WO2004100294A1 - High performance and safer electrolytes for lithium-ion electrochemical devices - Google Patents

High performance and safer electrolytes for lithium-ion electrochemical devices Download PDF

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Publication number
WO2004100294A1
WO2004100294A1 PCT/US2003/012096 US0312096W WO2004100294A1 WO 2004100294 A1 WO2004100294 A1 WO 2004100294A1 US 0312096 W US0312096 W US 0312096W WO 2004100294 A1 WO2004100294 A1 WO 2004100294A1
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WIPO (PCT)
Prior art keywords
lithium
fire resistant
libf
electrochemical devices
electrolytes
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PCT/US2003/012096
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French (fr)
Inventor
Joseph B. Kejha
Joel R. Mccloskey
W. Novis Smith
Original Assignee
Kejha Joseph B
Mccloskey Joel R
Smith W Novis
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kejha Joseph B, Mccloskey Joel R, Smith W Novis filed Critical Kejha Joseph B
Priority to US10/552,114 priority Critical patent/US20060204857A1/en
Priority to PCT/US2003/012096 priority patent/WO2004100294A1/en
Publication of WO2004100294A1 publication Critical patent/WO2004100294A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to fire resistant stable electrolytes for lithium-iori devices which have a low percent of high boiling point solvents in combination with ethylene carbonate and a high molar salt concentration. These electrolytes have similar performance characteristics as existing highly flammable electrolytes, and have a wider operating temperature span.
  • Prior art electrolytes that have high ionic conductivity are very flammable due to the inclusion of low boiling point flammable solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and dimethoxyethane (DME), or they have a low ionic cond ⁇ ctivity due to the inclusion of high boiling point non-flammable glycol ethers, o they have a high percent (40% or more) of propylene carbonate (PC) or garnma-butyrolactone (GBL), which makes them non-competitive in performance in lithium-ion batteries with graphitic anodes, where the PC or GBL reacts with the anode, and causes a very high irreversible capacity loss, and a sharp decline in capacity during cycling. Examples of such prior art high boiling point electrolytes are described in the following patents and publications:
  • Electrolyte published in the Journal of the Electrochemical Society, 149(1) A9- A12 (2002) describes a fire resistant electrolyte 1.5M LiBF ⁇ C/GBL 75% or 1:3 ratio, which has a shorter cycle life and a higher capacity decline than flammable electrolytes.
  • GBL or BC in combination with a polymer. This electrolyte is immobilized by a polymer.
  • the principal object of the invention is to provide electrolytes for lithium-ion electrochemical devices that have good ionic conductivity and are fire resistant.
  • a further object of the invention is to provide electrolytes of the character aforesaid, which provide improved cycling stability for the electrochemical devices in which they are incorporated.
  • a further object of the invention is to provide electrolytes of the character aforesaid which are useful in a variety of electrochemical devices, such as automotive and military batteries, and capacitors.
  • a further object of the invention is to provide electrolytes of the character aforesaid which are particularly suitable for mass production.
  • FIG. 1 is a graph of voltage versus time of a prior art flammable electrolyte in a lithium-ion electrochemical device having the composition IM LiPF 6 /EC/DMC/EMC(l : 1:1);
  • FIG. 1 A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 1 ;
  • FIG. 2 is a graph of voltage versus time of an identical electrochemical device as in FIG. 1, incorporating an electrolyte of the invention of the composition 2M LiBF 4 EC/GBL 20%;
  • FIG. 2A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 2;
  • FIG. 3 is a graph of voltage versus time of prior art fire resistant electrolyte in an identical electrochemical device as in FIG. 1, having therein the composition 1.5MLiBF 4 EC/GBL 75%;
  • FIG. 3A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 3;
  • FIG. 4 is a graph of voltage versus time of an identical electrochemical device as in FIG. 1, incorporating an electrolyte of the invention of the composition 1.5M LiBF 4 EC/PC 20%;
  • FIG. 4 A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 4;
  • FIG. 5 is a graph of voltage versus time of a prior art fire resistant electrolyte in an identical electrochemical device as in FIG. 1, having the composition IM LiBF 4 EC/PC 50%;
  • FIG 6 is a chart of the conductivity of the electrolytes of FIGS. 2 and 2A, for a temperature span of- 25° C to 70° C, and
  • FIG. 7 is a chart of the conductivity of the electrolytes of FIGS. 4 and 4A, for a temperature span of- 25° C to 70° C. It should, of course, be understood that the description and drawings herein are merely illustrative and that various modifications and changes can be made in the compositions disclosed without departing from the spirit of the invention.
  • An electrochemical device of the lithium-ion variety such as a lithium-ion cell (not shown) typically includes an anode, and a current collector in contact with the anode, a cathode and current collector in contact with the cathode, a separator and an electrolyte in contact with the anode and cathode, with the whole assembly contained in a moisture proof enclosure with exiting sealed terminals.
  • FIGS. 1 and 1 A the results obtained with a prior art electrolyte in a lithium-ion electrochemical device are illustrated, where the composition of the electrolyte is lM LiPF 6 /EC/DMC/EMC(l:l:l), and while it provides good performance the composition is highly flammable. Referring to FIGS.
  • FIGS. 3 and 3 A the results obtained with a prior art fire resistant electrolyte electrochemical device are illustrated.
  • FIGS. 3, 3 A The composition of FIGS. 3, 3 A was 1.5M LiBF 4 /EC/GBL 75% in a lithium-ion cell, with mesocarbon microbeads (MCMB), or boron coated graphite fiber anodes.
  • MCMB mesocarbon microbeads
  • FIGS. 2 and 2 A show that the composition of the invention (FIGS.2 & 2A) outperformed the prior art electrolyte (FIGS. 3, 3A)in less capacity decline at C/2 rate.
  • FIGS. 4, 4 A the results obtained with another electrolyte composition prepared in accordance with the invention in a lithium-ion electrochemical device are illustrated.
  • the described fire resistant electrolytes have very close performance (rate and cycle life) to the existing described flammable electrolytes of FIGS. 1 and 1 A, and are useable in lithium-ion and lithium-ion-polymer rechargeable batteries, and pseudocapacitors with graphitic, or other carbon anodes.
  • the high boiling point solvent EC carries most of the ionic conductivity load, and is stable with the carbon anode, while the low percentage of high boiling point GBL or PC or BC keeps the EC in a liquid state, especially at low temperatures.
  • the relatively high viscosity and thus lower conductivity of their mixtures, as well as the lower conductivity of the LiBF salt can be overcome by the higher molar content of the salt, which creates more of the necessary ionic bridges. Hence the ability to use 1.5M to 2M.
  • Prior art IM LiBF 4 is not good enough in these viscous electrolytes.
  • the LiBF 4 salt also has a low molecular weight as opposed to LiPF 6 , or other known salts which makes 1.5 to 3M or more loading in the electrolyte possible, and which also helps to maintain the liquid state of the EC, even at low temperatures.
  • EC and LiBF 4 form a eutectic solution in this range.
  • the LiBF salt is temperature resistant and less sensitive to moisture, which are additional benefits of the electrolytes of the invention.
  • the above high boiling point liquids with LiBF 4 salt make the electrolytes fire resistant under normal atmospheric (air) conditions, and temperatures created by ignition with a match, or electrical spark, for example, which makes them safer in military and automotive applications.
  • the useful range of LiBF is 1.5M to 3M.
  • the useful range of GBL, or PC, or BC is 10% to 30% by weight percent, and preferably 15% to 25% and more preferably approximately 20%.
  • Operating temperature of the above electrolytes is from (-) 20 °C to (+) 150 °C, and conductivities from 0.9mS to 10.4 mS (at 70°c) as shown in FIGS. 6 & 7. Similar mixtures as described above, but with IM to 2.0 M LiPF 6 salt or other salts are useful, but less satisfactory.
  • LiBF 4 and LiPF 6 or other salts in the range of 0.5M to 1.5M each, are useful.
