CA2384494A1 - Lithium metal dispersion in secondary battery anodes - Google Patents
Lithium metal dispersion in secondary battery anodes Download PDFInfo
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- CA2384494A1 CA2384494A1 CA002384494A CA2384494A CA2384494A1 CA 2384494 A1 CA2384494 A1 CA 2384494A1 CA 002384494 A CA002384494 A CA 002384494A CA 2384494 A CA2384494 A CA 2384494A CA 2384494 A1 CA2384494 A1 CA 2384494A1
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
Abstract
The present invention is a secondary battery having a high specific capacity and good cycleability, and that can be used safely. The secondary battery is manufactured to include an anode formed from a host material capable of absorbing and desorbing lithium in an electrochemical system such as a carbonaceous material, and lithium metal dispersed in the host material. The freshly prepared anode s of the invention are combined with a positive electrode including an active materia l, a separator that a separates the positive electrode and the negative electrode , and an electrolyte in communication with the positive electrode and the negative electrode. The present invention also includes a method of preparing a freshly prepared anode and a method of operating a secondary battery including the anode of the invention.
Description
LITHIUM METAL DISPERSION IN SECONDARY BATTERY ANODES
Cross-Reference To Related Applications This application is related to commonly owned copending provisional application Serial No. 60/257,994, filed December 22, 2000, and claims the benefit of the earlier filing date of this application under 35 U.S.C. ~ 119(e).
Field of the Igvention The present invention relates to secondary batteries having high specific capacities and particularly to anodes for secondary batteries comprising a host material such as a carbonaceous material capable of absorbing and desorbing lithium in an electrochemical system .and lithium metal dispersed in the host material.
Background of the Inv~tion Lithium and lithium-ion secondary or rechargeable batteries have recently found use in certain applications such as in cellular phones, camcorders, and laptop computers, and even more recently, in larger power applications such as in electric vehicles and hybrid electric vehicles. It is preferred in these applications that the s~;ondary batteries have the highest specific capacity possible but still provide ,_, safe operating conditions and good cycleability so that the high specific capacity is maintained in subsequent recharging and discharging cycles.
Although there are various constructions for secondary batteries, each construction includes a positive electrode (or cathode), a negative electrode (or - ~ anode), a separator that separates the cathode and anode, and an electrolyte in electrochemical communication with the cathode and anode. For secondary lithium batteries, lithium ions are transferred from the anode to the cathode through the electrolyte when the secondary battery is being discharged, i.e., used for its specific application. During this process, electrons are collected from the anode and pass to the cathode through an external circuit. When the secondary battery is being charged or recharged, the lithium ions are transferred from the cathode to the anode through the electrolyte.
Atty. Dln. No. 30208.241933 Historically, secondary lithium batteries were produced using non-lithiated compounds having high specific capacities such as TiSz, MoSl, Mn02 and V205, as the cathode active materials. These cathode active materials were coupled with a lithium metal anode. When the secondary battery was discharged, lithium ions were transferred from the lithium metal anode to the cathode through the electrolyte.
Unforhmately, upon cycling, the lithium metal developed dendrites that ultimately caused unsafe conditions in the battery. As a result, the production of these types of secondary batteries was stopped in the early 1990's in favor of lithium-ion batteries.
Lithium-ion batteries typically use lithium metal oxides such as LiCoOz and LiNi02 as cathode active materials coupled with a carbon-based anode.
In these batteries, the lithium dendrite formation on the anode is avoided thereby making the battery safer. However, the lithium, the amount of which determines the battery capacity, is totally supplied from the cathode. This limits the choice of cathode active materials because the active materials must contain removable lithium.
1 S Furthermore, the delithiated products corresponding to LiCo02 and LiNi02 that are formed during charging (e.g. LixCo02 and LiXNi02 where 0.4<x<1.0) and overcharging (i.e. LiXCo02 and LixNi02 where x<0.4) are not stable. In particular, these delithiated products tend to react with the electrolyte and generate heat, which raises safety concerns. ~ ':_: .~ .
~ummarv of the Invention The present invention is a secondary battery having a high specific .. . capacity and good cycleability and that operates safely. In accordance with the invention, the freshly prepared, secondary battery includes an anode that is formed of a host material capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material. Preferably, the lithium metal is a finely divided lithium powder and more preferably has a mean particle size of less than about 20 microns. The host material comprises one or more materials selected from the group consisting of carbonaceous materials, Si, Sn, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides and lithium metal oxides.
Cross-Reference To Related Applications This application is related to commonly owned copending provisional application Serial No. 60/257,994, filed December 22, 2000, and claims the benefit of the earlier filing date of this application under 35 U.S.C. ~ 119(e).
Field of the Igvention The present invention relates to secondary batteries having high specific capacities and particularly to anodes for secondary batteries comprising a host material such as a carbonaceous material capable of absorbing and desorbing lithium in an electrochemical system .and lithium metal dispersed in the host material.
Background of the Inv~tion Lithium and lithium-ion secondary or rechargeable batteries have recently found use in certain applications such as in cellular phones, camcorders, and laptop computers, and even more recently, in larger power applications such as in electric vehicles and hybrid electric vehicles. It is preferred in these applications that the s~;ondary batteries have the highest specific capacity possible but still provide ,_, safe operating conditions and good cycleability so that the high specific capacity is maintained in subsequent recharging and discharging cycles.
Although there are various constructions for secondary batteries, each construction includes a positive electrode (or cathode), a negative electrode (or - ~ anode), a separator that separates the cathode and anode, and an electrolyte in electrochemical communication with the cathode and anode. For secondary lithium batteries, lithium ions are transferred from the anode to the cathode through the electrolyte when the secondary battery is being discharged, i.e., used for its specific application. During this process, electrons are collected from the anode and pass to the cathode through an external circuit. When the secondary battery is being charged or recharged, the lithium ions are transferred from the cathode to the anode through the electrolyte.
