CN1214554A - Negative active material for lithium ion battery, negative electrode using the same and lithium ion battery using the same - Google Patents
Negative active material for lithium ion battery, negative electrode using the same and lithium ion battery using the same Download PDFInfo
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- CN1214554A CN1214554A CN98124588A CN98124588A CN1214554A CN 1214554 A CN1214554 A CN 1214554A CN 98124588 A CN98124588 A CN 98124588A CN 98124588 A CN98124588 A CN 98124588A CN 1214554 A CN1214554 A CN 1214554A
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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
- H01M4/58—Selection 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
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- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
A negative active material for a lithium ion battery comprises 50-95 wt.% graphitic carbon fibers and 5-50 wt.% graphitic carbon particles.
Description
The application is based on the application No.97-51257 that submits at korean industrial property office 1997.10.6, and its content at this as a reference.
The present invention relates to the negative active core-shell material of lithium ion battery, more particularly, relate to by the graphite-based composite anode active material that constitutes of carbon fiber and graphitic carbon particle radially.
Usually crystalline carbon and amorphous carbon are used as the lithium ion battery negative active material.Crystalline carbon such as graphite provide a discharge voltage stably, but discharge capacity is less relatively.On the contrary, amorphous carbon such as soft carbon provide a relative big discharge capacity with hard carbon, but a step discharge voltage.Wherein, crystalline carbon is by preferred, because it has a relatively little irreversible capacity.
Crystalline carbon is divided into fibrous type graphite, ball-type graphite and granular pattern graphite.Fibrous type graphite is divided into the carbon fiber of isotropic pitch (pitch) base and the carbon fiber of anisotropy asphaltic base.The anisotropy asphalt base carbon fiber is divided into isotropism type, radial mode, onion type, 1 type and 2 types at random at random, as shown in Figure 6.
In the preparation negative electrode, from above-mentioned crystalline carbon material, only select one type material for use.But, in this case, in negative active core-shell material, produce a plurality of spaces.In order to address this problem, U.S. patent No.5273842 discloses a kind of carbonaceous material that classification distributes that has.When this carbonaceous material was applied to negative electrode, a large amount of carbonaceous materials were used.The time of preparation carbonaceous material is elongated.
The open No.93-283061 of Japan Patent discloses a kind of negative electrode by the carbon fiber preparation of adding a small amount of isotropic pitch base in the carbon granule of the about 20 μ m of average diameter.This negative electrode has a loose structure.Thereby electrolyte is easy to be dispersed in the loose structure in the fast charging and discharging reaction.Yet electrode has a less packed density.Therefore the contact area between negative active core-shell material and the current collector is little, the contact impedance height.Therefore, negative active core-shell material comes off from current collector in repeated charge-discharge cycles.In addition, the low and disengaging of the insertion efficient of isotropic pitch base carbon fibre lithium ion.Therefore, use the finite capacity of the battery of this electrode.
One of purpose of the present invention is to provide a kind of negative active core-shell material, and it can provide the big contact surface between higher electrode packed density and electrode and the current-collector.
Another purpose is to provide one by the negative electrode of this negative active core-shell material preparation and the lithium ion battery of this negative electrode preparation.
In order to realize these and other purposes, the invention provides a kind of negative active core-shell material that is used for lithium ion battery, it comprises 50-95wt% graphite-based carbon fiber and 5-50wt% graphitic carbon particle.
And, the invention provides the negative electrode that is used for lithium ion battery, it comprises current collector, negative active core-shell material and an adhesive.
In addition, the present invention is by using the lithium ion battery of this negative active core-shell material preparation.
By detailed description, will become more obviously, be easier to understand more complete understanding of the present invention, its much additional superiority below in conjunction with accompanying drawing.
