CA1306001C - Lithium electrochemical cell containing diethylcarbonate asan electrolyte solvent additive - Google Patents
Lithium electrochemical cell containing diethylcarbonate asan electrolyte solvent additiveInfo
- Publication number
- CA1306001C CA1306001C CA000599186A CA599186A CA1306001C CA 1306001 C CA1306001 C CA 1306001C CA 000599186 A CA000599186 A CA 000599186A CA 599186 A CA599186 A CA 599186A CA 1306001 C CA1306001 C CA 1306001C
- Authority
- CA
- Canada
- Prior art keywords
- lithium
- electrochemical cell
- diethylcarbonate
- electrolyte
- solution
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
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
- H01M10/0569—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
ABSTRACT
An electrochemical cell comprising lithium as the anode, the lithium intercalating compound Lix CoO2(0< x <1) as the cathode, and a solution of a lithium salt in a mixed organic solvent of methylformate and diethylcarbonate as the electrolyte.
An electrochemical cell comprising lithium as the anode, the lithium intercalating compound Lix CoO2(0< x <1) as the cathode, and a solution of a lithium salt in a mixed organic solvent of methylformate and diethylcarbonate as the electrolyte.
Description
~3~
This invention relates in general to a lithium electrochemical cell and in particular, to a lithium electro-chemical cell including lithium as the anode, the lithium intercalating compound L~ CoO~(0< x <l) as the cathode, and a solution.o~ a lithium salt in a mixed organic solvent o~ methyl ~ormate (MF) and diethylcarbonate (DEC) as the electrolyte.
The ~ubJect matt~r of this application l~ rel~ted to the 3ubiect matter o~ U.S. Patent No. 4,7B6,499 lssued on Z2 November, 1988 ~or "Lithium Electrochemical Cell Includlng AProtlc Solvent-~lalkyl Carbon~te SolYent Mixture" an~ a~ ned to a common a~slgnee. In that patent, there ls de~cribed and claimed a lithlum electrochemical cell lncluding lithium as the anode, non-~toichiometric (NS)-VbO~3 a~ the cathode, and a solution of a lithium salt in a mixed organic ~olvent of methyl formate and diethylcarbonate as the electrolyte.
Another lithium intercalating compound, to wit, Li~CoO~
(0< x <l~ is particularly attractive for battery applications.
because o~ its inherently high energy content. However, the known Li~CoO~ cathode material/solvent combinations are susceptible to oxidation during charge and reduction during discharge that results in losses in cell capacity and cycle~ e. In addition to oxidation and reduction o~ the electrolyte, both the cathode and anode are subject to reaction with the solvent and electrolyte.
This can result in poor lithium cyclability and structural rearrangement o~ the active material which may limit rechargeability.
,. ' ,, ~.3~
The general object of this invention is to provide an improved lithium alectrochemical cell including Li~CoO~(0< x <1) as the cathode active material. A more particular object of the invention is to provide an intercalating solvent system ~or L~ CoO~
(0< x <1) that produces higher energy lithium cell~ also charact~rized by increased resistance to solvent oxidation and improved lithium cycling efficiencies.
It has now been ~ound that the a~orementioned objects can be attained by employing a system including lithium as the anode, LixCoOa(O< x ~1) as the cathode, and a solution of a lithium salt in a mixed organic solvent Oe MF and DEC as the electrolyte.
The solution can be, ~or example, 1 to 2 mol dm s LiA~
in the mixed organic solvent. Though the use o~ LiAsF,~ as th~
electrolyte salt is pre~erred, other electrolyte salts can be used such as the soluble salts o~`light metals, for example, tetra~luoroborates, tetrachloroaluminates, perchlorates, hexa~luorophosphates, and halides o~ lithium.
The mass percent o~ the DEC in the mixed organic solvent can vary ~rom 10 to 100 mass percent. The instant invention identi~ies and demonstrates that the addition o~ DLC to ester containing electrolytes, such as LiAsF~ in MF, results in signi~icant improvements in the electrolytes resistance to electrochemical oxidation and improved lithium cycling efficiencies. In addition, when these electrolytes containing the DEC additives are used in Li/LixCoO~ electrochemical cells, there is signiEicant improvements in the cell cycling behavior over cells without the DEC additive.
