WO2008094206A2 - Lithium-ion battery with improved self-discharge characteristics - Google Patents

Lithium-ion battery with improved self-discharge characteristics Download PDF

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Publication number
WO2008094206A2
WO2008094206A2 PCT/US2007/017326 US2007017326W WO2008094206A2 WO 2008094206 A2 WO2008094206 A2 WO 2008094206A2 US 2007017326 W US2007017326 W US 2007017326W WO 2008094206 A2 WO2008094206 A2 WO 2008094206A2
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WIPO (PCT)
Prior art keywords
lithium
ion cell
aqueous
basic species
electrolyte
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Application number
PCT/US2007/017326
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French (fr)
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WO2008094206A9 (en
WO2008094206A3 (en
Inventor
Brett Lucht
Joseph Dicarlo
Stuart Santee
Ang Xiao
Wentao Li
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Yardney Technical Products Inc.
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Publication of WO2008094206A2 publication Critical patent/WO2008094206A2/en
Publication of WO2008094206A3 publication Critical patent/WO2008094206A3/en
Publication of WO2008094206A9 publication Critical patent/WO2008094206A9/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the invention was made under an Air Force/subcontract from Yardney Technical Products and NSF/CIA Grant Contract No. URI 540161
  • This invention relates to lithium-ion batteries and cells and more particularly to an improved non-aqueous electrolyte therefore containing an additive which inhibits self-discharge normally exhibited upon thermal abuse or after extended calendar life.
  • Lithium-ion batteries have been intensely exploited for the past 20 years.
  • commercial cells have several problems, including increases in self discharge upon storage and prolonged use, especially at elevated temperatures and extreme sensitivity to protic impurities such as water.
  • Self discharge is defined as a loss of charge capacity from a secondary battery at full or partial state of charge upon storage.
  • HEV hybrid electric vehicles
  • EV electric vehicles
  • Another object of the invention in is therefore to decrease the sensitivity of cycle life in lithium-ion batteries and cells to trace impurities such as water.
  • a non-aqueous lithium-ion battery or cell electrolyte such as LiPF 6 dissolved in an organic carbonate
  • an additive comprising at least one Leiws basic species selected from ureas and acetamides, such as dimethyl acetamide, as well as certain other organic compounds such as N-methylpyrrolidone (NMP) .
  • NMP N-methylpyrrolidone
  • Figure 1 is a plot showing the discharge capacity of lithium-ion test cells with and without electrolyte additives according to the invention verses number of cycles conducted during the test, and
  • Figure 2 is a similar plot showing the discharge capacity of lithium-ion test cells with and without the same additives employed in the cells of Figure 1 but also including an added water impurity of about 0.5% H 2 O in each cell.
  • a preferred electrolyte for use in the invention may comprise, for example, between about 10 and 30 percent of a lithium salt such as lithium hexafluoraphosphate (LiPF 6 ) and between about 70 and 90 percent of an organic solvent such as ethylene carbonate (EC) with the addition of about 0.25 percent by volume of the Lewis basic species such as dimethyl acetamide (DMAC) .
