`
`(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION T REATY (PCT)
`
`
`
`
`
`(19)World Intellectual Property Organization
`
`
`International Bureau
`
`10/40
`
`(10) International Publication Number
`
`
`(43)International Publication Date
`
`
`26 April 2001 (26.04.2001)PCT WO 01/29920 Al
`
`
`
`
`(51)International Patent Classification 7: H0lM 6/18,
`
`
`
`
`Thomas, J. [US/US]; 1062 65th Street, Oakland, CA
`
`
`94608 (US). ROSS, Philip, N., Jr. [US/US]; 103 Alta
`
`
`Mesa Court, Moraga, CA 94556 (US).
`(21)International Application Number: PCT/US00/28975
`
`
`(74)Agent: SARTORIO, Henry, P.; Lawrence Berkeley Na-
`
`
`
`
`
`
`
`(22)International Filing Date: 18 October
`
`
`
`
`
`2000 (18.10.2000)tional Laboratory, Patent Dept., One Cyclotron Road, MS
`
`
`90-1121, Berkeley, CA 94720 (US).
`
`(25)Filing Language:
`English
`
`
`(26)Publication Language:
`English
`European patent (84)Designated States (regional): (AT, BE,
`
`
`
`
`(30)Priority Data:
`
`CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC,
`
`60/160,391 18 October 1999 (18.10.1999)
`NL, PT, SE).
`(71)Applicant (for all designated
`US): THEStates except
`
`
`
`Published:
`
`REGENTS OF THE UNIVERSITY OF CALIFORNIA
`
`
`
`
`[US/US]; 12th floor, 1111 Franklin Street, Oakland, CA With international
`
`search report.
`94607 (US).
`
`
`
`(81)Designated States (national): JP, KR, US.
`
`
`
`us
`
`For two-letter codes and other abbreviations, refer to the "Guid­
`
`
`
`
`ance Notes on Codes and Abbreviations" appearing at the begin­
`(for US only): _ (75) Inventors/Applicants RICHARDSON,
`
`
`ning of each regular issue of the PCT Gazette.
`
`
`=== (72) Inventors; and
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`;;;;;;;;
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`�
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`- �
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`I!!!!!!!
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`-===
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`N
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`-----------------------------------------
`
`FOR BATTERIES 0--., (54) Title: SHUTDOWN AND REDOX SHUTTLE ADDITIVES
`
`
`
`
`0--.,
`� (57) Abstract: A group of shutdown additives are provided in the electrolyte of rechargeable batteries or electrochemical storage
`
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`of overcharging to prevent and function compounds, molecular weight organic aromatic S or secondary cells. The additives are low
`
`
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`
`
`
`the cell. Some of the additives also function as redox shuttle additives at less server overcharging conditions. These additives can be
`
`
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`
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`which is fully charged and a positive electrode electrolyte or solid polymer 0 used in any rechargeable battery utilizing a non-aqueous
`> at about 4 V vs. Li/Li+. These include
`
`
`
`
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`
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`batteries for consumer electronics, communications, power tools. electric vehicles, and load
`;;-,- leveling.
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`11111111111111111111111 I lllll 1111111111111111 IIIII IIII I 111111111111111 lllll lllll
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`1
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`APPLE-1008
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`

`

`WO 01/29920
`
`PCT/US00/28975
`
`Shutdown and Redox Shuttle Additives for Batteries
`
`Related Applications
`
`This application claimspriority of Provisional Application Ser. No. 60/160,391
`
`filed 10/18/99, which is herein incorporated by reference.
`
`GovernmentRights
`
`The United States Governmenthasrights in this invention pursuant to Contract
`
`No. DE-AC03-76SF00098 between the United States Department of Energy and the
`
`University of California.
`
`Backgroundof the Invention
`
`The invention relates to rechargeable batteries, and more particularly to shutdown
`
`additives and redox shuttle additives for overcharge protection in rechargeable batteries.
`
`Reliable and inexpensive overcharge protection for multi-cell lithium (and other)
`
`battery stacks is a major obstacle to commercialization of these promising systems in
`
`electric vehicles and other high voltage applications. Overcharging not only can reduce
`
`rechargeable capacity andcell life, but can also create hazardous conditions. Even
`
`moderate overcharging oftransition metal oxide cathodes often leads to structural and
`
`compositional changesin the oxide matrix which havesignificant effects on their
`
`subsequent cycling behavior.
`
`The redox shuttle approach to overcharge protection employsan electrolyte
`
`additive that acts as an internal current shunt when the charging potential exceeds a
`
`characteristic onset potential for the additive. The ability of certain organic aromatic
`
`compound additives to extendcell life in transition metal oxide lithium solid polymer
`
`electrolyte cells under conditions of moderate to severe overcharging has been
`
`demonstrated,as illustrated in U.S. Patent 6,004,698 to Richardson et al. Other redox
`
`shuttle additives have been reported for both polymerelectrolyte, as described by F. Tran-
`
`2
`
`