Fig. 1 a is the negative electrode SEM photo of one embodiment of the invention;
Fig. 1 b is according to the schematic diagram of the negative electrode of embodiment of the present invention;
Fig. 2 a is the SEM photo according to the negative electrode of Comparative Examples 1;
Fig. 2 b is the schematic diagram according to the negative electrode of Comparative Examples 1;
Fig. 3 is a curve chart, shows respectively according to the graphite-based carbon fiber content of the negative electrode of embodiment 1-2 and Comparative Examples 1-3 and the relation between the resistivity;
Fig. 4 is a curve chart, shows respectively according to the charge and discharge cycles of the lithium ion battery of embodiment 1 and Comparative Examples 1 and the relation between the discharge capacity;
Fig. 5 is the profile according to the Coin shape lithium ion battery of one embodiment of the invention;
Fig. 6 a is the profile of isotropism type carbon fiber;
Fig. 6 b is the profile of radial mode carbon fiber;
Fig. 6 c is that onion type carbon fiber is a profile;
Fig. 6 d is the profile of 1 type carbon fiber at random; With
Fig. 6 e is that the stochastic pattern carbon fiber is a profile.
A preferred embodiment of the present invention will be described with reference to the drawings.
Negative active core-shell material according to the present invention comprises 50-95wt% graphite-based carbon fiber and 5-50wt % graphitic carbon particle.
By less than 50wt% graphite-based carbon fiber with the high packed density of negative electrode can not be provided greater than the negative active core-shell material that 50wt% graphite-based particle consists of.
Preferred graphite-based carbon fiber is radial mode graphite-based carbon fiber. Shown in Fig. 6 b, the graphite plane layer of radial mode graphite-based carbon fiber has outside edge. Thereby radial mode graphite-based carbon fiber is easy to realize insertion and the disengaging of lithium ion, and the battery of higher capacity can be provided.
The graphite-based carbon fiber preferably has the aspect ratio of diameter and the 3-100 μ m of 5-30 μ m. Have and be lower than 5 μ m diameters and aspect ratio and be less than the self discharge ratio that 3 carbon fiber has larger specific surface area and Geng Gao. Have greater than the diameter of 30 μ m and aspect ratio greater than 100 carbon fiber cause the lower packed density of negative electrode and battery than low capacity. In addition, from the situation of carbon fiber penetrating clapboard, the battery with this carbon fiber is easy to occur internal short-circuit. More preferably be, the diameter of graphite-based carbon fiber is 10-20 μ m, and its aspect ratio is 5-50.
Graphitic carbon particle has preferred diameter 3-10 μ m. Diameter is greater than the graphitic carbon particle of the 10 μ m space between the filling carbon fiber effectively. Thereby carbon granule causes the low packed density of negative electrode. Diameter demonstrates larger specific area less than the graphitic carbon particle of 3 μ m and than the polyelectrolyte reactivity. More preferably, the graphitic carbon particle diameter is 3-7 μ m. This graphitic carbon particle has preferred 1 * 10-3-5×10
-3The resistivity of Ω cm. Small size carbon granule with relative low-resistivity has the superiority of high conductivity and high charge-discharge efficient.
The method for preparing negative electrode is described now.
Can prepare a kind of slurry that is used for negative electrode by mixing above-mentioned negative active core-shell material, adhesive and solvent.Kynoar is preferably used as adhesive.The N-N-methyl-2-2-pyrrolidone N-is preferably used as solvent.Slurry is applied on the current collector, and is dried.A copper substrate preferably is used as current collector.Shown in Fig. 1 a and 1b, because carbon granule 3 space between the filling carbon fiber 1 effectively, this negative electrode has a higher packed density.Therefore, the contact area between negative active core-shell material and the current collector increases, and contact impedance reduces.Negative active core-shell material is not easy to separate from current collector in the reaction repeating to discharge and recharge.
Those skilled in the art can negative electrode of the present invention easy to manufacture and use, positive electrode, dividing plate and electrolytical lithium ion battery.Lithium ion battery preferably uses the transition metal such as the LiNi of lithiumation
xCo
1-xO
2(0.1≤x≤0.9), more preferably LiNi
xCo
1-xO
2(0.5≤x≤0.8) is as active positive electrode material.Lithium ion battery preferably uses lithium ion salt such as the LiPF in the dissolving ethylene carbonate
6And LiPF
4Nonaqueous electrolyte.And lithium ion battery can use lithium ion salt such as the LiPF in the mixture that dissolves ethylene carbonate and following solvent
6And LiPF
4Nonaqueous electrolyte, these solvents are from propylene carbonate, butylene carbonate, dimethyl carbonate, gamma-butyrolacton, sulfolane, 1,3-dioxalane, 2-methylfuran, oxolane, 1 are selected in 2-dimethoxy-ethane or the diethoxyethane.