  • a lithium salt such as lithium hexafluoraphosphate (LiPF 6 )
  • an organic solvent such as ethylene carbonate (EC)
  • EC ethylene carbonate
  • the non-aqueous electrolytes of the invention may employ a number of lithium salts such as lithium hexafluorophosphate (LiPF 6 ) , lithium hexafluoroarsenate (LiAsF 6 ) and lithium tetrafluoroborate (LiBF 4 ) , for example, as well as mixtures thereof .
  • the preferred lithium salt for use in the electrolytes is lithium hexafluorophosphate (LiPF 6 ) .
  • Other lithium salts as well as mixtures of salts may also be useful in the electrolytes of the invention.
  • organic solvents useful in the electrolytes of the invention are the organic carbonates, esters, ethers, glymes, organic nitriles, sulfones as well as mixtures thereof.
  • the organic carbonates are preferred and may be the cyclic organic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), triethylene carbonate (TEC), and butylene carbonate (IBC) or the acyclic carbonates such as dimethyl carbonate (DMC) , diethyl carbonate (DEC) , ethylmethyl carbonate (EMC) and mixtures thereof.
  • EC ethylene carbonate
  • PC propylene carbonate
  • TEC triethylene carbonate
  • IBC butylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • the invention is also directed to an electric current producing rechargeable Li-ion battery or cell comprising an anode; a cathode; and a non-aqueous electrolyte comprising a solution of a lithium salt in a non-aqueous organic solvent containing one of the above mentioned Lewis basic species such as dimethyl acetamide (DMAC), for example.
  • DMAC dimethyl acetamide
  • the anode of the Li-ion cell of the invention consists of a lithium intercalating compound such as a carbonaceous material such as mesocarbonmicrobead (MCMB) graphite and the cathode consists of a lithium intercalating transition metal compound such as LiCoO 2 ; LiNiO 2 ; LiNi ⁇ x Co x O 2 where x is 0.3 ⁇ x ⁇ 1.0; LiMn 2 O 4 ; LiV 2 O 5 ; LiM x N 1 ⁇ O 2 , where M and N are transition metals and x has a value between zero and one; LiFePO 4 ; LiCrS 2 ; and LiVS 2 , for example.
  • MCMB mesocarbonmicrobead
  • a number of 7 Ah prismatic lithium-ion cells were constructed using an MCMB graphite anode and a cathode consisting of LiNi 0-8 Co 0 . 2 O 2 along with a non-aqueous electrolyte composed of 1.0 M LiPF 6 in 1:1:1 ethylene carbonate (EC)/ diethyl carbonate (DEC)/ dimethyl carbonate (DMC) .
  • Some of the cells were made without the DMAC additive (Cells A&B) while the remaining cells (Cells C&D)were made with the additive.
  • the cells were stored sequentially 10 days at 55, 60, 65, 70, and 75 °C. After each storage temperature, the residual discharge capacity was measured followed by C/5, C/2 and C rate changes and discharges.
  • a number of lithium-ion coin cells were constructed using the same anode, cathode and electrolyte as employed in Example 1 (MCMB, 1.0 M LiPF 6 in 1:1:1 EC/DEC/DMC, LiNi 0 . 8 Co 0 . 2 O 2 ) with added water impurity (0.5%) with and without 1% DMAC.
  • the cells were subjected to charge ⁇ discharge over about 20 to of cycles at a rate of about 0.0015 itiAh. The decrease in sensitivity to trace water impurities can be observed in Figure 2.