Atty. Dln. No. 30208.241933 Historically, secondary lithium batteries were produced using non-lithiated compounds having high specific capacities such as TiSz, MoSl, Mn02 and V205, as the cathode active materials. These cathode active materials were coupled with a lithium metal anode. When the secondary battery was discharged, lithium ions were transferred from the lithium metal anode to the cathode through the electrolyte.
Unforhmately, upon cycling, the lithium metal developed dendrites that ultimately caused unsafe conditions in the battery. As a result, the production of these types of secondary batteries was stopped in the early 1990's in favor of lithium-ion batteries.
Lithium-ion batteries typically use lithium metal oxides such as LiCoOz and LiNi02 as cathode active materials coupled with a carbon-based anode.
In these batteries, the lithium dendrite formation on the anode is avoided thereby making the battery safer. However, the lithium, the amount of which determines the battery capacity, is totally supplied from the cathode. This limits the choice of cathode active materials because the active materials must contain removable lithium.
1 S Furthermore, the delithiated products corresponding to LiCo02 and LiNi02 that are formed during charging (e.g. LixCo02 and LiXNi02 where 0.4<x<1.0) and overcharging (i.e. LiXCo02 and LixNi02 where x<0.4) are not stable. In particular, these delithiated products tend to react with the electrolyte and generate heat, which raises safety concerns. ~ ':_: .~ .
~ummarv of the Invention The present invention is a secondary battery having a high specific .. . capacity and good cycleability and that operates safely. In accordance with the invention, the freshly prepared, secondary battery includes an anode that is formed of a host material capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material. Preferably, the lithium metal is a finely divided lithium powder and more preferably has a mean particle size of less than about 20 microns. The host material comprises one or more materials selected from the group consisting of carbonaceous materials, Si, Sn, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides and lithium metal oxides.
2 Atty. Dld. No. 30208.241933 Preferably, the host material comprises a carbonaceous material and more preferably comprises graphite.
The freshly prepared, secondary batteries of the invention include a positive electrode including an active material, a negative electrode comprising a host S material capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material, a separator separating the positive electrode and the negative electrode and an electrolyte in communication with the positive electrode and the negative electrode. Preferably, the cathode active material is a compound that can be lithiated at an electrochemical potential of 2.0 to 5.0 V
versus lithium. For example, the cathode active material can be Mn02, V205 or MoS2, or a mixture thereof. The lithium metal in the anode is preferably a finely divided lithium powder and more preferably has a mean particle size of less than about 20 microns. The host material comprises one or more materials selected from the group consisting of carbonaceous materials, Si, Sn, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides and lithium metal oxides.
Preferably, the host material in the negative electrode comprises a carbonaceous material and, more preferably, comprises graphite. The amount of lithium metal present in the negative electrode is preferably no more than the maximum amount su~cient to intercalate''ui;alloy with, or be absorbed by the host material in the negative electrode. For example, if the host material is carbon, the amount of lithium is preferably no more than the amount needed to make LiC6.
The present invention also includes a method of preparing a freshly _ . prepared anode for a secondary battery that includes the steps of providing a host material that is capable of absorbing and desorbing lithium in an electrochemical system, dispersing lithium metal in the host material and forming the host material and the lithium metal dispersed therein into an anode. The lithium metal and the host material is preferably mixed together with a non-aqueous liquid to produce a slurry and then applied to a current collector and dried to form the anode.
Alternatively, the anode can be formed by chemical means by immersing the host material in a suspension of lithium metal in a non-aqueous liquid, and then formed into an anode.
The freshly prepared, secondary batteries of the invention include a positive electrode including an active material, a negative electrode comprising a host S material capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material, a separator separating the positive electrode and the negative electrode and an electrolyte in communication with the positive electrode and the negative electrode. Preferably, the cathode active material is a compound that can be lithiated at an electrochemical potential of 2.0 to 5.0 V
versus lithium. For example, the cathode active material can be Mn02, V205 or MoS2, or a mixture thereof. The lithium metal in the anode is preferably a finely divided lithium powder and more preferably has a mean particle size of less than about 20 microns. The host material comprises one or more materials selected from the group consisting of carbonaceous materials, Si, Sn, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides and lithium metal oxides.
Preferably, the host material in the negative electrode comprises a carbonaceous material and, more preferably, comprises graphite. The amount of lithium metal present in the negative electrode is preferably no more than the maximum amount su~cient to intercalate''ui;alloy with, or be absorbed by the host material in the negative electrode. For example, if the host material is carbon, the amount of lithium is preferably no more than the amount needed to make LiC6.
The present invention also includes a method of preparing a freshly _ . prepared anode for a secondary battery that includes the steps of providing a host material that is capable of absorbing and desorbing lithium in an electrochemical system, dispersing lithium metal in the host material and forming the host material and the lithium metal dispersed therein into an anode. The lithium metal and the host material is preferably mixed together with a non-aqueous liquid to produce a slurry and then applied to a current collector and dried to form the anode.
Alternatively, the anode can be formed by chemical means by immersing the host material in a suspension of lithium metal in a non-aqueous liquid, and then formed into an anode.
3 Ariy. Dlct. No. 30208.241933 The present invention further includes a method of operating a secondary battery. First, a freshly prepared, secondary battery is provided that includes a positive electrode including an active material, a negative electrode comprising a host material capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material, a separator for separating the positive electrode and the negative electrode, and an electrolyte in communication with the positive electrode and the negative electrode. In particular, the secondary battery is manufactured with lithium metal dispersed in the host material of the anode. The freshly assembled battery is in a charged state and more preferably is in a fully charged state (with all the removable lithium present in the anode of the fre,~hly prepared battery). The freshly prepared secondary battery is initially discharged by transmitting lithium ions from the negative electrode to the positive electrode through the electrolyte. The secondary battery can then be charged or recharged by transmitting lithium ions from the positive electrode to the negative electrode through the electrolyte and then discharged again by transmitting lithium ions from the negative electrode to the positive electrode through the electrolyte. The charging and discharging steps can occur for numerous cycles while maintaining the high specific capacities of the cathode active materials and maintaining safe operating conditions.