~3~
The drawing compares cycling results obtained ~or additions o~ DEC and dimethylcarbonate (DMC) to LiAsF~ in MF
electrolyte in a Li/LixCoOl electrochemical cell.
The drawing shows the dramatic improvement in cycli~g behavior ~or the electrolyte containing DEC as opposed to DMC.
The Li/Li~CoO~ cells are cycled between either 4.3Vto 3.5V or 4.3V
to 2.5V where the charging rate is 0.5 mAcm~, the discharge rate is 2.0 mAcm~, and the temperature is 25~C. The LixCaO~ cathodes include a mixture o~ 80 weight percent Li~CoO~, 10 weight percent carbon diluent, and 10 weight percent Teflon binder. The cathode mixture is roll pressed onto aluminum substrate5 and sintered in a vacuum oven at 280~C ~or 1 hour. The cycling is per~ormed on identically prepared cells consisting o~ ~lag electrodes sealed in a glass pressure vessel where Celgard 2400 is used as separators and a glass ~iber wick ~or drawing electrolyte in between the electrode.
Interestingly, homologues o~ DEC such as DMC have been utilized in lithium cells and are known to be su~iciently stable towards lithium. However, although DMC and DEC show structural similarities, they behave very di~erently in the presence o~
lithium, both chemically and electrochemically. DMC produces a high cycling e~iciency o~ S0 percent as compared to DEC which is O percent. This is due to the reactive nature o~ DEC with lithium as opposed to the more stable DMC solvent. However, even though DMC is more stable with lithium, its addition to the LiAsF~-MF
electrolyte does not result in the improved results observed with DEC. ThereEore, where the success~ul use o~ DMC as a solvent in * denotes trade mark ~L3~ EiO~
lithium cells may imply the possible use oE a similar solvent such as DEC, this is not made obvious due to the lack o~ lithium stability o~ the neat DEC electrolyte, thus precluding such application~. Furthermore, one would not ~ind obvious tha discovery that a mixture o~ the unstable solvent DEC with ano~her solvent would produce an improved mixture suitably stable ~or use in a lithium cell. It is only through its addition to other ester electrolytes that the use o~ DEC in lithium cells is possible.
The use o~ DEC as a solvemt additive in electrolytes ~or use in either primary, rechargeable, or reserve electrochemical cells is not considered to be limited to the instance where lithium is the anode. That is, other light metals or composites may be applicable as the anode such as sodium, potassium and aluminum, or any conductively doped polymeric material or similar compound~ Moreover, the positive electrode or cathode, may be any oxide, sul~ide or combinations o~ titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ha~nium, tantalum, or tungsten or any conductively doped polymeric material or similar compound.
We wish it to be un~derstood that we do not desire to be limited to the exact details as described ~or obvious modi~ications will occur to a person skilled in the art~
!
This invention relates in general to a lithium electrochemical cell and in particular, to a lithium electro-chemical cell including lithium as the anode, the lithium intercalating compound L~ CoO~(0< x <l) as the cathode, and a solution.o~ a lithium salt in a mixed organic solvent o~ methyl ~ormate (MF) and diethylcarbonate (DEC) as the electrolyte.
The ~ubJect matt~r of this application l~ rel~ted to the 3ubiect matter o~ U.S. Patent No. 4,7B6,499 lssued on Z2 November, 1988 ~or "Lithium Electrochemical Cell Includlng AProtlc Solvent-~lalkyl Carbon~te SolYent Mixture" an~ a~ ned to a common a~slgnee. In that patent, there ls de~cribed and claimed a lithlum electrochemical cell lncluding lithium as the anode, non-~toichiometric (NS)-VbO~3 a~ the cathode, and a solution of a lithium salt in a mixed organic ~olvent of methyl formate and diethylcarbonate as the electrolyte.
Another lithium intercalating compound, to wit, Li~CoO~
(0< x <l~ is particularly attractive for battery applications.
because o~ its inherently high energy content. However, the known Li~CoO~ cathode material/solvent combinations are susceptible to oxidation during charge and reduction during discharge that results in losses in cell capacity and cycle~ e. In addition to oxidation and reduction o~ the electrolyte, both the cathode and anode are subject to reaction with the solvent and electrolyte.
This can result in poor lithium cyclability and structural rearrangement o~ the active material which may limit rechargeability.