Abstract

A non-aqueous lithium-ion cell electrolyte comprising a solution of a lithium salt in an organic solvent containing an additive comprising at least one Leiws basic species selected from the group of dimethyl acetamide (DMAC), tetramethylurea, dimethylpropylene urea, dimethylethylene urea, and N-methylpyrrolidone (NMP). The additive inhibits undesirable self discharge upon thermal abuse or after extended calendar life.

Description

LITHIUM-ION BATTERY WITH IMPROVED SELF-DISCHARGE
CHARACTERISTICS
Government Rights
The invention was made under an Air Force/subcontract from Yardney Technical Products and NSF/CIA Grant Contract No. URI 540161
Priorities
This application claims priority to our earlier filed provisional application Serial No. 60/835,521, filed on August 4, 2006.
Field of the invention
This invention relates to lithium-ion batteries and cells and more particularly to an improved non-aqueous electrolyte therefore containing an additive which inhibits self-discharge normally exhibited upon thermal abuse or after extended calendar life.
Background of the Invention
Lithium-ion batteries have been intensely exploited for the past 20 years. However, commercial cells have several problems, including increases in self discharge upon storage and prolonged use, especially at elevated temperatures and extreme sensitivity to protic impurities such as water.
Self discharge is defined as a loss of charge capacity from a secondary battery at full or partial state of charge upon storage. In order to develop high energy lithium-ion batteries for hybrid electric vehicles (HEV) and electric vehicles (EV) applications, the self discharge performance of lithium-ion batteries, and the sensitivity of cell life to trace water impurities that are frequently incorporated therein during production must be improved.
Upon storage at elevated temperatures, or extended time at room temperature, the chemical and electrochemical side reactions of the battery materials results in an increase in the self discharge of lithium-ion batteries. While the mechanism of self discharge is not fully understood, there are two primary proposed models. The first involves the generation of an absorbed electron-ion- electrolyte complex (Yazani, R.; Reynier Y. F. Electrochim Acta. 47 (2002) 1217) . The second involves a shuttle mechanism where decomposition products from the anode "shuttle" electrons to the cathode (Sloop, S. E.: Kerr, J.B.; Kinoshita, K.J., Power Sources 119-121 (2003) 330).
The production of most lithium-ion batteries is conducted in a dry room (less than 2% relative humidity) . However, even under these conditions, it is impossible to completely prevent any contamination of the electrolyte or electrode materials with' trace water impurities. The presence of water in lithium ion cells leads to decreases in cycle life and calendar life and increases in the impedance of the cell.
It is therefore an important object of the invention to inhibit increases in self discharge of lithium-ion batteries, typically occurring in lithium-ion batteries and cells that have been thermally abused or aged.
Another object of the invention in is therefore to decrease the sensitivity of cycle life in lithium-ion batteries and cells to trace impurities such as water. Summary of the Invention
The above and other objects of the invention are achieved by the addition to a non-aqueous lithium-ion battery or cell electrolyte, such as LiPF6 dissolved in an organic carbonate, for example, of an additive comprising at least one Leiws basic species selected from ureas and acetamides, such as dimethyl acetamide, as well as certain other organic compounds such as N-methylpyrrolidone (NMP) . It has been unexpectedly found that these additives exhibit a two-fold effect which (1) significantly inhibit the increases in self discharge which are observed in lithium- ion batteries and cells that have been thermally abused or after extended calendar life and which (2) decrease the sensitivity of capacity lost to water impurities.
Description of the Drawings
Figure 1 is a plot showing the discharge capacity of lithium-ion test cells with and without electrolyte additives according to the invention verses number of cycles conducted during the test, and
Figure 2 is a similar plot showing the discharge capacity of lithium-ion test cells with and without the same additives employed in the cells of Figure 1 but also including an added water impurity of about 0.5% H2O in each cell.
Description of the Preferred Embodiments