`

`WO 01/29920
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`PCT/US00/28975
`
`Van et al., Electrochim. Acta, 44, 2789 (1999), and 4 volt lithium ion cells, as shown in
`US. Patent 5,763,119 to Adachi.
`Overcharging of batteries can create hazardous conditions, leading to explosion,
`fire, and/or release oftoxic materials. External protection mechanismsthat stop charging
`whenavoltage, temperature, or internal pressure limit is reached are currently in use, but
`these are subject to failure or abuse (such as using a charger designed for a different
`battery). Redox shuttle additives provide an internal, automatic overcharge protection
`mechanism that allows charging currentto pass through the cell without overchargingit.
`Theability of such additives to extendcelllife in lithium and lithium ion cells under
`conditions of moderate to severe overcharging has been demonstrated. However, for
`many applications, the issue of safety takes precedence over the desire for cell life
`extension. A mechanism that renders the battery harmless on overcharging is acceptable
`even thoughit endsits usefullife. Thus “shutdown”additives that achieve this goal are
`desired. Someof these may act as redox shuttles under moderate overcharge conditions
`and as shutdown additives when the overcharge conditions are more severe. Both redox
`shuttle and shutdown additives maybepresent in the samecell.
`
`Summary of the Invention
`Accordinglyit is an object ofthe invention to provide shutdown additives for
`
`rechargeable batteries.
`It is also an object of the invention to provide shutdown additives for rechargeable
`batteries that also act as redox shuttle additives at lower overcharge conditions.
`It is another object of the invention to provide shutdown additives, which may
`also act as redox shuttle additives, for rechargeable lithium orlithium ion batteries,
`
`particularly 4 V lithium ionbatteries.
`The inventionis a group of shutdown additives for the electrolyte of rechargeable
`batteries or electrochemical storage or secondary cells, and the rechargeable batteries or
`electrochemical storage cells with these additives. The additives are low molecular
`weight organic aromatic compounds, and function to prevent overcharging ofthe cell.
`Whenoneor more ofthe additives is addedto the electrolyte of a rechargeable cell, it will
`
`3
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`PCT/US00/28975
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`be oxidizedat the positive electrode at a potential specific to the additive(s). The product
`of this oxidation increases the resistance ofthe cell by meansof polymerization,
`precipitation,electrolyte depletion, chemical reaction, or other mechanism. This prevents
`further charging ofthe cell, thereby preventing developmentof unsafe conditions.
`Someofthe additives also function as redox shuttle additives at less severe
`
`overcharging conditions. When oneor moreofthem is addedto the electrolyte of a
`rechargeablecell, it is oxidized at the positive electrode to its respective radical cation at
`certain potentials. The cation diffuses throughtheelectrolyte to the negative electrode,
`whereit is reduced to its original neutral state. This allows the additive(s) to transport an
`electrical charge through the cell without damageto the cell under conditions that would,
`in the absence ofthe additive(s), causeit to lose capacity or fail. Under more severe
`overcharging conditions, the cation transport through theelectrolyte is insufficient, and
`the additives are oxidizedat the positive electrode to shut off the cell.
`
`These additives could find use in any rechargeablebattery utilizing a non-aqueous
`or solid polymerelectrolyte and a positive electrode whichis fully charged at about 4 V
`vs. Li/Li”. These include batteries for consumer electronics, communications, power
`tools, electric vehicles, and loadleveling.
`
`Brief Description of the Drawings
`Fig. 1 is a cross-sectional view ofa rechargeable battery or electrochemicalcell.
`Fig. 2 is a graph ofthe onset potentials of two shutdownadditives of the
`invention.
`
`Fig. 3 is a graphof the onset potentials of seven shutdown/redox shuttle additives
`of the invention compared to twopriorart additives.
`
`Fig. 4 is a graph ofthe onset potentials of seventeen shutdown/redoxshuttle
`
`additives of the invention.
`
`Detailed Description of the Invention
`
`The invention applies to rechargeable batteries or electrochemical storagecells,
`e.g. lithium andlithium ionbatteries, of the type which are well known in theart, e.g. as
`
`4
`
`