1. the preparation of radial mode graphite-based carbon fiber
The first insoluble quinoline (QI) is removed from coal tar asphalt.Coal tar asphalt has multiple compound.In these compositions, a QI is a macromolecular compound.If QI is not removed from coal tar asphalt, the fusing point of coal tar asphalt uprises.The mesophase pitch of handling from this coal tar asphalt can not easily be pulled into has the suitable content and the fiber of structure.
The pitch of therefrom removing a QI converts a kind of anisotropy bulk density mesophase pitch to by being heated under 430 ℃ of nitrogen environments.Then, mesophase pitch is drawn as fiber.Fiber is through the processing of an oxidation-stabilized step.Oxidation-stabilized step is that it removes the fusing composition from fiber by heating under 350 ℃ of air ambients.More particularly, oxidation-stabilized is to introduce oxygen in fiber.The oxygen of introducing in fiber with hydrogen reaction, and reactant separates from fiber.By the circulation condensation, the fusing composition is given effect that keeps the fibrous type shape of carburising step of back from fiber separation.Oxidation-stabilized fiber is clayed into power, then 900-1400 ℃ of carbonization 1 hour.The fiber of carbonization at 2500-3000 ℃ by graphitization 0.5 hour.
2. the preparation of graphitic carbon particle
The one QI is removed from coal tar asphalt.The pitch of therefrom removing a QI converts a kind of anisotropy bulk density mesophase pitch to by being heated under 430 ℃ of nitrogen environments.Then, mesophase pitch is oxidized down stable at 350 ℃.Oxidation-stabilized pitch is clayed into power, then 900-1400 ℃ of carbonization 1 hour.The particle of carbonization at 2500-3000 ℃ by graphitization 0.5 hour.
3. the negative electrode for preparing a kind of composite anode active material and this composite anode active material of use
Radial mode graphite-based carbon fiber and graphite-based carbon fiber grain with weight ratio 90: 10 by roll-in-mixing 1 hour.Each carbon fiber and carbon granule have an intrinsic apparent density.Therefore, be difficult to mixed carbon fibre and carbon granule under solid state.In order to address this problem, carbon fiber and carbon granule are introduced into polyethylene-big envelope (envelope), and this polyethylene-big envelope is by the metallic roll roll-in then.Carbon fiber and carbon granule mix mixed by this roll-in.The roll-in blend mixture was dried 24 hours under 200 ℃ of vacuum states.Vacuum drying step is in order to remove moisture from composite anode active material.
By to contain weight ratio be 90: 10 add vacuum drying composite anode active material as the N-N-methyl-2-2-pyrrolidone N-of solvent with as the solution of the Kynoar of adhesive, the negative electrode active material slip is produced.Prepare negative electrode by the thick negative electrode active material slip of coating 18 μ m on the copper current current-collector.Negative electrode was 100 ℃ of vacuumizes 0.5 hour.Electrode after the vacuumize under the pressure of 30Kgf/cm by roll-in and be cut into the plectane that diameter is 16mm.
4.2016 the manufacturing of type Coin-shaped battery
Fig. 5 shows such Coin-shaped battery structure.The negative electrode that comprises negative active core-shell material 30 and copper current current-collector 1 is soldered on the stainless steel casing 5.The nickel current collector 1 of porous ' be soldered to and cover 35, lithium metal 30 are soldered to nickel current collector 1 ' be used as counterelectrode.Insulating washer 20 is loaded into and covers 35.Dissolving 1M LiPF
6Carbonic acid ethylidene ester and the mixture of dimethyl carbonate (1vol/1vol) be used as electrolyte 15.Microporous polypropylene membrane is used as dividing plate 25.
Except by preparing the composite anode active material, repeat embodiment 1 with 50: 50 hybrid radial types of weight ratio graphite-based carbon fiber and graphitic carbon particle.
Except comprising an aluminium current collector and LiNi
xCo
1-xO
2The positive electrode of (0.1≤x≤0.9) active material is used as outside the counterelectrode, repeats embodiment 1.
Embodiment 4
Except comprising an aluminium current collector and LiNi
xCo
1-xO
2The positive electrode of (0.5≤x≤0.8) active material is used as outside the counterelectrode, repeats embodiment 2.