These and other features and advantages of the present invention will become more readily apparent to those skilled in the art upon consideration of the following detailed description and accompanying drawing, which describe both the . preferred and alternative embodiments of the present invention.
Brief Description of the ~rawint~
Fig. 1 illustrates a simplified secondary battery construction including a cathode, anode, separator and electrolyte, in accordance with the invention.
Detailed Description of the Preferred Embodiments o~the Invention In the drawings and the following detailed description, preferred embodiments are described in detail to enable practice of the invention.
Although the
These and other features and advantages of the present invention will become more readily apparent to those skilled in the art upon consideration of the following detailed description and accompanying drawing, which describe both the . preferred and alternative embodiments of the present invention.
Brief Description of the ~rawint~
Fig. 1 illustrates a simplified secondary battery construction including a cathode, anode, separator and electrolyte, in accordance with the invention.
Detailed Description of the Preferred Embodiments o~the Invention In the drawings and the following detailed description, preferred embodiments are described in detail to enable practice of the invention.
Although the
4 Atty. Dld. No. 30208.241933 invention is described with reference to these specific preferred embodiments, it will be understood that the invention is not limited to these preferred embodiments. But to the contrary, the invention includes numerous alternatives, modifications and equivalents as will become apparent from consideration of the following detailed description and accompanying drawing.
As illustrated in Figure 1, the present invention is a secondary battery I O that comprises a positive electrode or cathode 12, a negative electrode or anode 14, a separator 16 for separating the positive electrode and the negative electrode, and an electrolyte in electrochemical communication with the positive electrode and the negative electrode. The se<;ondary battery 10 also includes a current collector 20 that is in electrical contact with the cathode and a current collector 22 that is in electrical contact with the anode. The current collectors 20 and 22 are in electrical contact with one another through an external circuit (not shown). The secondary battery 10 can have any construction known in the art such as a '5elly roll" or stacked construction.
The cathode 12 is formed of an active material, which is typically combined with a carbonaceous material and a binder polymer. The active material used in the cathode 12 is preferably a material that can be lithiated at a useful voltage (e.g. 2.0 to 5.0 V versus lithium). Preferably, non-lithiated materials such as Mn02, V20s or MoS2, or mix ~tures there can be used as the active material, and more preferably, MnOZ is used. However, Iithiated materials such as LiMn20a 'that caa be further lithiatod can also be used. The non-lithiated active materials are preferred because they generally have higher specific capacities than the lithiated active materials in this construction and thus can provide increased power over secondary batteries that include lithiated active materials. Furthermore, because the anode 14 includes lithium as discussed below, it is not necessary that the cathode 12 include a lithiated material for the secondary battery 10 to operate. The amount of active material provided in the cathode 12 is preferably sufficient to accept the removable lithium metal present in the anode 14. For example, if Mn02 is the cathode active material, then one mole of Mn02 is preferably present in the cathode 12 per mole of lithium in the anode 14 to produce LiMnOi in the cathode upon discharge.
As illustrated in Figure 1, the present invention is a secondary battery I O that comprises a positive electrode or cathode 12, a negative electrode or anode 14, a separator 16 for separating the positive electrode and the negative electrode, and an electrolyte in electrochemical communication with the positive electrode and the negative electrode. The se<;ondary battery 10 also includes a current collector 20 that is in electrical contact with the cathode and a current collector 22 that is in electrical contact with the anode. The current collectors 20 and 22 are in electrical contact with one another through an external circuit (not shown). The secondary battery 10 can have any construction known in the art such as a '5elly roll" or stacked construction.
The cathode 12 is formed of an active material, which is typically combined with a carbonaceous material and a binder polymer. The active material used in the cathode 12 is preferably a material that can be lithiated at a useful voltage (e.g. 2.0 to 5.0 V versus lithium). Preferably, non-lithiated materials such as Mn02, V20s or MoS2, or mix ~tures there can be used as the active material, and more preferably, MnOZ is used. However, Iithiated materials such as LiMn20a 'that caa be further lithiatod can also be used. The non-lithiated active materials are preferred because they generally have higher specific capacities than the lithiated active materials in this construction and thus can provide increased power over secondary batteries that include lithiated active materials. Furthermore, because the anode 14 includes lithium as discussed below, it is not necessary that the cathode 12 include a lithiated material for the secondary battery 10 to operate. The amount of active material provided in the cathode 12 is preferably sufficient to accept the removable lithium metal present in the anode 14. For example, if Mn02 is the cathode active material, then one mole of Mn02 is preferably present in the cathode 12 per mole of lithium in the anode 14 to produce LiMnOi in the cathode upon discharge.
5 Atty. Dlct. No. 30208.241933 When cathode active materials are used that can be lithiated such as those described above, the removable lithium that is cycled in the battery is fully provided by the anode 14 and the battery is assembled or prepared in a fully charged state, as is preferred. Nevertheless, the cathode 12 can also include a minor amount of one or more lithiated active materials (e.g. LiCo42 or LiNi02) that do not further absorb lithium at a voltage between 2.0V and S.OV and the battery can still be provided in a primarily charged state. In this event, the cathode preferably has less than SO% (molar) and more preferably less than 10% (molar) of the Iithiated material (e.g. LiCo02 or LiNi02) as the active material. Because LiCoOz and LiNi02 do not further absorb lithium, the presence of these materials in the cathode 12 does not reduce the amount of cathode active material needed to accept the removable lithium from the anode 14.