  • the above electrolytes are particularly useful with zero irreversible capacity loss cathodes, as described in our prior Pat. Appl. #PCT/US02/36878, which is incorporated herein by reference.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Secondary Cells (AREA)

Abstract

Fire resistant stable electrolytes for use in lithium-ion based electrochemical devices, which include lithium salts in high molar concentration with various solvents, such as ethylene carbonate, and with a low % of butylene carbonate or propylene carbonate or gamma butyrolactone, and which devices may include a cathode with a lithium compound additive, and a graphitic anode.

Description

HIGH PERFORMANCE AND SAFER ELECTROLYTES FOR LITHIUM-ION ELECTROCHEMICAL DEVICES
BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
This invention relates to fire resistant stable electrolytes for lithium-iori devices which have a low percent of high boiling point solvents in combination with ethylene carbonate and a high molar salt concentration. These electrolytes have similar performance characteristics as existing highly flammable electrolytes, and have a wider operating temperature span.
DESCRIPTION OF THE PRIOR ART
Prior art electrolytes that have high ionic conductivity (=high rate capability) are very flammable due to the inclusion of low boiling point flammable solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and dimethoxyethane (DME), or they have a low ionic condμctivity due to the inclusion of high boiling point non-flammable glycol ethers, o they have a high percent (40% or more) of propylene carbonate (PC) or garnma-butyrolactone (GBL), which makes them non-competitive in performance in lithium-ion batteries with graphitic anodes, where the PC or GBL reacts with the anode, and causes a very high irreversible capacity loss, and a sharp decline in capacity during cycling. Examples of such prior art high boiling point electrolytes are described in the following patents and publications:
The article entitled "Polyacrylonitrile Electrolyte Based Li-ion Batteries" published in Electrochenical Acta (1998), 43 (16-17), 2399 - 2412 describes fire resistant polyacrylonitrile (pan) based electrolytes such as IM LiPF6/EC/PC 50%, however this electrolyte does not have equal conductivity with flammable electrolytes and is in combination with a polymer.
The article entitled "PeoLike Polymer Electrolytes With High Room- Temperature Conductivity" published in the Journal of the Electrochemical society (1997), 144(6), Li36-Li38 describes fire resistant electrolytes such as IM LiPF6 PEGDME, however, this electrolyte is less conductive than flammable electrolytes.
The US Patent No. 5,252,3413 of Alamgir et al. entitled "Solid Polymer Electrolyte Lithium Batteries" describes a fire resistant electrolyte IM LiCLCO4/EC PC 50% however it has less conductivity than flammable electrolytes and is in combination with a polymer. The article entitled "Laminated Thjn Li-ion Batteries Using a Liquid
Electrolyte" published in the Journal of the Electrochemical Society, 149(1) A9- A12 (2002) describes a fire resistant electrolyte 1.5M LiBF^C/GBL 75% or 1:3 ratio, which has a shorter cycle life and a higher capacity decline than flammable electrolytes.
The U.S. Patent No. 6,280,881 of Wendsjo et al. entitled "Lithium
Secondary Battery" describes a fire resistant electrolyte IM LiBF4/EC/PC in a 1:1 or 50/50 ratio. This electrolyte does not have the narrow ratio range of EC, PC, or
GBL or BC in combination with a polymer. This electrolyte is immobilized by a polymer.
Most of the prior art fire resistant electrolytes described above are one molar in lithium salt concentration, and they are in combination with a polymer. It should be noted, that although the individual salts or high boiling point liquids are known, what is not known is the optimum narrow ratio of solvents in combination with the molar content of the salts in the mixtures necessary to achieve an equivalent performance to liquid flammable (lower boiling point) electrolytes in lithium-ion, or lithium-ion-polymer batteries with graphitic anodes. The combinations described produce fire resistant electrolytes (due to their high flash points and boiling points) that are useful in lithium-ion electrochemical devices, and provide many positive advantages over equivalent flammable electrolytes.