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`PCT/US00/28975
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`described in U.S. Patents 6,004,698 and 5,763,119, which are herein incorporated by
`reference. The materials of which the standard parts of the batteries or cells of the
`invention are made,as wellas the configuration of the battery or cell, can be found in
`these and other references.
`
`Fig. 1 illustrates a battery or cell 12 that is formed within a nonreactive outer case
`
`or shell 12 with an optional insulating innerlining 14 inside case 12 that form sidewalls
`of battery 12. A negative electrode current collector 20 is positioned against one sidewall
`of battery 12, and a negative electrode 24, which formsthe negative electrode material,is
`positioned next to andin contact with negative electrode current collector 20.
`Alternatively, negative electrode 24 and negative electrode currentcollector 20 may form
`a unitary structure, referred to as negative electrode 24. Similarly, a positive electrode
`current collector 36 is positioned against an opposed sidewallof battery 12, and a positive
`electrode 32, which formsthe positive electrode material, is positioned next to andin
`
`contact with positive electrode current collector 36. Alternatively, positive electrode 32
`andpositive electrode currentcollector 36 may form a unitary structure, referred to as
`positive electrode 32.
`
`Between negative electrode 24 andpositive electrode 32 is solid polymer
`electrolyte 28, which is ionically conducting and also serves as an insulator or separator
`between the negative electrode 24 and positive electrode 32. In somebatteries it may be
`possible that the electrolyte is liquid. In accordance with the invention,electrolyte 28
`includes the shutdown or shutdown/redox shuttle additives of the invention.
`
`The shutdown (SD) and shutdown/redox shuttle (SD/RS) additivesof the
`invention have commonstructural features including an aromatic ring and electro-
`withdrawing substituents which give them high oxidation potentials andstabilize the
`resulting oxidized species. They fall into several structural subcategories. Some
`additives can be considered to be membersof more than one of these subgroups.
`Category A: halogenated benzenes and naphthalenes
`
`Category B: substituted methoxybenzenes
`
`Category C: substituted benzodioxoles
`
`Category D: alkyl polyethers
`
`5
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`

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`Category E: substituted nitrogen-containing heterocycles
`The following compoundsin Table | act as cell shutdown additives:
`
`
`
`
`
`
`
`
`621-23-8
`1,3,5-trimethoxybenzene
`
`3|2-methoxyethy] ether 111-96-6
`
`4|tri(ethylene glycol) dimethy] ether 112-49-2 5.20
`
`
`5|tetra(ethylene glycol) dimethyl! ether|143-24-8 5.25|Db|
`1,2,4-trifluorobenzene
`367-23-7
`
`
`1,2,3,4-tetrafluorobenzene
` 2,4,6-trimethoxypyrimidine
`
`13106-85-9
`
`2,6-dimethoxy-1,4-benzoquinone
`530-55-2
`
`
`10|2,4-dimethoxybenzonitrile 4107-65-7 4.50
`
`
`9334-10-3
`
`
`
`
`Table I
`
`
`
`
`
`
`
`The onset potential graphsfor the first two additives in Table I (SD 1, SD 2) are
`shownin Fig. 2.
`
`In addition, the following additives in Table II can act both as redox shuttles under
`moderate overcharge conditions,and as cell shutdown additives when subjected to more
`severe overcharging:
`
`
`
`SD/RS#|;Compound Name CAS No. Onset Category
`
`
`
`Table II
`
`
`
`Potential
`
`
`
`
`
`
`LBNL3|34cdimethonybenzonirile|204831|450[8|
`
`
`
`
`
`[LBNL§|12-dimetoxy~inivobenoane|700.01|45s]8|
`
`
`[LBNL9[3.45-rimetoxybenzonite|885.354|440[3|
`
`
`
`
`
`
`
`6
`
`

`

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`PCT/US00/28975
`
`
`
`
`LBNL10|octafluoronaphthalene 313-72-4
`
`LBNL11|2,3-dimethoxybenzonitrile 5653-623|450|B_|
`LBNL12|
`3,5-dimethoxybenzonitrile
`
`
`LBNL 13|2,3,4-trimethoxybenzonitrile 43020-38-8
`
`LBNL14 |
`1,2,3-trimethoxybenzene
`634-36-6
`
`
`
`
`LBNL 15|1,2,4-trimethoxybenzene 135-77-3 3.72
`
`
`
`
`LBNL16|3,4-difluoroanisole 115144-40-6 4.57 A,B
`
`
`
`
`LBNL 17|pentafiuoroanisole 389-40-2 5.05 A,B
`
`
`A
`
`LBNL 18|1,2,4,5-tetrafluorobenzene 327-54-8
`
`
`
`LBNL 19|1,2,3-trifluorobenzene 1489-53-8
`
`LBNL20|1,3,5-trifluorobenzene 372-38-3
`
`
`19179-31-8|445|B|
`
`
`
`
`
`
`
`
`LBNL21|1,2,3,5-tetrafluorobenzene 2367-82-0
`
`
`
`
`
`
`LBNL22|2,3,4-trifluorobenzonitrile 143879-80-5
`
`
`
`
`
`
`
`
`LBNL23|2,3,6-trifluorobenzonitrile 136514-17-5
`
`LBNL 24|3,4,5-trifluorobenzonitrile 134227-45-5
`
`This invention provides new additives for batteries or electrochemical storagecells,
`
`particularly for 4 volt cells incorporating liquid or preferably polymerelectrolytes. The
`
`prior art redox shuttle additives by Sony researchers described in U.S. Patent 5,763,119
`
`are dimethoxybenzenes with a single halide substituent, having molecular structure “‘a”
`
`shown below, where X is a halogen,e.g. fluorine (SONY 1) or bromine (SONY 2).
`
`OCH;
`as’
`xtJ
`
`Ss
`
`OCH;
`
`OCH
`
`3
`
`OCH3
`
`OCH3
`
`OCH,
`
`F
`
`Br
`
`a
`
`SONY1
`
`SONY 2
`
`They have onsetpotentials ranging from 3.93 to 4.10 V vs. Li/Li’. The onset
`
`potentials for the two best-performing SONYadditives are shown in Fig.3, labelled
`
`SONY 1 and SONY 2. While SONY2is capable of providing some overcharge
`
`protection in lithium cobalt cells, a significant capacity penalty is incurred due to an
`
`7
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`inability to fully charge the cells before the onset potential is reached. Similar limitations
`would apply to their use in lithium manganese oxide or lithium nickel oxide cells.
`Seven additives of the present invention (LBNL 1 —7 in TableII, with molecular
`
`structures shown below)are also includedin the onsetpotential graph of Fig. 3. LBNL 1
`
`and LBNL2 differ from additives described in U.S. Patent 5,763,119 in being difluoro-
`
`substituted dimethoxybenzenes rather than monohalo-compounds. LBNL3 is also a
`
`dimethoxybenzene,but it contains no halogen, havinganitrile group in a position para to
`
`amethoxy- group. LBNL 4 - 7 are 4-substituted 1,2-(methylenedioxy)benzenes. The
`
`structures of LBNL 8 — 17 are also shown below. The LBNL additives have redox shuttle
`
`onset potentials of about 4.25 V or higher. Lithium manganese oxidecells containing
`
`these additives can be charged to their full normal capacity at 4.2 V. Thesecells are
`
`protected from overcharging and maintain their original discharge capacities for at least
`
`five cycles under conditions of severe overcharging (50% greater charge capacity than
`p.
`
`normal).
`
`OCH;
`
`OCH3
`
`OCH3
`
`F
`
`F
`
`F
`
`OCH;
`
`LBNL 1
`
`LBNL 2
`
`OCH;
`
`OCH;
`
`C|N
`
`LBNL 3
`
`7
`
`8
`
`