The anode 14 is formed of a host material 24 capable of absorbing and desorbing Lithium in an electrochemical system with lithium metal 26 dispersed in the l 5 host material. For example, the lithium prESent in the anode 14 can intercalate in, alloy with or be absorbed by the host material when the battery (and particularly the anode) is recharged The host material includes materials capable of absorbing and desorbing lithium in an. electrochemical system such as carbonaceous materials;
materials containing Si'Sn, tin oxides or composite tin alloys; transition metal oxides such as CoO; Lithium metal nitrides such as Li3_xCoxN where 0<x<0.5, and lithium metal oxides 'such as Li4Ti5012. The lithium metal 2b is preferably provided in the anode 14 as a finely divided lithium powder. 1n addition, the lithium metal 26 ,. . preferably has a mean particle size of less than about 20 microns, more preferably less than about 10 microns. The lithium metal can be provided as a pyrophoric powder or as a stabilized Low pyrophorosity powder, e.g., by treating the lithium metal powder with COi.
The anode 14 is typically capable of reversibly lithiating and delithiating at an electrochemical potential relative to lithium metal of from greater than 0.0 V to less than or equal fo 1.5. If the electrochemical potential is 0.0 or less versus lithium, then the lithium metal will nqt reenter the anode 14 during charging.
Alternatively, if the electrochemical potential is greater than 1.5 V versus Lithium then
The anode 14 is formed of a host material 24 capable of absorbing and desorbing Lithium in an electrochemical system with lithium metal 26 dispersed in the l 5 host material. For example, the lithium prESent in the anode 14 can intercalate in, alloy with or be absorbed by the host material when the battery (and particularly the anode) is recharged The host material includes materials capable of absorbing and desorbing lithium in an. electrochemical system such as carbonaceous materials;
materials containing Si'Sn, tin oxides or composite tin alloys; transition metal oxides such as CoO; Lithium metal nitrides such as Li3_xCoxN where 0<x<0.5, and lithium metal oxides 'such as Li4Ti5012. The lithium metal 2b is preferably provided in the anode 14 as a finely divided lithium powder. 1n addition, the lithium metal 26 ,. . preferably has a mean particle size of less than about 20 microns, more preferably less than about 10 microns. The lithium metal can be provided as a pyrophoric powder or as a stabilized Low pyrophorosity powder, e.g., by treating the lithium metal powder with COi.
The anode 14 is typically capable of reversibly lithiating and delithiating at an electrochemical potential relative to lithium metal of from greater than 0.0 V to less than or equal fo 1.5. If the electrochemical potential is 0.0 or less versus lithium, then the lithium metal will nqt reenter the anode 14 during charging.
Alternatively, if the electrochemical potential is greater than 1.5 V versus Lithium then
6 Atty. Dlct. No. 30208.241933 the battery voltage will be undesirably low. Preferably, the amount of lithium metal 26 present in the anode 14 is no more than the maximum amount sufficient to intercalate in, alloy with, or be absorbed by the host material in the anode 14 when the battery is recharged. For example, if the host material 24 is carbon, the amount of lithium 26 is preferably no more than the amount sufficient to make LiC6. In other words, the molar ratio of lithium to carbon in the anode is preferably no more than 1:6.
In accordance with the invention, the anode 14 can be prepared by providing a host material that is capable of absorbing and desorbing lithium in an electrochemical system, dispersing lithium metal in the host material, and forming the host material and the lithium metal dispersed therein into an anode.
Preferably, the lithium metal and the host material are mixed with a non-aqueous liquid such as tetrahydmfuran (THF) and a binder, and formed into a slurry. The slurry is then used to form the anode 14, for example, by coating the current collector 22 with the slurry and then drying the sluny. The lithium metal can also be provided in the anode by immersing the host material in a suspension containing lithium metal in a non aqueous liquid such a hydrocarbon solvent (e.g. hexane). The lithium metal used in the suspension is preferably a finely divided lithium powder as discussed above. The host material can be foiined into the shape of the anode and then dipped into the lithium metal suspension or it can be combined with the lithium metal suspension to form a slurry and then applied to the current collector and dried to form the anode.
The non-aqueous liquid used to form the suspension can be removed by drying the " . anode (e.g. at an elevated temperature). No matter what method is used, the lithium metal is preferably distributed as well as possible into the host material.
Accordingly, as discussed above, the lithium metal 26 preferably has a mean particle size of less than about 20 microns, more preferably less than about 10 microns.
The host material 24 in the anode 14 can include one or more materials capable of absorbing and desorbing lithium in an electrochemical system such as carbonaceous materials; materials containing Si, Sn, tin oxides or composite tin alloys; transition metal oxides such as CoO; lithium metal nitrides such as Li3_xCoxN
where 0<x<0.5; and lithium metal oxides such as Li4Tis01a. Preferably, as mentioned
In accordance with the invention, the anode 14 can be prepared by providing a host material that is capable of absorbing and desorbing lithium in an electrochemical system, dispersing lithium metal in the host material, and forming the host material and the lithium metal dispersed therein into an anode.
Preferably, the lithium metal and the host material are mixed with a non-aqueous liquid such as tetrahydmfuran (THF) and a binder, and formed into a slurry. The slurry is then used to form the anode 14, for example, by coating the current collector 22 with the slurry and then drying the sluny. The lithium metal can also be provided in the anode by immersing the host material in a suspension containing lithium metal in a non aqueous liquid such a hydrocarbon solvent (e.g. hexane). The lithium metal used in the suspension is preferably a finely divided lithium powder as discussed above. The host material can be foiined into the shape of the anode and then dipped into the lithium metal suspension or it can be combined with the lithium metal suspension to form a slurry and then applied to the current collector and dried to form the anode.
The non-aqueous liquid used to form the suspension can be removed by drying the " . anode (e.g. at an elevated temperature). No matter what method is used, the lithium metal is preferably distributed as well as possible into the host material.
Accordingly, as discussed above, the lithium metal 26 preferably has a mean particle size of less than about 20 microns, more preferably less than about 10 microns.
The host material 24 in the anode 14 can include one or more materials capable of absorbing and desorbing lithium in an electrochemical system such as carbonaceous materials; materials containing Si, Sn, tin oxides or composite tin alloys; transition metal oxides such as CoO; lithium metal nitrides such as Li3_xCoxN
where 0<x<0.5; and lithium metal oxides such as Li4Tis01a. Preferably, as mentioned
7 Ariy. Dlct. No. 30208.24 Z 933 above, the host material 24 preferably includes graphite. In addition, the host material 24 preferably includes a small amount of carbon black (e.g. less than 5% by weight) as a conducting agent.
As shown in Figure 1, the cathode 12 is separated from the anode 14 by an electronic insulating separator 16. Typically, the separator 16 is formed of a material such as polyethylene, polypropylene, or polyvinylidene fluoride (PVDF).
The secondary battery 10 further includes an electrolyte that is in electrochemical communication with the cathode 12 and anode 14. The electrolyte can be non-aqueous liquid, gel or solid and preferably comprises a lithium salt, e.g., LiPF6. The electrolyte is provided throughout the battery 10 and particularly within the cathode 12, anode 14 and separator 16. Typically, the electrolyte is a liquid, and the cathode 12, anode 14 and separator 16 are porous materials that are soaked in the electrolyte to provide electrochemical communication between these components.
As mentioned above, the battery 10 includes current collectors 20 and 22, which are used to transmit electrons to an external circuit. Preferably, the current collector 20 is made of aluminum foil and current collector 22 is made of copper foil.
The battery 10 of the invention can be prepared by methods known in the art and preferably has a layer thickness within the following ranges (from left to . .:,; .:. .
right in Figure 1):
Layer thickness Current collector (20) 20-40 ~n Cathode (12) 70-100 ~n Separator (16) 25-35 ~n Anode (14) 70-100 wm Current collector (22) 20-40 ~Cm The battery 10 also includes an electrolyte dispersed throughout the cathode 12, anode 14 and separator 16, and a casing (not shown).
In operation, the freshly prepared secondary battery 10 is initially in a charged state, more preferably a fully charged state, and is initially discharged by transmitting lithium ions from the anode 14 to the cathode 12 through the electrolyte.
At the same time, electrons are transmitted from the anode 14 to the cathode IZ
through the current collector 22, the external circuit, and the current collector 20. The
As shown in Figure 1, the cathode 12 is separated from the anode 14 by an electronic insulating separator 16. Typically, the separator 16 is formed of a material such as polyethylene, polypropylene, or polyvinylidene fluoride (PVDF).
The secondary battery 10 further includes an electrolyte that is in electrochemical communication with the cathode 12 and anode 14. The electrolyte can be non-aqueous liquid, gel or solid and preferably comprises a lithium salt, e.g., LiPF6. The electrolyte is provided throughout the battery 10 and particularly within the cathode 12, anode 14 and separator 16. Typically, the electrolyte is a liquid, and the cathode 12, anode 14 and separator 16 are porous materials that are soaked in the electrolyte to provide electrochemical communication between these components.
As mentioned above, the battery 10 includes current collectors 20 and 22, which are used to transmit electrons to an external circuit. Preferably, the current collector 20 is made of aluminum foil and current collector 22 is made of copper foil.
The battery 10 of the invention can be prepared by methods known in the art and preferably has a layer thickness within the following ranges (from left to . .:,; .:. .
right in Figure 1):
Layer thickness Current collector (20) 20-40 ~n Cathode (12) 70-100 ~n Separator (16) 25-35 ~n Anode (14) 70-100 wm Current collector (22) 20-40 ~Cm The battery 10 also includes an electrolyte dispersed throughout the cathode 12, anode 14 and separator 16, and a casing (not shown).
In operation, the freshly prepared secondary battery 10 is initially in a charged state, more preferably a fully charged state, and is initially discharged by transmitting lithium ions from the anode 14 to the cathode 12 through the electrolyte.
At the same time, electrons are transmitted from the anode 14 to the cathode IZ
through the current collector 22, the external circuit, and the current collector 20. The
8 Atty. Dlct. No. 30208.241933 secondary battery 10 can then be charged or recharged by transmitting lithium ions from the cathode 12 to the anode 14 through the electrolyte and then discharged again as discussed above. The charging and discharging steps can occur for numerous cycles while maintaining the high specific capacities of the cathode active materials and maintaining safe operating conditions.
The secondary battery 10 can be used for various types of applications.
For example, the secondary battery can be used in portable electronics such as cellular phones, camcorders, and laptop computers, and in large power applications such as for electric vehicles and hybrid electric vehicles.
The present invention provides secondary batteries having a high specific capacity, safe operating conditions and good cycleability. In particular, because lithium metal is provided in the anode, non-lithiated materials can be used as the prefeaed cathode active material in the secondary battery. These non-lithiated materials have higher specific capacities than the lithiated materials presently used in lithium-ion batteries. Unlike traditional lithium secondary batteries having non-lithiated cathode active materials and metallic lithium anodes, it has been discovered that secondary batteries produced using non-lithiated cathode active materials combined with the anodes of the invention operate safely and do not generate lithium dendrites upon cycling.''' Furthermore, the secondary batteries of the present invention are safer to operate than lithium-ion batteries, which become unstable when lithium is removed from the cathode during charging. In particular, because the cathode active material in the secondary batteries of the invention is typically in a fully charged state when the battery is freshly prepared, it is more stable then the cathode materials used in lithium-ion batteries. Moreover, the batteries of the invention can be charged and discharged numerous times while maintaining safe operating conditions and the high specific capacities of the cathode active materials.
It is understood that upon reading the above description of the present invention and reviewing the accompanying drawings, one skilled in the art could make changes and variations therefrom. These changes and variations are included in the spirit and scope of the following appended claims.
The secondary battery 10 can be used for various types of applications.
For example, the secondary battery can be used in portable electronics such as cellular phones, camcorders, and laptop computers, and in large power applications such as for electric vehicles and hybrid electric vehicles.
The present invention provides secondary batteries having a high specific capacity, safe operating conditions and good cycleability. In particular, because lithium metal is provided in the anode, non-lithiated materials can be used as the prefeaed cathode active material in the secondary battery. These non-lithiated materials have higher specific capacities than the lithiated materials presently used in lithium-ion batteries. Unlike traditional lithium secondary batteries having non-lithiated cathode active materials and metallic lithium anodes, it has been discovered that secondary batteries produced using non-lithiated cathode active materials combined with the anodes of the invention operate safely and do not generate lithium dendrites upon cycling.''' Furthermore, the secondary batteries of the present invention are safer to operate than lithium-ion batteries, which become unstable when lithium is removed from the cathode during charging. In particular, because the cathode active material in the secondary batteries of the invention is typically in a fully charged state when the battery is freshly prepared, it is more stable then the cathode materials used in lithium-ion batteries. Moreover, the batteries of the invention can be charged and discharged numerous times while maintaining safe operating conditions and the high specific capacities of the cathode active materials.
It is understood that upon reading the above description of the present invention and reviewing the accompanying drawings, one skilled in the art could make changes and variations therefrom. These changes and variations are included in the spirit and scope of the following appended claims.
9 Arty. Dlct. No. 30208.241933
Claims (40)
1. A freshly prepared anode for a secondary battery comprising a host material that is capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material.
2. The anode according to Claim 1, wherein the lithium metal is a finely divided lithium powder.
3. The anode according to Claim 2, wherein the lithium powder has a mean particle size of less than about 20 microns.
4. The anode according to Claim 1, being capable of reversibly lithiating and delithiating at an electrochemical potential relative to lithium metal of from greater than 0.0 V to less than or equal to 1.5 V.
5. The anode according to Claim 1, wherein the host material comprises one or more materials capable of reversibly lithiating and delithiating at an electrochemical potential versus lithium of from greater than 0.0 V to less than or equal to 1.5 V.
6. The anode according to Claim 1, wherein the host material comprises one or more materials selected from the group consisting of carbonaceous materials, Si, Sn, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides and lithium metal oxides.
7. The anode according to Claim 1, wherein the host material comprises a carbonaceous material.
8. The anode according to Claim 7, wherein the carbonaceous material is graphite.
9. The anode according to Claim 8, wherein the host material further comprises carbon black.
10. The anode according to Claim 1, wherein the amount of lithium metal in said anode is no more than the maximum amount sufficient to intercalate in, alloy with, or be absorbed by the host material in said anode when the anode is recharged.
11. A secondary battery including the anode of Claim 1.
12. A freshly prepared, secondary battery comprising:
a positive electrode including an active material;
a negative electrode comprising a host material that is capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material;
a separator for separating the positive electrode and the negative electrode; and an electrolyte in communication with the positive electrode and the negative electrode.
a positive electrode including an active material;
a negative electrode comprising a host material that is capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material;
a separator for separating the positive electrode and the negative electrode; and an electrolyte in communication with the positive electrode and the negative electrode.
13. The secondary battery according to Claim 12, wherein the positive electrode includes a compound that can be lithiated at an electrochemical potential of 2.0 to 5.0V versus lithium as the active material.
14. The secondary battery according to Claim 13, wherein the active material in the positive electrode is selected from the group consisting of MnO2, V2O5 and MoS2, and mixtures thereof.
15. The secondary battery according to Claim 13, wherein the active material in the positive electrode comprises MnO2.
16. The secondary battery according to Claim 13, wherein the active material in the positive electrode is LiMn2O4.
17. The secondary battery according to Claim 12, wherein the lithium metal in said anode is a finely divided lithium powder.
18. The secondary battery according to Claim 17, wherein the lithium metal in said anode has a mean particle size of less than about 20 microns.
19. The secondary battery according to Claim 12, wherein the anode is capable of reversibly lithiating and delithiating at an electrochemical potential relative to lithium metal of from greater than 0.0 V to less than or equal to 1.5 V.
20. The secondary battery according to Claim 12, wherein the host material in said anode comprises one or more materials capable of reversibly lithiating and delithiating at an electrochemical potential versus lithium of from greater than 0.0 V to less than or equal to 1.5 V.
21. The secondary battery according to Claim 12, wherein the host material in said anode comprises one or more materials selected from the group consisting of carbonaceous materials, Si, Sn, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides and lithium metal oxides.
22. The secondary battery according to Claim 12, wherein the host material in said anode comprises a carbonaceous material.
23. The secondary battery according to Claim 22, wherein the carbonaceous material is graphite.
24. The secondary battery according to Claim 23, wherein the host material further comprises carbon black.
25. The secondary battery according to Claim 12, wherein the amount of lithium metal in said negative electrode is no more than the maximum amount sufficient to intercalate in, alloy with, or be absorbed by the host material in said anode when said battery is recharged.
26. The secondary battery according to Claim 12, wherein the amount of active material in said cathode is sufficient to accept the removable lithium metal present in said anode.
27. The secondary battery according to Claim 12, being in a fully charged state.
28. A method of preparing an anode for a secondary battery comprising:
providing a host material that is capable of absorbing and desorbing lithium in an electrochemical system;
dispersing lithium metal in the host material; and forming the host material and the lithium metal dispersed therein into an anode.
providing a host material that is capable of absorbing and desorbing lithium in an electrochemical system;
dispersing lithium metal in the host material; and forming the host material and the lithium metal dispersed therein into an anode.
29. The method according to Claim 28, wherein said dispersing step comprises mixing the lithium metal, the host material and a non-aqueous liquid together to form a slurry.
30. The method according to Claim 29, wherein said forming step comprising applying the slurry to a current collector and drying the slurry.
31. The method according to Claim 28, wherein said dispersing step comprises immersing the host material in a suspension containing lithium metal and a non-aqueous liquid.
32. The method according to Claim 31, wherein said dispersing step comprises immersing the host material in a suspension of lithium metal in a hydrocarbon.
33. The method according to Claim 28, wherein said dispersing step comprises dispersing a finely divided lithium metal powder in the host material.
34. The method according to Claim 33, wherein said dispersing step comprises dispersing lithium metal having a mean particle size of less than about 20 microns in the host material.
35. The method according to Claim 28, wherein said providing step includes providing a host material comprising one or more materials capable of reversibly lithiating and delithiating at an electrochemical potential versus lithium of from greater than 0.0 V to less than or equal to 1.5 V.
36. The method according to Claim 28, wherein said providing step comprises providing a host material comprising one or more materials selected from the group consisting of carbonaceous materials, Si, Sn, tin oxides, composite tin alloys, transition metal oxides, lithium metal nitrides, and lithium metal oxides.
37. The method according to Claim 28, wherein said providing step comprises providing a host material comprising a carbonaceous material.
38. The method according to Claim 37, wherein said providing step comprises providing a host material wherein the carbonaceous material is graphite.
39. The method according to Claim 38, wherein said providing step comprises providing a host material wherein the host material further comprises carbon black.
40. A method of operating a secondary battery comprising the steps of:
(a) providing a freshly prepared, secondary battery comprising a positive electrode including an active material, a negative electrode comprising a host material capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material, a separator for separating the positive electrode and the negative electrode, and an electrolyte in communication with the positive electrode and the negative electrode;
(b) initially discharging the secondary battery by transmitting lithium ions from the negative electrode to the positive electrode through the electrolyte;
(c) charging the secondary battery by transmitting lithium ions from the positive electrode to the negative electrode through the electrolyte;
(d) discharging the secondary battery by transmitting lithium ions from the negative electrode to the positive electrode through the electrolyte;
(e) repeating steps (c) and (d).
(a) providing a freshly prepared, secondary battery comprising a positive electrode including an active material, a negative electrode comprising a host material capable of absorbing and desorbing lithium in an electrochemical system and lithium metal dispersed in the host material, a separator for separating the positive electrode and the negative electrode, and an electrolyte in communication with the positive electrode and the negative electrode;
(b) initially discharging the secondary battery by transmitting lithium ions from the negative electrode to the positive electrode through the electrolyte;
(c) charging the secondary battery by transmitting lithium ions from the positive electrode to the negative electrode through the electrolyte;
(d) discharging the secondary battery by transmitting lithium ions from the negative electrode to the positive electrode through the electrolyte;
(e) repeating steps (c) and (d).
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/025,946 US6706447B2 (en) | 2000-12-22 | 2001-12-19 | Lithium metal dispersion in secondary battery anodes |
| JP2001391121A JP2002313324A (en) | 2000-12-22 | 2001-12-25 | Anode for use in lithium metal dispersed system secondary battery |
| FR0205144A FR2833760B1 (en) | 2001-12-19 | 2002-04-24 | DISPERSION OF LITHIUM METAL IN SECONDARY BATTERY ANODES |
| DK200200615A DK200200615A (en) | 2001-12-19 | 2002-04-24 | Lithium metal dispersion in secondary battery nodes |
| GB0209424A GB2383465B (en) | 2001-12-19 | 2002-04-25 | Lithium metal dispersion in secondary battery enodes |
| DE10218510A DE10218510B4 (en) | 2001-12-19 | 2002-04-25 | A process-fresh negative electrode for a rechargeable battery, rechargeable battery and method for producing a negative electrode |
| CNB02124684XA CN1290209C (en) | 2001-12-19 | 2002-04-29 | Dispersion of lithium metal in anode of secondarycell |
| CA2384494A CA2384494C (en) | 2000-12-22 | 2002-05-01 | Lithium metal dispersion in secondary battery anodes |
| US10/324,611 US8980477B2 (en) | 2000-12-22 | 2002-12-20 | Lithium metal dispersion in secondary battery anodes |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25799400P | 2000-12-22 | 2000-12-22 | |
| US10/025,946 US6706447B2 (en) | 2000-12-22 | 2001-12-19 | Lithium metal dispersion in secondary battery anodes |
| CA2384494A CA2384494C (en) | 2000-12-22 | 2002-05-01 | Lithium metal dispersion in secondary battery anodes |
Publications (2)
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| CA2384494A1 true CA2384494A1 (en) | 2003-11-01 |
| CA2384494C CA2384494C (en) | 2016-11-15 |
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|---|---|---|---|
| CA2384494A Expired - Lifetime CA2384494C (en) | 2000-12-22 | 2002-05-01 | Lithium metal dispersion in secondary battery anodes |
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| CN (1) | CN1290209C (en) |
| CA (1) | CA2384494C (en) |
| DE (1) | DE10218510B4 (en) |
| DK (1) | DK200200615A (en) |
| FR (1) | FR2833760B1 (en) |
| GB (1) | GB2383465B (en) |
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| US20050130043A1 (en) * | 2003-07-29 | 2005-06-16 | Yuan Gao | Lithium metal dispersion in electrodes |
| US8231810B2 (en) | 2004-04-15 | 2012-07-31 | Fmc Corporation | Composite materials of nano-dispersed silicon and tin and methods of making the same |
| US7771874B2 (en) | 2005-06-29 | 2010-08-10 | Fmc Corporation | Lithium manganese compounds and methods of making the same |
| US7588623B2 (en) | 2005-07-05 | 2009-09-15 | Fmc Corporation Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
| US20090035663A1 (en) | 2006-10-13 | 2009-02-05 | Fmc Corporation, Lithium Division | Stabilized lithium metal powder for li-ion application, composition and process |
| US8021496B2 (en) | 2007-05-16 | 2011-09-20 | Fmc Corporation | Stabilized lithium metal powder for Li-ion application, composition and process |