Embodiment 5
Except comprising an aluminium current collector and LiNi
xCo
1-xO
2The positive electrode of (0.5≤x≤0.8) active material is used as outside the counterelectrode, repeats embodiment 1.
Comparative Examples 1
1. the preparation of radial mode graphite-based carbon fiber
The one QI is removed from coal tar asphalt.The pitch of therefrom removing a QI converts a kind of anisotropy bulk density mesophase pitch to by being heated under 430 ℃ of nitrogen environments.Then, mesophase pitch is drawn as fiber.This fiber quilt is through an oxidation-stabilized step.Oxidation-stabilized fiber is clayed into power, then 900-1400 ℃ of carbonization 1 hour.The fiber of carbonization at 2500-3000 ℃ by graphitization 0.5 hour.
2. the preparation of negative electrode
By to contain weight ratio be 90: 10 add negative active core-shell material as the N-N-methyl-2-2-pyrrolidone N-of solvent with as the solution of the Kynoar of adhesive, prepare a kind of negative electrode active material slip.By thick negative electrode of negative active core-shell material slurrying of coating 18 μ m on the copper current current-collector.The negative electrode quilt was 100 ℃ of vacuumizes 0.5 hour.Electrode after the vacuumize under the pressure of 30Kgf/cm by roll-in and be cut into the plectane that diameter is 16mm.
3.2016 the manufacturing of type Coin-shaped battery
The negative electrode that comprises negative active core-shell material and copper current current-collector is soldered to stainless steel casing.The nickel current collector of porous is soldered to and covers, and the lithium metal is soldered to the nickel current collector, is used as counterelectrode.Insulating washer is loaded into and covers.Dissolving 1MLiPF
6Carbonic acid ethylidene ester and the mixture (1vo/1vol) of dimethyl carbonate be used as electrolyte.Microporous polypropylene membrane is used as dividing plate.
Comparative Examples 2
1. the preparation of radial mode graphite-based carbon fiber
The one QI is removed from coal tar asphalt.The pitch of therefrom removing a QI converts a kind of anisotropy bulk density mesophase pitch to by being heated under 430 ℃ of nitrogen environments.Then, mesophase pitch is drawn as fiber.This fiber quilt is through an oxidation-stabilized step.Oxidation-stabilized fiber is clayed into power, then 900-1400 ℃ of carbonization 1 hour.The fiber of carbonization at 2500-3000 ℃ by graphitization 0.5 hour.
2. the preparation of graphitic carbon particle
The one QI is removed from coal tar asphalt.The pitch of therefrom removing a QI converts a kind of anisotropy bulk density mesophase pitch to by being heated under 430 ℃ of nitrogen environments.Then, mesophase pitch is oxidized stable at 350 ℃.Oxidation-stabilized pitch is clayed into power, then 900-1400 ℃ of carbonization 1 hour.The particle of carbonization at 2500-3000 ℃ by graphitization 0.5 hour.
3. the negative electrode for preparing composite anode active material and this negative active core-shell material of use
Radial mode graphite-based carbon fiber and graphitic carbon particle were mixed 1 hour by roll-in with weight ratio 10: 90.The mixture that roll-in mixes under 200 ℃ of vacuum states dry 24 hours.
By to contain weight ratio be 90: 10 add vacuum drying negative active core-shell material as the N-N-methyl-2-2-pyrrolidone N-of solvent with as the solution of the Kynoar of adhesive, prepare a kind of negative electrode active material slip.By negative electrode of negative electrode active material slip preparation that coating 18 μ m are thick on the copper current current-collector.The negative electrode quilt was 100 ℃ of vacuumizes 0.5 hour.Electrode after the vacuumize under the pressure of 30Kgf/cm by roll-in and be cut into the plectane that diameter is 16mm.
4.2016 the manufacturing of type Coin-shaped battery
The negative electrode that comprises negative active core-shell material and copper current current-collector is soldered to stainless steel casing.The nickel current collector of porous is soldered to and covers, and the lithium metal is soldered to the nickel current collector, is used as counterelectrode.Insulating washer is loaded into lid.Dissolving 1M LiPF
6Carbonic acid ethylidene ester and the mixture (1vo/1vol) of dimethyl carbonate be used as electrolyte.Microporous polypropylene membrane is used as dividing plate.
