 13. The battery
a lithium metal , alloy or intercalation anode , the anode may comprises a garnetcelllithium
of claim 12 wherein the tape cast layer
ion conductor.
also be composed of any active metal , in particular, other 14. The battery cell of claim 1 wherein the second
alkali metals , such as sodium . It should be noted that there material layer comprises a garnet lithium ion conductor.
are many alternative ways of implementing both the process 15. The battery cell of claim 1 wherein the second
and compositions of the present invention . Accordingly, the 40 material layer comprises a ceramic lithium ion conductor
present embodiments are to be considered as illustrative and comprising lithium titanium phosphate.
not restrictive, and the invention is not to be limited to the 16. The battery cell of claim 12 wherein the second
details given herein . material layer comprises a ceramic lithium ion conductor
All references cited herein are incorporated by reference comprising lithium titanium phosphate.
for all purposes.

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( 54 ) LITHIUM METAL — SEAWATER BATTERY ( 58 ) Field of Classification Search

Related U.S. Application Data 4,405,995 A 9/1983 Shirai

( 56 ) References Cited 2002/0012846 A1 1/2002 Skotheim et al.

( 56 ) References Cited Zhang et al . , “ Electrochemical Lithium Intercalation in VO.sub .

Separator Air electrode Transfer electrolyte

Prismatic air electrode

Separator Air electrode Transfer electrolyte

Lit conductive solid electrolyte LiC, electrode

3.4 3.2 2.8 2.6 2.4

5.0 4.0 3.0 2.0 1.0 0.0 0

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