SUMMARY OF THE INVENTION It has now been found that safe fire resistant electrolytes for lithium-ion batteries are available, which electrolytes have high conductivity, minimal reactivity and good cycle life, and which can be made by using a lower percent of the high boiling solvent gamma-butyrolactone (GBL) in combination with ethylene carbonate (EC), and a high molar concentration (M) of the salt, such as 2M of lithium tetrafluoroborate (LiBF4) salt, or a low percent of high boiling point solvents, such as propylene carbonate (PC) or butylene carbonate (BC) in combination with ethylene carbonate (EC), and a high molar concentration, such as 1.5M to 2M of lithium tetrafluoroborate salt, or their mixtures.
The principal object of the invention is to provide electrolytes for lithium-ion electrochemical devices that have good ionic conductivity and are fire resistant. A further object of the invention is to provide electrolytes of the character aforesaid, which provide improved cycling stability for the electrochemical devices in which they are incorporated.
A further object of the invention is to provide electrolytes of the character aforesaid which are useful in a variety of electrochemical devices, such as automotive and military batteries, and capacitors.
A further object of the invention is to provide electrolytes of the character aforesaid which are particularly suitable for mass production.
Other objects and advantageous features of the invention will be apparent from the description and claims. DESCRIPTION OF THE DRAWINGS
The nature and characteristic features of the invention will be more readily understood from the following description taken in connection with the accompanying drawings forming part hereof in which: FIG. 1 is a graph of voltage versus time of a prior art flammable electrolyte in a lithium-ion electrochemical device having the composition IM LiPF6/EC/DMC/EMC(l : 1:1);
FIG. 1 A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 1 ;
FIG. 2 is a graph of voltage versus time of an identical electrochemical device as in FIG. 1, incorporating an electrolyte of the invention of the composition 2M LiBF4 EC/GBL 20%;
FIG. 2A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 2;
FIG. 3 is a graph of voltage versus time of prior art fire resistant electrolyte in an identical electrochemical device as in FIG. 1, having therein the composition 1.5MLiBF4 EC/GBL 75%;
FIG. 3A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 3;
FIG. 4 is a graph of voltage versus time of an identical electrochemical device as in FIG. 1, incorporating an electrolyte of the invention of the composition 1.5M LiBF4 EC/PC 20%;
FIG. 4 A is a graph illustrating capacity versus cycles of the device with the electrolyte therein of FIG. 4;
FIG. 5 is a graph of voltage versus time of a prior art fire resistant electrolyte in an identical electrochemical device as in FIG. 1, having the composition IM LiBF4 EC/PC 50%; FIG 6 is a chart of the conductivity of the electrolytes of FIGS. 2 and 2A, for a temperature span of- 25° C to 70° C, and
FIG. 7 is a chart of the conductivity of the electrolytes of FIGS. 4 and 4A, for a temperature span of- 25° C to 70° C. It should, of course, be understood that the description and drawings herein are merely illustrative and that various modifications and changes can be made in the compositions disclosed without departing from the spirit of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS When referring to the preferred embodiments, certain terminology will be utilized for the sake of clarity. Use of such terminology is intended to encompass not only the described embodiments, but also technical equivalents which operate and function in substantially the same way to bring about the same result.
An electrochemical device of the lithium-ion variety, such as a lithium-ion cell (not shown) typically includes an anode, and a current collector in contact with the anode, a cathode and current collector in contact with the cathode, a separator and an electrolyte in contact with the anode and cathode, with the whole assembly contained in a moisture proof enclosure with exiting sealed terminals. Referring to FIGS. 1 and 1 A, the results obtained with a prior art electrolyte in a lithium-ion electrochemical device are illustrated, where the composition of the electrolyte is lM LiPF6/EC/DMC/EMC(l:l:l), and while it provides good performance the composition is highly flammable. Referring to FIGS. 2 and 2 A results are illustrated which were obtained with an electrolyte prepared in accordance with the invention, in a lithium-ion electrochemical device, with mesocarbon microbeads (MCMB) or boron coated graphite fiber anodes. The electrolyte of the invention contained 2M LiBF salt in an EC/GBL
20% mixture (or 4:1 ratio) and provided similar performance as the prior art electrolyte of FIGS. 1, 1A in rate capability, and cycle life, as well as capacity decline at C/2 rate.
Referring to FIGS. 3 and 3 A the results obtained with a prior art fire resistant electrolyte electrochemical device are illustrated.
The composition of FIGS. 3, 3 A was 1.5M LiBF4/EC/GBL 75% in a lithium-ion cell, with mesocarbon microbeads (MCMB), or boron coated graphite fiber anodes. The results obtained when compared to FIGS. 2 and 2 A show that the composition of the invention (FIGS.2 & 2A) outperformed the prior art electrolyte (FIGS. 3, 3A)in less capacity decline at C/2 rate.
Referring to FIGS. 4, 4 A the results obtained with another electrolyte composition prepared in accordance with the invention in a lithium-ion electrochemical device are illustrated.
The composition of FIGS. 4, 4A was 1.5 M LiBF4 in EC/PC 20%, (or 4:1 ratio) in a lithium-ion electrochemical device with MCMB anode, and the results compared to the prior art electrolyte of FIG. 5, illustrated that it outperformed the prior art electrolyte composition of IM LiBF4/EC PC 50% in cycle life, and in C/2 rate capability. (Flat tops of the peaks in the graph indicate high resistance=low conductivity). Both lithium-ion cells are identical and have MCMB anodes.
The described fire resistant electrolytes have very close performance (rate and cycle life) to the existing described flammable electrolytes of FIGS. 1 and 1 A, and are useable in lithium-ion and lithium-ion-polymer rechargeable batteries, and pseudocapacitors with graphitic, or other carbon anodes.
It has also been discovered that the high boiling point solvent EC carries most of the ionic conductivity load, and is stable with the carbon anode, while the low percentage of high boiling point GBL or PC or BC keeps the EC in a liquid state, especially at low temperatures. The relatively high viscosity and thus lower conductivity of their mixtures, as well as the lower conductivity of the LiBF salt can be overcome by the higher molar content of the salt, which creates more of the necessary ionic bridges. Hence the ability to use 1.5M to 2M. Prior art IM LiBF4 is not good enough in these viscous electrolytes. The LiBF4 salt also has a low molecular weight as opposed to LiPF6, or other known salts which makes 1.5 to 3M or more loading in the electrolyte possible, and which also helps to maintain the liquid state of the EC, even at low temperatures. We also have found that EC and LiBF4 form a eutectic solution in this range. The LiBF salt is temperature resistant and less sensitive to moisture, which are additional benefits of the electrolytes of the invention.
The above high boiling point liquids with LiBF4 salt make the electrolytes fire resistant under normal atmospheric (air) conditions, and temperatures created by ignition with a match, or electrical spark, for example, which makes them safer in military and automotive applications. The useful range of LiBF is 1.5M to 3M. The useful range of GBL, or PC, or BC is 10% to 30% by weight percent, and preferably 15% to 25% and more preferably approximately 20%. Operating temperature of the above electrolytes is from (-) 20 °C to (+) 150 °C, and conductivities from 0.9mS to 10.4 mS (at 70°c) as shown in FIGS. 6 & 7. Similar mixtures as described above, but with IM to 2.0 M LiPF6 salt or other salts are useful, but less satisfactory. Also a combination of LiBF4 and LiPF6 or other salts in the range of 0.5M to 1.5M each, are useful. The above electrolytes are particularly useful with zero irreversible capacity loss cathodes, as described in our prior Pat. Appl. #PCT/US02/36878, which is incorporated herein by reference.
It will thus be seen that electrolyte compositions have been provided with which the objects of the invention are achieved.

Claims

WE CLAIM:
1. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises:
LiBF4 salt in the range of 1.5 to 3.0 molar concentration in the mixture of ethylene carbonate in the range of 70 to 90% by weight percentage, and gamma-butyrolactone in the range of 10 to 30% by weight percentage.
2. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises:
LiBF4 salt in the range of 1.5 to 3.0 molar concentration in the mixture of ethylene carbonate in the range of 70 to 90% by weight percentage, and propylene carbonate in the range of 10 to 30% by weight percentage.
3. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises:
LiBF salt in the range of 1.5 to 3 molar concentration in the mixture of ethylene carbonate in the range of 70 to 90% by weight percentage, and butylene carbonate in the range of 10 to 30% by weight percentage.
4. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises: two molar LiBF salt concentration in the mixture of ethylene carbonate of 80% by weight percentage, and gamma-butyrolactone of 20% by weight percentage.
5. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises:
1.5 molar LiBF4 salt concentration in the mixture of ethylene carbonate of 80% by weight percentage, and propylene carbonate of 20% by weight percentage.
6. A fire resistant stable electrolyte composition for ϋthium-ion batteries and other lithium based electrochemical devices which comprises:
1.5 molar LiBF4 salt concentration in the mixture of ethylene carbonate of 80% by weight percentage, and butylene carbonate of 20% by weight percentage.
7. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises a mixture of electrolytes as described in claims 1, 2 and 3.
8. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises a mixture of electrolytes as described in claims 4y 5 and 6.
9. A fire resistant stable electrolyte composition as described in claims 1 to 8 inclusive for lithium-ion based electrochemical devices in which said LiBF4 salt is replaced by; at least one other lithium salt in the range of 1.0 to 2.0 molar concentration.
10. A fire resistant stable electrolyte composition for lithium-ion based electrochemical devices which comprises:
LiBF4 salt in the range of 1.5 to 3.0 molar concentration in approximately 100% ethylene carbonate.
11. A fire resistant stable electrolyte composition as described in claims 1-8 inclusive to which said LiBF4 salt has at least one other lithium salt added thereto in the range of 0.5 M to 1.5 M.
12. A fire resistant stable electrolyte as described in claims 1-11 inclusive, in combination with lithium-ion based based electrochemical devices, which have a cathode with a lithium compound additive.
PCT/US2003/012096 2003-04-17 2003-04-17 High performance and safer electrolytes for lithium-ion electrochemical devices WO2004100294A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5079109A (en) * 1989-05-16 1992-01-07 Kabushiki Kaisha Toshiba Nonaqueous electrolyte secondary battery
US5571635A (en) * 1994-04-15 1996-11-05 National Research Council Of Canada Electrolyte for a secondary cell
US5578395A (en) * 1994-03-08 1996-11-26 Sanyo Electric Co., Ltd. Lithium secondary battery
US6284412B1 (en) * 1995-11-15 2001-09-04 Asahi Kasei Kogyo Kabushiki Kaisha Hybrid polymeric electrolyte and non-aqueous electrochemical device comprising the same
US6346351B1 (en) * 1996-09-30 2002-02-12 Danionics A/S Lithium salt/carbonate electrolyte system, a method for the preparation thereof, the use thereof and a battery containing the electrolyte system
US6465134B1 (en) * 1999-02-19 2002-10-15 Sony Corporation Gel electrolyte and gel electrolyte battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5079109A (en) * 1989-05-16 1992-01-07 Kabushiki Kaisha Toshiba Nonaqueous electrolyte secondary battery
US5578395A (en) * 1994-03-08 1996-11-26 Sanyo Electric Co., Ltd. Lithium secondary battery
US5571635A (en) * 1994-04-15 1996-11-05 National Research Council Of Canada Electrolyte for a secondary cell
US6284412B1 (en) * 1995-11-15 2001-09-04 Asahi Kasei Kogyo Kabushiki Kaisha Hybrid polymeric electrolyte and non-aqueous electrochemical device comprising the same
US6346351B1 (en) * 1996-09-30 2002-02-12 Danionics A/S Lithium salt/carbonate electrolyte system, a method for the preparation thereof, the use thereof and a battery containing the electrolyte system
US6465134B1 (en) * 1999-02-19 2002-10-15 Sony Corporation Gel electrolyte and gel electrolyte battery

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