Comparative Examples 3
1. the preparation of graphitic carbon particle
The one QI is removed from coal tar asphalt.The pitch of therefrom removing a QI converts a kind of anisotropy bulk density mesophase pitch to by being heated under 430 ℃ of nitrogen environments.Then, mesophase pitch is oxidized stable at 350 ℃.Oxidation-stabilized pitch is clayed into power, then 900-1400 ℃ of carbonization 1 hour.The particle of carbonization at 2500-3000 ℃ by graphitization 0.5 hour.
2. the preparation of negative electrode
By to contain weight ratio be 90: 10 add vacuum drying negative active core-shell material as the N-N-methyl-2-2-pyrrolidone N-of solvent with as the solution of the Kynoar of adhesive, prepare a kind of negative electrode active material slip.By thick negative electrode of negative active core-shell material slurrying of coating 18 μ m on the copper current current-collector.The negative electrode quilt was 100 ℃ of vacuumizes 0.5 hour.Electrode after the vacuumize under the pressure of 30Kgf/cm by roll-in and be cut into the plectane that diameter is 16mm.
3.2016 the manufacturing of type Coin-shaped battery
The negative electrode that comprises negative active core-shell material and copper current current-collector is soldered to stainless steel casing.The nickel current collector of porous is soldered to and covers, and the lithium metal is soldered to the nickel current collector, is used as counterelectrode.Insulating washer is loaded into lid.Dissolving 1M LiPF
6Carbonic acid ethylidene ester and the mixture (1vo/1vol) of dimethyl carbonate be used as electrolyte.Microporous polypropylene membrane is used as dividing plate.
Fig. 1 a and Fig. 2 a show a SEM photo according to embodiment 1 and Comparative Examples 1 respectively.(Fig. 1 electrode a) is compared with the electrode of Comparative Examples 2 has higher packed density to embodiment 1.Thereby the electrode of embodiment 1 has bigger contact area between current collector and the negative active core-shell material and lower contact impedance.Consequently, the problem from current collector transfer negative active core-shell material is overcome.
Fig. 3 shows the resistivity of the electrode of embodiment 1, embodiment 2, Comparative Examples 1, Comparative Examples 2 and Comparative Examples 3.The resistivity of electrode is measured by Van der Paw method.As shown in Figure 3, the amount of and carbon granule big when the amount of carbon fiber hour, it is big that the resistivity of electrode becomes.The electrode of embodiment 1 and embodiment 2 is compared with the electrode of Comparative Examples 1 has a less resistivity.Therefore, the electrode of example 1 and example 2 has bigger conductivity and charge/discharge efficient.By only using carbon granule, Comparative Examples 3 has a lower resistivity and a higher conductivity, but has a lower charge/discharge efficient.
Fig. 4 shows the charge/discharge result according to the battery of embodiment 1 and Comparative Examples 1.As shown in Figure 4, compare with Comparative Examples 1, embodiment 1 has a bigger discharge capacity, a better height ratio charge/discharge characteristics and a better cycle life.
Table 1 shows according to the electrode of embodiment 1 and Comparative Examples 1 and the various characteristics of battery.The capacity of battery is measured at 0.2C.The starting efficiency of battery is the percentage of initial discharge capacity and initial charge capacity.In addition, the reversible capacity of table 1 is an initial discharge capacity.
(table 1)
| The packed density of electrode | The starting efficiency of battery | The reversible capacity of battery | The resistivity of | |
| Embodiment | ||||
| 1 | ?1.65g/cm 3 | ????93.5％ | 32mAh/g | 1.291Ω·cm |
| Comparative Examples 1 | ?1.44g/cm 3 | ????92.4％ | 297mAh/g | 2.007Ω·cm |
As shown in table 1, embodiment 1 has the higher packed density and the low resistivity of electrode.And embodiment 1 has a bigger reversible capacity and starting efficiency, that is, and and the charge/discharge efficient of battery.
Owing to describe the present invention in detail with reference to preferred embodiment, those skilled in the art can carry out various modification and replacement in the situation of spirit of the present invention that does not break away from the claim defined and protection range.
Claims (7)
1. be used for the negative active core-shell material of lithium ion battery, comprise:
The graphite-based carbon fiber of 50-95wt%; With
The graphitic carbon particle of 5-50wt%.
2. according to the negative active core-shell material that is used for lithium ion battery of claim 1, wherein the graphite-based carbon fiber is the radial mode carbon fiber.
3. according to the negative active core-shell material that is used for lithium ion battery of claim 1, wherein the graphite-based carbon fiber has the diameter of 5-30 μ m and the aspect ratio of 3-100.
4. according to the negative active core-shell material that is used for lithium ion battery of claim 1, wherein graphitic carbon particle has the diameter of 3-10 μ m.
5. according to the negative active core-shell material that is used for lithium ion battery of claim 1, wherein graphitic carbon particle has 1 * 10
-3-5 * 10
-3The resistivity of Ω cm.
6. be used for the negative electrode of lithium ion battery, comprise:
A current collector;
Negative active core-shell material with graphitic carbon particle of the graphite-based carbon fiber of 50-95wt% and 5-50wt%; With
Adhesive.
7. the lithium ion battery of negative active core-shell material preparation that has the graphitic carbon particle of the graphite-based carbon fiber of 50-95wt% and 5-50wt% by use.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970051257A KR19990030823A (en) | 1997-10-06 | 1997-10-06 | Anode active material for lithium ion secondary battery, negative electrode plate and lithium ion secondary battery manufactured using same |
| KR51257/97 | 1997-10-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1214554A true CN1214554A (en) | 1999-04-21 |
Family
ID=19522278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98124588A Pending CN1214554A (en) | 1997-10-06 | 1998-10-06 | Negative active material for lithium ion battery, negative electrode using the same and lithium ion battery using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH11191408A (en) |
| KR (1) | KR19990030823A (en) |
| CN (1) | CN1214554A (en) |
| DE (1) | DE19846015A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100433423C (en) * | 2004-04-12 | 2008-11-12 | 三星Sdi株式会社 | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US7781103B2 (en) | 2004-04-12 | 2010-08-24 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| CN113272993A (en) * | 2018-12-28 | 2021-08-17 | 松下知识产权经营株式会社 | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| US11217783B2 (en) | 2017-12-22 | 2022-01-04 | Samsung Sdi Co., Ltd. | Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19938822A1 (en) * | 1999-08-19 | 2001-02-22 | Zae Bayern | Production of a lithium intercalation electrode used in batteries, PEM fuel cells and super capacitors comprises depositing a carbon layer on the surface of a skeleton material by introducing a carbon-containing gas into the material |
| JP4853692B2 (en) * | 2000-04-28 | 2012-01-11 | ソニー株式会社 | Graphite powder and method for producing the same |
| US6555271B1 (en) * | 2000-06-20 | 2003-04-29 | Graftech Inc. | Anode for lithium-ion battery |
| US7358010B2 (en) | 2002-07-22 | 2008-04-15 | Lodestar Inc. | Fluorinated carbon for metal/fluorinated carbon batteries |
| KR101031920B1 (en) * | 2008-04-29 | 2011-05-02 | 쇼와 덴코 가부시키가이샤 | Anode active material for lithium secondary battery and Method for preparing thereof and Lithium secondary battery containing the same for anode |
-
1997
- 1997-10-06 KR KR1019970051257A patent/KR19990030823A/en not_active Application Discontinuation
-
1998
- 1998-10-06 DE DE19846015A patent/DE19846015A1/en not_active Withdrawn
- 1998-10-06 JP JP10284241A patent/JPH11191408A/en active Pending
- 1998-10-06 CN CN98124588A patent/CN1214554A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100433423C (en) * | 2004-04-12 | 2008-11-12 | 三星Sdi株式会社 | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US7781103B2 (en) | 2004-04-12 | 2010-08-24 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US8110168B2 (en) | 2004-04-12 | 2012-02-07 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US8440352B2 (en) | 2004-04-12 | 2013-05-14 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US11217783B2 (en) | 2017-12-22 | 2022-01-04 | Samsung Sdi Co., Ltd. | Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode |
| CN113272993A (en) * | 2018-12-28 | 2021-08-17 | 松下知识产权经营株式会社 | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11191408A (en) | 1999-07-13 |
| KR19990030823A (en) | 1999-05-06 |
| DE19846015A1 (en) | 1999-04-08 |
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