`

`wo 01 [29920
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`PCT/US00/28975
`
`rN,
`
`r\,
`
`OT"\
`
`rN
`
`Cl
`
`Br
`
`NO»
`
`C
`
`IN
`
`LBNL 4
`
`LBNL 5
`
`LBNL 6
`
`LBNL 7
`
`crs
`
`on
`
`NO°
`
`LBNL 8
`
`OCH3
`
`OCHs
`
`OCH;
`
`i
`N
`
`LBNL 9
`
`FOF
`
`OCHs
`
`F
`
`F
`
`F
`
`F
`
`FOF
`
`LBNL 10
`
`C
`[
`N
`
`LBNL11
`
`9
`
`

`

`WO 01/29920
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`PCT/US00/28975
`
`OCH,
`
`OCH3
`
`OCH,
`
`OCH3
`
`C|
`
`OCH3
`
`Ww
`
`Cl
`
`lN
`
`LBNL 12
`
`LBNL 13
`
`OCH3
`
`OCH3
`
`OCH3.
`
`OCH3
`
`OCH;
`
`OCH3
`
`LBNL 14
`
`LBNL 15
`
`OCH3
`
`OCH3
`
`F
`
`F
`
`F
`
`F
`
`F
`
`F
`
`r
`
`LBNL 16
`
`LBNL 17
`
`10
`
`10
`
`

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`WO 01/29920
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`The onset potentials of seventeen shutdown/redox shuttle additives (LBNL 1 — 17
`in Table II) are shown in Fig. 4.
`
`The additives of the invention fall within the general subgroups of Categories A —
`
`E, with certain exclusions, and are more specifically identified as follows.
`
`Category A includes halogenated benzenes without any methoxy groups(it also
`
`can include halogenated benzenes with methoxy groups, but these will be discussed under
`
`category B). The halogenated benzenesinclude benzenes with only halogen substituents,
`
`such as trifluorobenzene andtetrafluorobenzene; there are preferably at least three
`
`halogen substituents. Various isomers of the tri- and tetra- fluorobenzenesare included
`
`in Tables I and II (SD 6, LBNL 19, LBNL 20; SD 7, LBNL 18, LBNL 21). The structures
`
`of these compoundsare as follows:
`
`ms
`
`F
`
`F
`
`
`
`Sh[ )Le
`
`NZ
`
`FoF
`
`Also included in Category A are halogenated naphthalenes, such as
`
`octafluoronaphthalene (LBNL10).
`
`The halogenated benzenescan also include benzenes with halogens and other
`
`(non-methoxy) substituents, suchas trifluorobenzonitrile (LBNL 22-24), which have the
`
`following structure where X is another substituent, e.g. nitrile:
`
`wt
`
`e 1
`
`1
`
`11
`
`

`

`WO 01/29920
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`PCT/US00/28975
`
`Category B includes substituted methoxybenzenes with no halogens. There are
`again preferably at least three substituents. These additives include benzenes with only
`methoxy groups, such as trimethoxybenzene (SD 2, LBNL 14-15), and benzenes with
`methoxy groupsand other (non-halogen) substituents, such as dimethoxybenzonitrile (SD
`10, LBNL 3, LBNL 11-12), dimethoxynitrobenzene (LBNL8), trimethoxybenzonitrile
`
`(LBNL 9, LBNL 13), and the related compound dimethoxybenzoquinone (SD 9). The
`
`structures of these compoundsare as follows, where X is a (non-halogen) substituent such
`
`as nitro- ornitrile group:
`
`OCH;
`OCHS
`y ZA
`
`OCH.
`xh
`UA OCH3
`
`ocH,—L “|
`
`X
`
`X
`
`OCH;
`
`O
`
`O
`
`OCH;
`
`2,6-dimethoxy-1,4-benzoquinone
`
`CategoryBalso includes substituted methoxybenzenes with halogens (which
`
`overlaps with Category A since they would also be halogenated benzenes). However,this
`
`group of halogenated methoxybenzene additives excludes dimethoxybenzenes with a
`
`12
`
`12
`
`

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`WO 01/29920
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`PCT/US00/28975
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`single halogen substituent (which are shown in U.S. Patent 5,763,119). This group of
`
`additives does include halogenated anisoles (benzenes with a single methoxy group), such
`
`as difluoroanisole (SD 1, LBNL 16) and pentafluoroanisole (LBNL 17), and also includes
`
`dimethoxybenzenes with at least two halogen substituents, such as the previously
`
`described difluorodimethoxybenzenes (LBNL 1-2). The structure of a halogenated
`
`anisole is as follows:
`
`OCH3
`
`a.™~
`FT ]ZX
`
`F
`
`Category C is the substituted benzodioxoles or methylenedioxybenzenes,
`
`illustrated below, where X is a substituent. These include both halogenated compounds
`
`(LBNL5-6) and nonhalogenated compounds (LBNL 4, LBNL 7) shown above.
`
`o\
`O
`
`AA
`
`X
`
`Category D is alkyl! polyethers, such as methoxyethyl ether (SD 3) andtri- or tetra-
`
`(ethylene glycol) dimethyl ether (SD 4-5), illustrated below.
`
`13
`
`13
`
`

`

`WO 01/29920
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`2-methoxyethyl ether
`
`tri(ethylene glycol) dimethyel ether
`
`O
`
`O
`
`O
`
`O
`
`O
`
`tetra(ethylene glycol) dimethyel ether
`
`Category E is substituted nitrogen-containing heterocycles, such as
`trimethoxypyrimidine (SD 8),illustrated below along with generic substituted
`
`pyrimidines (X, Y, Z can be hydrogen).
`
`OCH
`
`oy
`AAcen,
`
`OCH3
`
`2,4,6-trimethoxypyrimidine
`
`xX
`
`Xx
`
`N~ SN
`Loe
`
`Xx
`
`aa
`bod YA Mex
`
`N
`
`Y
`
`Y
`
`14
`
`

`

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`The amount of additive can vary widely. The minimum is probably about | % by
`weight. The maximum can be very high. The additive could replace all of the solvent in
`some cases, though this might be prohibitively expensive. Typically, 1 molar solutions
`have been usedfor testing in complete cells. This is because the electrolyte is 1 molar Li
`salt, and is therefore depleted of Li whenall of the addditve is in the oxidized form.
`Adjustments (increases) to the Lisalt concentration would probably be made in designing
`a cell that would incorporate a large amountof additive.
`Changes and modificationsin the specifically described embodiments can be
`carried out without departing from the scopeofthe invention whichis intended to be
`limited only by the scope of the appendedclaims.
`
`15
`
`15
`
`

`

`WO 01/29920
`
`PCT/US00/28975
`
`Claims
`
`1. A battery or electrochemical storage cell, comprising a positive electrode, a
`negative electrode, an electrolyte between the positive and negative electrodes, and a
`
`shutdown additive in the electrolyte, wherein the shutdown additive is selected from:
`
`A. halogenated benzenes, without additional substituents, and with additional
`
`substituents but excluding methoxy substituents, and halogenated naphthalenes,
`B. substituted methoxybenzenes, without additional substituents, and with
`
`additional substituents, including halogens, but excluding monohalodimethoxybenzenes,
`
`C. substituted benzodioxoles,
`
`D. alkyl polyethers,
`
`E. substituted nitrogen containing heterocycles.
`
`2. The battery or cell of Claim 1 wherein the additive is a halogenated benzene
`
`without additional substituents, a halogenated benzene with additional substituents but
`
`excluding methoxy substituents, or a halogenated naphthalene.
`
`3. The battery or cell of Claim 2 wherein the additive is selected from
`
`trifluorobenzene,tetrafluorobenzene,trifluorobenzonitrile, and octafluoronaphthalene.
`
`4. The battery or cell of Claim 1 wherein the additive is a substituted
`
`methoxybenzene without additional substituents, a substituted methoxybenzene with
`
`additional substituents excluding halogens, or a substituted methoxybenzene with
`
`additional halogen substituents but excluding monohalodimethoxybenzenes.
`
`5. The battery or cell of Claim 4 wherein the additive is selected from
`
`trimethoxybenzene, dimethoxybenzonitrile, trimethoxybenzonitrile,
`
`dimethoxynitrobenzene,difluoroanisole, pentafluoroanisole, and
`
`difluorodimethoxybenzene.
`
`16
`
`16
`
`

`

`WO 01/29920
`
`PCT/US00/28975
`
`6. The battery or cell of Claim 1 wherein the additive is a substituted
`
`benzodioxole.
`
`7. The battery or cell of Claim 1 wherein the additive is an alkyl polyether.
`
`8. The battery or cell of Claim 1 wherein the additive is a substituted nitrogen
`
`containing heterocycle.
`
`9. The battery or cell of Claim 1 wherein the electrolyte is a solid polymer.
`
`10. The battery or cell of claim 1 wherein the battery or cell is a lithium battery or
`
`cell.
`
`11. The battery or cell of Claim 10 wherein the battery or cell is a 4 V lithium
`
`battery or cell.
`
`12. A method of preventing overcharging of a battery or electrochemical storage
`
`cell, comprising providing a shutdown additive in the electrolyte of the battery orcell,
`
`wherein the shutdown additive is selected from: A. halogenated benzenes, without
`
`additional substituents, and with additional substituents but excluding methoxy
`
`substituents, and halogenated naphthalenes, B. substituted methoxybenzenes, without
`
`additional substituents, and with additional substituents, including halogens, but
`
`excluding monohalodimethoxybenzenes, C. substituted benzodioxoles, D.alkyl
`
`polyethers, E. substituted nitrogen containing heterocycles.
`
`13. An electrolyte with additive composition for a battery or electrochemical
`
`storage cell, comprising an electrolyte and a shutdown additive in the electrolyte, wherein
`
`the shutdown additive is selected from: A. halogenated benzenes, without additional
`
`substituents, and with additional substituents but excluding methoxy substituents, and
`
`halogenated naphthalenes, B. substituted methoxybenzenes, without additional
`
`17
`
`17
`
`

`

`WO 01/29920
`
`PCT/US00/28975
`
`substituents, and with additional substituents, including halogens, but excluding
`
`monohalodimethoxybenzenes, C. substituted benzodioxoles, D. alkyl polyethers, E.
`
`substituted nitrogen containing heterocycles.
`
`14. The composition of Claim 13 wherein the electrolyte is a solid polymer.
`
`15. The composition of Claim 13 wherein the shutdown additive is selected from
`
`the additives listed in Tables I andII.
`
`18
`
`18
`
`

`

`WO 01/29920
`
`PCT/US00/28975
`
`+PIEEENISSSSS/
`
`
`
`[ARRooh
`LLLLLLLLLD
`
`99s
`
`FIG. 1
`
`
`
`3.0
`
`3.5
`
`5.0
`4.5
`4.0
`Anode Potential vs Li/Li’ (V)
`
`5.5
`
`6.0
`
`FIG. 2
`
`19
`
`19
`
`
`
`

`

`WO 01/29920
`
`PCT/US00/28975
`
`300
`
`250
`
`200
`
`150
`
`100
`
`
`
`Current(nA)
`
`300
`
`250
`
`200
`
`150
`
`100
`
`
`
`Current(nA)
`
`50
`50
`
`4.0
`
`4.5
`
`AnodePotentialvs Li/Li*
`
`5.0
`
`FIG 3
`
`3.5
`
`4.0
`
`4.5
`
`§.0
`
`5.5
`
`6.0
`
`Anode Potential vs Li/Li
`
`FIG.4
`
`20
`
`20
`
`