,. ' ,, ~.3~
The general object of this invention is to provide an improved lithium alectrochemical cell including Li~CoO~(0< x <1) as the cathode active material. A more particular object of the invention is to provide an intercalating solvent system ~or L~ CoO~
(0< x <1) that produces higher energy lithium cell~ also charact~rized by increased resistance to solvent oxidation and improved lithium cycling efficiencies.
It has now been ~ound that the a~orementioned objects can be attained by employing a system including lithium as the anode, LixCoOa(O< x ~1) as the cathode, and a solution of a lithium salt in a mixed organic solvent Oe MF and DEC as the electrolyte.
The solution can be, ~or example, 1 to 2 mol dm s LiA~
in the mixed organic solvent. Though the use o~ LiAsF,~ as th~
electrolyte salt is pre~erred, other electrolyte salts can be used such as the soluble salts o~`light metals, for example, tetra~luoroborates, tetrachloroaluminates, perchlorates, hexa~luorophosphates, and halides o~ lithium.
The mass percent o~ the DEC in the mixed organic solvent can vary ~rom 10 to 100 mass percent. The instant invention identi~ies and demonstrates that the addition o~ DLC to ester containing electrolytes, such as LiAsF~ in MF, results in signi~icant improvements in the electrolytes resistance to electrochemical oxidation and improved lithium cycling efficiencies. In addition, when these electrolytes containing the DEC additives are used in Li/LixCoO~ electrochemical cells, there is signiEicant improvements in the cell cycling behavior over cells without the DEC additive.
~3~
The drawing compares cycling results obtained ~or additions o~ DEC and dimethylcarbonate (DMC) to LiAsF~ in MF
electrolyte in a Li/LixCoOl electrochemical cell.
The drawing shows the dramatic improvement in cycli~g behavior ~or the electrolyte containing DEC as opposed to DMC.
The Li/Li~CoO~ cells are cycled between either 4.3Vto 3.5V or 4.3V
to 2.5V where the charging rate is 0.5 mAcm~, the discharge rate is 2.0 mAcm~, and the temperature is 25~C. The LixCaO~ cathodes include a mixture o~ 80 weight percent Li~CoO~, 10 weight percent carbon diluent, and 10 weight percent Teflon binder. The cathode mixture is roll pressed onto aluminum substrate5 and sintered in a vacuum oven at 280~C ~or 1 hour. The cycling is per~ormed on identically prepared cells consisting o~ ~lag electrodes sealed in a glass pressure vessel where Celgard 2400 is used as separators and a glass ~iber wick ~or drawing electrolyte in between the electrode.
Interestingly, homologues o~ DEC such as DMC have been utilized in lithium cells and are known to be su~iciently stable towards lithium. However, although DMC and DEC show structural similarities, they behave very di~erently in the presence o~
lithium, both chemically and electrochemically. DMC produces a high cycling e~iciency o~ S0 percent as compared to DEC which is O percent. This is due to the reactive nature o~ DEC with lithium as opposed to the more stable DMC solvent. However, even though DMC is more stable with lithium, its addition to the LiAsF~-MF
electrolyte does not result in the improved results observed with DEC. ThereEore, where the success~ul use o~ DMC as a solvent in * denotes trade mark ~L3~ EiO~
lithium cells may imply the possible use oE a similar solvent such as DEC, this is not made obvious due to the lack o~ lithium stability o~ the neat DEC electrolyte, thus precluding such application~. Furthermore, one would not ~ind obvious tha discovery that a mixture o~ the unstable solvent DEC with ano~her solvent would produce an improved mixture suitably stable ~or use in a lithium cell. It is only through its addition to other ester electrolytes that the use o~ DEC in lithium cells is possible.
The use o~ DEC as a solvemt additive in electrolytes ~or use in either primary, rechargeable, or reserve electrochemical cells is not considered to be limited to the instance where lithium is the anode. That is, other light metals or composites may be applicable as the anode such as sodium, potassium and aluminum, or any conductively doped polymeric material or similar compound~ Moreover, the positive electrode or cathode, may be any oxide, sul~ide or combinations o~ titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ha~nium, tantalum, or tungsten or any conductively doped polymeric material or similar compound.