It has been observed in accordance with the invention that the undesirable self discharge characteristics of rechargeable lithium-ion batteries and cells employing an electrolyte solution of a lithium salt such as hexafluoraphosphate (LiPF6) in an organic solvent such as ethylene carbonate (EC) , for example, that is normally exhibited upon thermal abuse or after extended calendar life can be substantially inhibited by the addition of a small amount of a Leiws basic species selected from the group of acetamides, such as dimethyl acetamide (DMAC) , ureas such as tetramethylurea, dimethylpropylene urea and dimethylethylene urea, and certain other organic compounds including N- methylpyrrolidone (NMP) . It has also been unexpectedly observed that the sensitivity of these same rechargeable lithium-ion batteries and cells to capacity lost to water impurities is significantly decreased.
It has been further discovered in accordance with the invention that these significant two-fold benefits can be achieve by the addition to the electrolyte of any one of the selected Lewis basic species in relative small amounts of between about 0.01 and 1.0 volume percent of the total electrolyte composition. Preferably, the Lewis basic species is added in an amount of about 0.25 percent of the lithium-ion electrolyte solution. A preferred electrolyte for use in the invention may comprise, for example, between about 10 and 30 percent of a lithium salt such as lithium hexafluoraphosphate (LiPF6) and between about 70 and 90 percent of an organic solvent such as ethylene carbonate (EC) with the addition of about 0.25 percent by volume of the Lewis basic species such as dimethyl acetamide (DMAC) .
The non-aqueous electrolytes of the invention may employ a number of lithium salts such as lithium hexafluorophosphate (LiPF6) , lithium hexafluoroarsenate (LiAsF6) and lithium tetrafluoroborate (LiBF4) , for example, as well as mixtures thereof . The preferred lithium salt for use in the electrolytes is lithium hexafluorophosphate (LiPF6) . Other lithium salts as well as mixtures of salts may also be useful in the electrolytes of the invention.
Among the organic solvents useful in the electrolytes of the invention are the organic carbonates, esters, ethers, glymes, organic nitriles, sulfones as well as mixtures thereof. The organic carbonates are preferred and may be the cyclic organic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), triethylene carbonate (TEC), and butylene carbonate (IBC) or the acyclic carbonates such as dimethyl carbonate (DMC) , diethyl carbonate (DEC) , ethylmethyl carbonate (EMC) and mixtures thereof.
In another aspect, the invention is also directed to an electric current producing rechargeable Li-ion battery or cell comprising an anode; a cathode; and a non-aqueous electrolyte comprising a solution of a lithium salt in a non-aqueous organic solvent containing one of the above mentioned Lewis basic species such as dimethyl acetamide (DMAC), for example.
The anode of the Li-ion cell of the invention consists of a lithium intercalating compound such as a carbonaceous material such as mesocarbonmicrobead (MCMB) graphite and the cathode consists of a lithium intercalating transition metal compound such as LiCoO2; LiNiO2; LiNi^xCoxO2 where x is 0.3<x<1.0; LiMn2O4; LiV2O5; LiMxN1^O2 , where M and N are transition metals and x has a value between zero and one; LiFePO4; LiCrS2; and LiVS2 , for example. The invention will be further described by reference to the following examples.
Example 1
A number of 7 Ah prismatic lithium-ion cells were constructed using an MCMB graphite anode and a cathode consisting of LiNi0-8Co0.2O2 along with a non-aqueous electrolyte composed of 1.0 M LiPF6 in 1:1:1 ethylene carbonate (EC)/ diethyl carbonate (DEC)/ dimethyl carbonate (DMC) . Some of the cells were made without the DMAC additive (Cells A&B) while the remaining cells (Cells C&D)were made with the additive. The cells were stored sequentially 10 days at 55, 60, 65, 70, and 75 °C. After each storage temperature, the residual discharge capacity was measured followed by C/5, C/2 and C rate changes and discharges. After storage at 70° C, the residual discharge capacity for the cells containing 1% DMAC (C&D) was 74% of the initial capacity, while the cells without DMAC (A&B) had only 59% of the initial capacity. The inhibition of increases in self-discharge can be observed in Figure 1.
Example 2
A number of lithium-ion coin cells were constructed using the same anode, cathode and electrolyte as employed in Example 1 (MCMB, 1.0 M LiPF6 in 1:1:1 EC/DEC/DMC, LiNi0.8Co0.2O2) with added water impurity (0.5%) with and without 1% DMAC. The cells were subjected to charge\discharge over about 20 to of cycles at a rate of about 0.0015 itiAh. The decrease in sensitivity to trace water impurities can be observed in Figure 2.

Claims

What is claimed is:
1. A non-aqueous lithium-ion cell electrolyte comprising a solution of a lithium salt in an organic solvent containing an additive comprising at least one Leiws basic species selected from the group of dimethyl acetamide (DMAC) , tetramethylurea, dimethylpropylene urea, dimethylethylene urea, and N-methylpyrrolidone (NMP) .
2. A non-aqueous lithium-ion cell electrolyte according to claim 1, wherein said Leiws basic species is present in the electrolyte in amounts of between about 0.01 and 1.0 percent by volume of said electrolyte solution.
3. A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein said Leiws basic species is present in the electrolyte in an amount of about 0.25 percent by volume of said electrolyte solution.
4. A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein said electrolyte comprises between about 10 and 30 percent by volume of a lithium salt and between about 70 and 90 percent by volume of an organic solvent with the addition of about 0.25 percent by volume of dimethyl acetamide (DMAC).
5. A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein said Lewis basic species is dimethyl acetamide (DMAC) .
6. A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein Lewis basic speices is dimethylpropylene urea .
7. A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein said Leiws basic species is dimethylethylene urea
8. A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein said Lewis basic species is tetramethylurea .
9. A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein said Lewis basic species is N- methylpyrrolidone (NMP) .
10 . A non-aqueous lithium-ion cell electrolyte according to claim 2, wherein said lithium salt is selected from the group consisting of lithium hexaflurophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6) and lithium tetrafluoroborate (LiBF4) as well as mixtures thereof.
11. A non-aqueous lithium-ion cell electrolyte according to claim 10, wherein the solvent is selected from the group of organic carbonates, esters, ethers, glymes, organic nitrides, sulfonesas well as mixtures thereof.
12. An electric current producing lithium-ion cell comprising an anode, a cathode and a non-aqueous electrolyte comprising a solution of a lithium salt in a non-aqueous organic solvent containing a Lewis basic species selected from the group of dimethyl acetamide (DMAC), tetramethylurea, dimethylpropylene urea, dimethylethylene urea, and N-methylpyrrolidone (NMP) .
13. An electric current producing lithium-ion cell according to claim 12, wherein said intercalating compound is a carbonaceous material.
14. An electric current producing Lithium-ion cell according to claim 12, wherein said carbonaceous material is mesocarbonmicrobead (MCMB) graphite.
15. An electric current producing Lithium-ion cell according to claim 13, wherein said cathode consists of a lithium intercalating transition metal compound selected from the group of LiCoO2, LiNiO2 and LiNi^xCoxO2 where x is 0.3<x<1.0; LiMn2O4; LiV2O5; LiMxN^xO2, where M and N are transition metals and x has a value between zero and one.
PCT/US2007/017326 2006-08-04 2007-08-03 Lithium-ion battery with improved self-discharge characteristics WO2008094206A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US83552106P 2006-08-04 2006-08-04
US60/835,521 2006-08-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013040326A1 (en) * 2011-09-15 2013-03-21 Robert Bosch Gmbh Stable electrolyte materials for li-air battery systems
CN114695961A (en) * 2022-03-25 2022-07-01 上海瑞浦青创新能源有限公司 Electrolyte for lithium ion battery and lithium ion battery using same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634636A (en) * 1983-12-13 1987-01-06 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetylene composite
US20030170549A1 (en) * 2002-02-01 2003-09-11 Japan Storage Battery Co., Ltd. Non-aqueous electrolyte battery
US6852446B2 (en) * 2001-11-09 2005-02-08 Yardney Technical Products, Inc. Non-aqueous electrolytes for lithium electrochemical cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634636A (en) * 1983-12-13 1987-01-06 Asahi Kasei Kogyo Kabushiki Kaisha Polyacetylene composite
US6852446B2 (en) * 2001-11-09 2005-02-08 Yardney Technical Products, Inc. Non-aqueous electrolytes for lithium electrochemical cells
US20030170549A1 (en) * 2002-02-01 2003-09-11 Japan Storage Battery Co., Ltd. Non-aqueous electrolyte battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013040326A1 (en) * 2011-09-15 2013-03-21 Robert Bosch Gmbh Stable electrolyte materials for li-air battery systems
US10116021B2 (en) 2011-09-15 2018-10-30 Robert Bosch Gmbh Stable electrolyte materials for Li-air battery systems
CN114695961A (en) * 2022-03-25 2022-07-01 上海瑞浦青创新能源有限公司 Electrolyte for lithium ion battery and lithium ion battery using same

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WO2008094206A9 (en) 2008-12-18
WO2008094206A3 (en) 2008-10-16

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