`

`INTERNATIONAL SEARCH REPORT
`
`International application No.
`
`PCT/US00/28975
`
`CLASSIFICATION OF SUBJECT MATTER
`A.
`IPC(7)
`HOIM 6/18, 10/40
`US CL
`429/307, 231.95 , 252/62.2
`According to International Patent Classification (IPC) or to both national classification and IPC
`B.
`FIELDS SEARCHED
`
`Minimum documentation searched (classification system followed by classification symbols)
`U.S.
`: 429/307, 231.95 ; 252/62.2
`
`Documentation searched other than minimum documentation to the extent that such documentsare includedin the fields searched
`
`Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)
`Please See Continuation Sheet
`
`DOCUMENTS CONSIDERED TO BE RELEVANT
`Citation of document, with indication, where appropriate, of the relevant passages
`
`Relevant to claim No.
`
`25-40, column 5, lines 31-40, column 6, lines 6-11, column 7, lines 49-66 and abstract.
`
`US 6,045,952 A (KERRetal) 04 April 2000 (04.04.2000), column 2, lines 24-30,
`column 4, lines 65-67, and abstract.
`
`1-2, 9-11
`
`US 4,801,359 A (JEANNEet al) 31 January 1989 (31.01.1989), column 22, lines 47-50.
`
`US 5,789,585 A (LEEetal) 04 August 1998 (04.08.1998), column 4, lines 12-19, column
`5, line 64 to column 6, line 56.
`
`13-14
`1, 7, 10, 12-13
`
`[| Further documents are listed in the continuation of Box C.
`*
`Special categories of cited documents:
`
`UI
`“T”
`
`document defining the general state of the art which is not considered to be
`ofparticular relevance
`
`earlier application or patent published on or after the imtermationa!filing date
`
`document which may throw doubts on priority claim(s) or which is cited to
`establish the publication date of another citation or other special reason (as
`specified)
`
`documentreferring to an oral disclosure, use, exhibition or olher means
`
`“x”
`
`“y"
`
`See patent family annex.
`later document published after the internationalfiling date or priority
`date and not in conflic! with the application but cited 10 understand the
`principle or theory underlying the invention
`document of particular relevance: the claimed invention cannot be
`considered novel or cannot be considered to invoive an inventive step
`when the documentis taken alone
`
`documentof particular relevance; the claimed invention cannot be
`considered to involve an inventive step when the documentis
`combined with one or more other such documents, such combination
`being obvious to a person skilled in the art
`
`document published prior to the internationalfiting date but later than the
`priority date claimed
`
`“&”
`
`document member of the same patent! family
`
`“A”
`
`“E”
`
`“L”
`
`“O”
`
`“p”
`
`
`
`
` US 6,004,698 A (RICHARDSONet al) 21 December 1999 (21.12.1999), column 4, lines|1-2, 9-10, 12-14
`
`
`Date of the actual completion of the international search
`
`28 December 2000 (28.12.2000)
`Name and mailing address of the [SA/US
`Commissioner of Patents and Trademarks
`Box PCT
`Washington. D.C.
`Facsimile No. (703)305-3230
`
`20231
`
`Form PCT/ISA/210 (second sheet) (July 1998)
`
`21
`
`Date ofm4 ofthe international search report
`8 JAN 2001
`8
`Authorized officer
`ay
`Jean Proctor
`Paralegal Specialist
`
`Laura S Weiner
`
`Telephone No. 703-308-0661
`
`21
`
`

`

`INTERNATIONAL SEARCH REPORT
`
`International application No.
`
`PCT/US00/28975
`
`Box I Observations where certain claims were found unsearchable (Continuation of Item 1 offirst sheet)
`
`This international report has not been established in respect of certain claims under Article 17(2)(a) for the following reasons:
`
`Claim Nos.:
`because they relate to subject matter not required to be searched by this Authority, namely:
`
`Claim Nos.:
`15
`becausethey relate to parts of the international application that do not comply with the prescribed requirements to
`such an extent that no meaningful international search can becarried out, specifically:
`Claim 15 has the phrase "selected from additives listed in Tables I and II". These additives needto be listed in the
`claim.
`
`Claim Nos.:
`
`Box II Observations where unity of invention is lacking (Continuation of Item 2 offirst sheet)
`
`This International Searching Authority found multiple inventionsin this international application, as follows:
`
`because they are dependentclaims andare not drafted in accordance with the second andthird sentences of Rule
`
`
`HOU
`
`As all required additional search fees were timely paid by the applicant, this international search report coversall
`searchable claims.
`
`As all searchable claims could be searched withouteffort justifying an additional fee, this Authority did not invite
`payment of any additionalfee.
`
`As only someofthe required additional search fees were timely paid by the applicant, this international search
`report covers only those claims for which fees were paid, specifically claims Nos.:
`
`4. [|
`
`No required additional search fees were Limely paid by the applicant. Consequently, this international search report
`is restricted to the inventionfirst mentioned in the claims; it is covered by claims Nos.:
`
`Remark on Protest[] The additional search fees were accompanied by the applicant’s protest.
`[|
`No protest accompanied the paymentof additional search fees.
`
`Form PCT/ISA/210 (continuation offirst sheet(1)) (July 1998)
`
`22
`
`22
`
`

`

`INTERNATIONAL SEARCH REPORT
`
`International application No.
`
`PCT/US00/28975
`
`Continuation of B. FIELDS SEARCHEDItem 3: EAST
`search terms: additive, redox shuttle, overcharge protection, solid polymerelectrolyte,benzene, methoxybenzene, benzodioxole,
`electrolyte, overcharging, battery, cell
`
`
`
`Form PCT/ISA/210 (extra sheet) (July 1998)
`
`23
`
`23
`
`