| CN102122709A (en) * | 2011-01-25 | 2011-07-13 | 天津中能锂业有限公司 | Lithium ion battery electrode added with lithium powder, preparation method thereof and lithium ion battery |
| CN102306827B (en) * | 2011-08-18 | 2014-04-02 | 江门三捷电池实业有限公司 | Safe lithium ion battery |
| EP3105803B1 (en) * | 2014-02-13 | 2020-01-15 | Albemarle Germany GmbH | Stabilized (partly) lithiated graphite materials, process for preparing them and use for lithium batteries |
| CN105449165B (en) | 2014-06-05 | 2018-01-02 | 宁德新能源科技有限公司 | - rich pole piece of lithium ion battery and preparation method thereof |
| TWI597887B (en) * | 2014-11-13 | 2017-09-01 | 日本曹達股份有限公司 | Negative electrode composition for power storage device, negative electrode including the same, and power storage device, and method for producing negative electrode for power storage device |
| KR102172070B1 (en) * | 2017-01-09 | 2020-10-30 | 주식회사 엘지화학 | Patterning of Lithium metal and electrochemical device prepared thereby |
| CN106654160A (en) * | 2017-01-24 | 2017-05-10 | 武汉理工力强能源有限公司 | Electrode plate activation method for negative electrode based on passivation metal lithium powder |
| CN108346794A (en) * | 2017-01-25 | 2018-07-31 | 武汉理工力强能源有限公司 | A kind of preparation method based on metallic lithium powder Yu graphite cathode battery |
| CN108346828A (en) * | 2017-01-25 | 2018-07-31 | 武汉理工力强能源有限公司 | A kind of soft-package battery preparation method based on metallic lithium powder Yu barium oxide material |
| CN108346779A (en) * | 2017-01-25 | 2018-07-31 | 武汉理工力强能源有限公司 | A kind of preparation method of the lithium metal battery with ultra high energy density |
| DE102017208218A1 (en) * | 2017-05-16 | 2018-11-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | A method of making an alkali metal coated substrate by means of a mediator layer and a mediator layer, and a coated substrate |
| CN113381009B (en) | 2020-03-10 | 2023-06-02 | 中国科学院物理研究所 | Lithium supplementing material and preparation method and application thereof |
| CN112133901B (en) * | 2020-10-22 | 2021-11-30 | 隆能科技(南通)有限公司 | Lithium-carbon composite material and preparation method thereof |
| CN115149106B (en) | 2021-08-27 | 2023-06-06 | 合肥国轩高科动力能源有限公司 | Pre-lithiation method of lithium ion battery and lithium ion battery |
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| JPS63178449A (en) * | 1987-01-16 | 1988-07-22 | Hitachi Maxell Ltd | Nonaqueous electrolyte secondary battery |
| US4945014A (en) * | 1988-02-10 | 1990-07-31 | Mitsubishi Petrochemical Co., Ltd. | Secondary battery |
| US5244757A (en) * | 1991-01-14 | 1993-09-14 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
| JP3291750B2 (en) * | 1992-02-25 | 2002-06-10 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery and method of manufacturing the same |
| EP0573266B1 (en) * | 1992-06-01 | 1999-12-08 | Kabushiki Kaisha Toshiba | Lithium secondary battery and method of manufacturing carbonaceous material for negative electrode of the battery |
| EP0601832B1 (en) * | 1992-12-07 | 1999-05-19 | Honda Giken Kogyo Kabushiki Kaisha | Alkaline ion-absorbing/desorbing carbon material, electrode material for secondary battery using the carbon material and lithium battery using the electrode material |
| DE69415911T2 (en) * | 1993-09-17 | 1999-06-10 | Toshiba Kawasaki Kk | Lithium secondary battery |
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| US5707756A (en) * | 1994-11-29 | 1998-01-13 | Fuji Photo Film Co., Ltd. | Non-aqueous secondary battery |
| US5753387A (en) * | 1995-11-24 | 1998-05-19 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
| US5958622A (en) * | 1996-03-28 | 1999-09-28 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Negative electrode material for lithium secondary batteries |
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| JPH10223259A (en) * | 1997-02-03 | 1998-08-21 | Toyota Central Res & Dev Lab Inc | Lithium secondary battery and manufacture thereof |
| US6156457A (en) * | 1997-03-11 | 2000-12-05 | Kabushiki Kaisha Toshiba | Lithium secondary battery and method for manufacturing a negative electrode |
| JPH1125975A (en) * | 1997-07-02 | 1999-01-29 | Toyota Central Res & Dev Lab Inc | Negative electrode active material |
| JPH11120993A (en) * | 1997-10-17 | 1999-04-30 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| DE19839217C2 (en) * | 1998-08-28 | 2001-02-08 | Fraunhofer Ges Forschung | Pasty masses, layers and layer structures, cells and processes for their production |
| KR100359605B1 (en) * | 1999-10-13 | 2002-11-07 | 사단법인 고등기술연구원 연구조합 | Lithium secondary battery cathode composition, lithium secondary battery cathode and lithium secondary battery employing the same, and method for preparing the same |
| JP4274663B2 (en) * | 2000-02-17 | 2009-06-10 | 三菱重工業株式会社 | Nonaqueous electrolyte secondary battery |
-
2002
- 2002-04-24 DK DK200200615A patent/DK200200615A/en not_active Application Discontinuation
- 2002-04-24 FR FR0205144A patent/FR2833760B1/en not_active Expired - Lifetime
- 2002-04-25 DE DE10218510A patent/DE10218510B4/en not_active Expired - Lifetime
- 2002-04-25 GB GB0209424A patent/GB2383465B/en not_active Expired - Lifetime
- 2002-04-29 CN CNB02124684XA patent/CN1290209C/en not_active Expired - Lifetime
- 2002-05-01 CA CA2384494A patent/CA2384494C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1427490A (en) | 2003-07-02 |
| FR2833760A1 (en) | 2003-06-20 |
| GB2383465A (en) | 2003-06-25 |
| CN1290209C (en) | 2006-12-13 |
| GB0209424D0 (en) | 2002-06-05 |
| DK200200615A (en) | 2003-06-20 |
| CA2384494C (en) | 2016-11-15 |
| DE10218510B4 (en) | 2007-07-26 |
| FR2833760B1 (en) | 2011-03-25 |
| GB2383465B (en) | 2005-05-18 |
| DE10218510A1 (en) | 2003-07-10 |
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