We wish it to be un~derstood that we do not desire to be limited to the exact details as described ~or obvious modi~ications will occur to a person skilled in the art~
!
Claims (5)
1. An electrochemical cell comprising lithium as the anode, the lithium intercalating compound Lix CoO2(0< x <1) as the cathode, and a solution of a lithium salt in a mixed organic solvent of methylformate and diethylcarbonate as the electrolyte.
2. An electrochemical cell according to claim 1 wherein the mass percent of the diethylcarbonate can vary from about 10 to 100 mass percent in the electrolyte.
3. An electrochemical cell according to claim 2 wherein the solution of lithium salt is 1-2 mol dm-3 LiAsF6 in methylformate.
4. An electrochemical cell according to claim 1 wherein the Lix CoO2 cathode consists of a mixture of about 80 weight percent LixCoO2, about 10 weight percent carbon diluent and about 10 weight percent Teflon binder roll pressed onto aluminum substrates and sintered in a vacuum oven at 280°C for 1 hour.
5. An electrochemical cell according to claim 4 wherein the mass percent of the diethylcarbonate can vary from about 10 to about 100 mass percent in the electrolyte and wherein the solution of lithium salt is 1-2 mol dm-3 LiAsF6 in methylformate.
.
.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US215,664 | 1988-07-06 | ||
| US07/215,664 USH723H (en) | 1988-07-06 | 1988-07-06 | Lithium electrochemical cell containing diethylcarbonate as an electrolyte solvent additive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1306001C true CA1306001C (en) | 1992-08-04 |
Family
ID=22803877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000599186A Expired - Fee Related CA1306001C (en) | 1988-07-06 | 1989-04-19 | Lithium electrochemical cell containing diethylcarbonate asan electrolyte solvent additive |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | USH723H (en) |
| CA (1) | CA1306001C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147739A (en) * | 1990-08-01 | 1992-09-15 | Honeywell Inc. | High energy electrochemical cell having composite solid-state anode |
| US5284721A (en) * | 1990-08-01 | 1994-02-08 | Alliant Techsystems Inc. | High energy electrochemical cell employing solid-state anode |
| US7927742B2 (en) | 2004-10-29 | 2011-04-19 | Medtronic, Inc. | Negative-limited lithium-ion battery |
| JP5068660B2 (en) | 2004-10-29 | 2012-11-07 | メドトロニック，インコーポレイテッド | How to charge a lithium-ion battery |
| US9065145B2 (en) * | 2004-10-29 | 2015-06-23 | Medtronic, Inc. | Lithium-ion battery |
| US7563541B2 (en) * | 2004-10-29 | 2009-07-21 | Medtronic, Inc. | Lithium-ion battery |
| US8105714B2 (en) * | 2004-10-29 | 2012-01-31 | Medtronic, Inc. | Lithium-ion battery |
| US7582387B2 (en) * | 2004-10-29 | 2009-09-01 | Medtronic, Inc. | Lithium-ion battery |
| US7811705B2 (en) * | 2004-10-29 | 2010-10-12 | Medtronic, Inc. | Lithium-ion battery |
| US8980453B2 (en) * | 2008-04-30 | 2015-03-17 | Medtronic, Inc. | Formation process for lithium-ion batteries |
| US9077022B2 (en) | 2004-10-29 | 2015-07-07 | Medtronic, Inc. | Lithium-ion battery |
| US7641992B2 (en) * | 2004-10-29 | 2010-01-05 | Medtronic, Inc. | Medical device having lithium-ion battery |
| US7807299B2 (en) * | 2004-10-29 | 2010-10-05 | Medtronic, Inc. | Lithium-ion battery |
| US7662509B2 (en) * | 2004-10-29 | 2010-02-16 | Medtronic, Inc. | Lithium-ion battery |
| US9287580B2 (en) | 2011-07-27 | 2016-03-15 | Medtronic, Inc. | Battery with auxiliary electrode |
| US20130149560A1 (en) | 2011-12-09 | 2013-06-13 | Medtronic, Inc. | Auxiliary electrode for lithium-ion battery |
-
1988
- 1988-07-06 US US07/215,664 patent/USH723H/en not_active Abandoned
-
1989
- 1989-04-19 CA CA000599186A patent/CA1306001C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| USH723H (en) | 1990-01-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |