Patent Application
20120241666
The present invention relates to a cathode active material precursor and a cathode active material for a rechargeable lithium battery including hollow nanofibrous carbon, and production method thereof, and more specifically, to a cathode active material precursor and a cathode active material for a rechargeable lithium battery including hollow nanofibrous carbon which can dramatically improve electric conductivity that is a shortcoming of the olivine-type lithium iron phosphate since cathode active material of an olivine-type lithium iron phosphate is charged outside or inside the hollow nanofibrous carbon and which can secure high energy density suitable for high-capacity batteries since the cathode active material is also charged inside the hollow nanofibrous carbon without wasting any space of the carbon, and production method thereof.
Demand for a rechargeable lithium battery as power supplies or power sources for electric vehicles, portable small electronic devices including cellular phones, portable PDAs (Personal Digital Assistances), notebook PCs (Personal Computers), MP3 players, and others has recently been rapidly increased. Accordingly, requirements in high capacity maintenance and lifecycle extension for a rechargeable lithium battery have also been increased.
Lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), and lithium metal composite oxide (LiNi1-xCoxO2 (0<x<1), Li(Ni—Co—Mn)O2, Li(Ni—Co—Al)O2 and others) are used as cathode active material for a rechargeable lithium battery. In addition, inexpensive and highly stable Spinel lithium manganese oxide (LiMn2O4), Olivine-type lithium iron phosphate (LiFePO4), lithium manganese phosphate (LiMnPO4), and lithium-iron composite phosphorous oxides (LixFe1-yMyPO4) are also receiving attention, wherein M is one or more selected from the group consisting of Mn, Cr, Co, Cu, Ni, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, 0.05≦x≦1.2, and 0≦y≦0.8.
However, although the cathode active material such as lithium cobalt oxide, lithium nickel oxide or lithium metal composite oxide is excellent in basic properties of batteries, the cathode active material is not sufficient in terms of thermal stability, overcharge safety and other properties. Therefore, the cathode active material has drawbacks that a safety device is additionally required to improve these properties, and the price of the active material itself is expensive. Furthermore, the lithium manganese oxide (LiMn2O4) has a fatal defect of bad lifecycle performance due to structural change called Jahn-Teller distortion caused by trivalent manganese cations. The lithium manganese oxide (LiMn2O4) does not sufficiently satisfy needs for high energy density due to low electric capacity. Accordingly, Olivine-type lithium iron phosphate and lithium manganese phosphate make it difficult to expect superior battery properties due to considerably low electric conductivity, and they do not sufficiently satisfy needs for high capacity either due to low operating potential.
Therefore, although various researches have been conducted to solve such problems, effective solutions have not been suggested yet until now.
For instance, International Patent Publication No. WO 2007/093856 regarding a preparation method of lithium manganese phosphate and Korean Patent Publication No. 2002-0027286 regarding a preparation method of an olivine-type lithium iron phosphate including iron alone or composite metal suggest a method of mixing carbons in order to improve load characteristics of an anode support by improving electric conductivity of the cathode active material when using, as cathode active material, an olivine-type lithium iron phosphate including manganese, iron, or composite metal. However, the effect of improving electric conductivity of lithium iron phosphate through mixing of a carbon composition is not enough.
Korean Patent Publication No. 10-2009-0053192 discloses an olivine-type lithium iron phosphate including manganese or iron alone, or composite metal. Specifically, this patent document suggests a method of improving electric conductivity of the cathode active material by growing nanofibrous carbon (carbon nanotubes or carbon nanofibers) having an oxygen-including functional group bonded to the surface of a cathode active material or a cathode active material. However, in this case, a process of growing nanofibrous carbon on the surface of active material is additionally required to result in lower productivity, and the cathode active material makes it difficult to expect improvement of energy density for application to high-capacity batteries.
Therefore, it is required to develop a method of producing cathode active material at a higher productivity which has a suitable energy density for application to high-capacity batteries, is excellent in safety as well as stability, maintains superior characteristics of the batteries, and enables cycle lives of the batteries to be extended.
Therefore, an object of the present invention is to provide a method of producing a cathode active material precursor for a rechargeable lithium battery having improved electric conductivity, energy density, stability and safety, and cycle life characteristics, and the cathode active material precursor for a rechargeable lithium battery produced by the same.
Another object of the present invention is to provide a method of producing a cathode active material for a rechargeable lithium battery having the above-mentioned properties, and the cathode active material for a rechargeable lithium battery produced by the same.
In order to solve the above problems, the present invention provides a composite cathode active material precursor for a rechargeable lithium battery including: hollow nanofibrous carbon; and a cathode active material precursor bonded to the skeleton of the hollow nanofibrous carbon, wherein the cathode active material precursor including a metal composite represented by the following Formula 1-1 or Formula 1-2.
Ma(PO4)b.nH2O (Formula 1-1)
M(OH)c.nH2O (Formula 1-2)
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, a represents a number of 1 to 3, b represents a number of 1 to 2, c represents a number of 2 to 6, and n represents a number of 0 to 10.
In one embodiment of the present invention, the cathode active material precursor is joined inside or outside the skeleton of the hollow nanofibrous carbon, and the hollow nanofibrous carbon is single-walled carbon nanotubes or multi-walled carbon nanotubes.
In one embodiment of the present invention, the hollow nanofibrous carbon has a diameter of 1 to 200 nm, and the metal composite is a crystal of which primary particles have an average particle diameter of 10 to 500 nm and of which secondary particles have an average particle diameter of 1 to 20 μm.
In one embodiment of the present invention, a composite cathode active material precursor includes: hollow nanofibrous carbon; and a cathode active material bonded to the skeleton of the hollow nanofibrous carbon, wherein the cathode active material is represented by the following Formula 2, and the cathode active material includes a carbon substance.
LidMPO4 (Formula 2)
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, and d represents a number of 0.5 to 1.5.
In one embodiment of the present invention, the cathode active material is an olivine-type lithium iron phosphate surrounded by a carbon substance, and the hollow nanofibrous carbon is single-walled carbon nanotubes or multi-walled carbon nanotubes.
In one embodiment of the present invention, the hollow nanofibrous carbon has a diameter of 1 to 200 nm, and the carbon substance is one or more selected from the group consisting of sucrose, citric acid, starch, oligosaccharide, and pitch.
In order to solve the foregoing problems, the present invention provides a production method of a composite cathode active material precursor for a rechargeable lithium battery including the steps of: (a) uniformly dispersing hollow nanofibrous carbon into an aqueous solution of metal salt including metal M of a metal composite of the following Formula 1-1 or Formula 1-2 to prepare a dispersion; (b) continuously flowing the dispersion and spraying an aqueous phosphate solution into a flow of the dispersion to form a metal composite precipitate of the following Formula 1-1 or Formula 1-2 represented by the following Chemical Formula 1, and flowing a solution including the precipitate into a reactor; (c) stirring a reaction system in the reactor or vibrating ultrasonic waves in the reaction system using Sonochemistry, thereby allowing the metal composite to be precipitated inside and outside the skeleton of the hollow nanofibrous carbon to form a cathode active material precursor; and (d) separating the cathode active material precursor to recover, wash, and dry the cathode active material precursor.
[Chemical Formula 1]
Ma(PO4)b. nH2O (Formula 1-1)
M(OH)c.nH2O (Formula 1-2)
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, a represents a number of 1 to 3, b represents a number of 1 to 2, c represents a number of 2 to 6, and n represents a number of 0 to 10.
In one embodiment of the present invention, the ultrasonic vibration is conducted at the multibubble sonoluminescence (MBSL) condition.
In order to solve the above-mentioned and other problems, the present invention provides a production method of a composite cathode active material including the steps of: (e) titrating a lithium salt and an aqueous carbon substance solution into an aqueous dispersion of the cathode active material precursor produced by the above-mentioned method to stir and mix those raw materials; (f) drying the mixture; and (g) calcining the dried mixture in an inert gas atmosphere to obtain a composite cathode active material, wherein the composite cathode active material includes hollow nanofibrous carbon, and a cathode active material bonded to the skeleton of the hollow nanofibrous carbon, and the cathode active material is represented by the following Formula 2.
LidMPO4 (Formula 2)
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, and d represents a number of 0.5 to 1.5.
In one embodiment of the present invention, the cathode active material is an olivine-type lithium iron phosphate which includes a carbon substance or which is surrounded by the carbon substance.
In order to solve another problems, the present invention provides a production method of a composite cathode active material further including the steps of: (e) milling a lithium salt and a cathode active material precursor produced by the above-mentioned method to mix those raw materials; and (f) calcining the mixture in an inert gas atmosphere to obtain a composite cathode active material, wherein the composite cathode active material includes hollow nanofibrous carbon, and a cathode active material bonded to the skeleton of the hollow nanofibrous carbon, and the cathode active material is represented by the following Chemical Formula 2.
LidMPO4 (Formula 2)
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, and d represents a number of 0.5 to 1.5.
In one embodiment of the present, the hollow nanofibrous carbon in the dispersion of the step (a) has a content of 0.1 to 10 weight % based on the total weight of the dispersion, and the hollow nanofibrous carbon is dispersed using a ultrasonic dispersion method or a high-pressure dispersion method in the step of preparing the dispersion of the step (a).
Furthermore, the step (b) is conducted in a method of spraying the aqueous phosphate solution into the dispersion using a spray nozzle while flowing the dispersion continuously and slowly using a metering pump, and the step (c) includes precipitation reaction of the crystal which is performed at a temperature range of 5 to 70° C. under an inert gas atmosphere.
In one embodiment of the present invention, the calcinations is performed at a temperature range of 400 to 800° C. under an inert gas atmosphere.
A composite cathode active material for a rechargeable lithium battery according to the present invention includes a carbon substance or is surrounded by the carbon substance, has conductivity, and also includes an olivine-type lithium iron phosphate as a cathode active material filled outside or inside hollow nanofibrous carbon. Therefore, the composite cathode active material for a rechargeable lithium battery can substantially improve electric conductivity that is a drawback of conventional olivine-type lithium iron phosphate, and can secure high energy density suitable for high-capacity batteries since the cathode active material is also filled inside the hollow nanofibrous carbon without wasting any space of the hollow nanofibrous carbon. Furthermore, the rechargeable lithium battery produced using a composite cathode active material for a rechargeable lithium battery of the present invention can improve cycle life characteristics of the batteries and improve stability and safety while maintaining basic electrical properties of the batteries. Furthermore, a production method of a composite cathode active material for a rechargeable lithium battery of the present invention is capable of producing a composite cathode active material having the above-mentioned properties at superior reproducibility and productivity.
Hereinafter, the foregoing composite cathode active material precursor, composite cathode active material, and a production method thereof of the present invention will be described in detail. However, the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided such that this disclosure will be thorough and complete and will fully convey the scope of the present invention to those skilled in the art.
In case that
[Chemical Formula 1]
Ma(PO4)b.nH2O (Formula 1-1)
M(OH)c.nH2O (Formula 1-2)
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, a represents a number of 1 to 3, b represents a number of 1 to 2, c represents a number of 2 to 6, and n represents a number of 0 to 10.
The hollow nanofibrous carbon 101 may be single-walled carbon nanotubes or multi-walled carbon nanotubes. The hollow nanofibrous carbon 101 has a diameter of 1 to 200 nm preferably, 1 to 100 nm more preferably, and 1 to 50 nm most preferably. Since the surface area of the olivine-type lithium iron phosphate is decreased if the hollow nanofibrous carbon has a diameter of exceeding 200 nm, effects of the olivine-type lithium iron phosphate are greatly lowered compared to when the hollow nanofibrous carbon has a diameter of not exceeding 200 nm. Accordingly, it is difficult to realize tap density or energy density suitable for application to a high capacity rechargeable lithium battery since secondary particles of the olivine-type lithium iron phosphate have an increased diameter. Primary particles of the metal phosphate, metal phosphate composite or hydrates thereof may have an average particle diameter of 10 to 500 nm, and secondary particles of the metal phosphate, metal phosphate composite or hydrates thereof may have an average particle diameter of 1 to 20 μm.
When
LidMPO4 [Chemical Formula 2]
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, and d represents a number of 0.5 to 1.5. The hollow nanofibrous carbon may be single-walled carbon nanotubes or multi-walled carbon nanotubes. The hollow nanofibrous carbon may have a diameter of 1 to 200 nm.
Referring to
First, hollow nanofibrous carbon is uniformly dispersed into an aqueous metal salt solution including metal M to prepare a dispersion, wherein M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb. Applicable metal salt forms may be selected from the group consisting of acetate, nitrate, sulfate, carbonate, citrate, phthalate, perchlorate, acetylacetonate, acrylate, formate, oxalate, halide, oxyhalide, boride, sulfide, alkoxide, ammonium, acetylacetone, and combinations thereof, and the metal salt forms are not particularly limited if they are industrially available. The hollow nanofibrous carbon has a content range of 0.1 to 10 weight % based on the total weight of the dispersion. The content of the hollow nanofibrous carbon may be preferably 0.1 to 5 weight %, more preferably 0.1 to 3 weight %. The hollow nanofibrous carbon may be dispersed using an ultrasonic dispersion method or a high-pressure dispersion method. Subsequently, precipitates of metal phosphate, composite metal phosphate or hydrates thereof represented by Formula 1-1 of Chemical Formula 1 are formed, or precipitates of metal hydroxide, composite metal hydroxide or hydrates thereof represented by Formula 1-2 of Chemical Formula 1 are formed by spraying an aqueous phosphate solution into a flow of the dispersion using, for example, a spray nozzle while continuously flowing the dispersion. Then, a solution including the precipitates is flown into a reactor.
[Chemical Formula 1]
Ma(PO4)b.nH2O (Formula 1-1)
M(OH)c.nH2O (Formula 1-2)
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, a represents a number of 1 to 3, b represents a number of 1 to 2, c represents a number of 2 to 6, and n represents a number of 0 to 10.
Phosphate for preparing metal phosphate, composite metal phosphate or hydrates thereof represented by Formula 1-1 of Chemical Formula 1 is added in an amount of 40 to 80% based on the total weight of metal salts in the dispersion. For instance, the phosphate is added in an amount according to the stoichiometric ratio. Examples of phosphate may include diammonium phosphate, sodium phosphate, monosodium phosphate, sodium pyrophosphate, sodium polyphosphate, calcium phosphate, and others. Although monosodium phosphate is more preferable from the viewpoint of the environmentally friendly process, industrially available phosphates are not particularly limited. Furthermore, a basic aqueous solution for preparing metal hydroxide, composite metal hydroxide or hydrates thereof represented by Formula 1-2 of Chemical Formula 1 is added in an amount of 15 to 70% based on the total weight of metal salts in the dispersion. For instance, the basic aqueous solution is added in an amount according to the stoichiometric ratio. Examples of hydroxide may include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and others. Although sodium hydroxide is more preferable, industrially available hydroxides are not particularly limited.
An operation of continuously flowing the dispersion may be carried out using, for example, a metering pump, and an operation of spraying an aqueous phosphate solution or aqueous basic solution into a flow of the dispersion may be performed by a method of spraying the aqueous phosphate solution or aqueous basic solution into the dispersion using, for example, a spray nozzle.
Subsequently, a reaction system is sufficiently stirred to a low speed in the reactor or ultrasonic waves are vibrated in the reaction system using Sonochemistry so that crystals of the metal phosphate, composite metal phosphate or hydrates thereof, or metal hydroxide, composite metal hydroxide or hydrates thereof are precipitated inside as well as outside the skeleton of the hollow nanofibrous carbon and bonded to the skeleton of the carbon as referred to
Therefore, a cathode active material precursor of a structure illustrated in
Primary particles of the obtained composite cathode active material precursor have an average particle diameter of 500 nm, preferably 200 nm, and more preferably 10 to 100 nm, and secondary particles of the composite cathode active material precursor have an average particle diameter of 1 to 20 microns, preferably 1 to 10 microns, and more preferably 1 to 5 microns in the state that crystals of metal phosphate or composite metal phosphate hydrate are commonly existed inside and outside hollow nanofibrous carbon. The particles are preferably formed in a spherical shape.
The aqueous lithium salt solution is mixed with the aqueous dispersion by stirring the aqueous lithium salt solution and the aqueous dispersion after titrating an aqueous lithium salt solution into an aqueous dispersion of a cathode active material precursor obtained by uniformly dispersing the composite cathode active material precursor obtained by the above-described method into water. Types of lithium salts suitable for preparing an olivine-type lithium iron phosphate of the Chemical Formula 2 using metal phosphate, composite metal phosphate or hydrates thereof represented by the Formula 1-1 of the Chemical Formula 1 may include acetate, nitrate, sulfate, carbonate, hydroxide, and phosphate such as lithium phosphate (Li3PO4), and the lithium salts are not particularly limited if they are industrially available. Furthermore, carbonaceous raw material is added in an aqueous dispersion of the cathode active material precursor to further increase electric conductivity of the composite anode material.
It is more preferable to use lithium hydroxide as a lithium salt in the wet process, and to use lithium carbonate or lithium phosphate as the lithium salt in the dry process. Suitable types of lithium salts suitable for preparing an olivine-type lithium iron phosphate of the Chemical Formula 2 using metal hydroxide, composite metal hydroxide or hydrates thereof represented by the Formula 1-2 of the Chemical Formula 1 may include lithium dihydrogen phosphate (LiH2PO4) and lithium phosphate, and the lithium salts are not particularly limited if they are industrially available. Furthermore, carbonaceous raw materials are added in an aqueous dispersion of the cathode active material precursor to further increase electric conductivity of the composite anode material. Suitable types of carbonaceous raw materials in the composite cathode active material may include sucrose, citric acid, oligosaccharide, starch and pitch, and the carbonaceous raw materials are not particularly limited if they are industrially available.
Consequently, a composite cathode active material according to one aspect of the present invention having a structure illustrated in
LidMPO4 [Chemical Formula 2]
where M represents one or more metal elements selected from the group consisting of Mn, Cr, Fe, Co, Ni, Cu, V, Mo, Ti, Zn, Al, Ga, Mg, B and Nb, and d represents a number of 0.5 to 1.5.
The cathode active material located inside or outside the carbon skeleton means a cathode active material precipitated and joined inside and outside a carbon substance such as carbon fibers.
First, the cathode active material precursor and lithium salt are mixed and milled to dry the mixture. Subsequently, a composite cathode active material according to one aspect of the present invention having a structure illustrated in
The production method of a composite cathode active material for a rechargeable lithium battery of the present invention is capable of producing a composite cathode active material having the above-mentioned properties at superior reproducibility and productivity.
A rechargeable lithium battery of the present invention is a rechargeable lithium battery in which the cathode includes the composite cathode active material according to the present invention in a lithium battery including an anode and a cathode enabling absorption and release of lithium ions, a separator interposed between the anode and cathode, and an electrolyte.
Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples. However, the following examples and comparative examples are provided for illustrative purposes only, and the scope of the present invention should not be limited thereto in any manner.
2 weight % of hollow nanofibrous carbon was uniformly dispersed into an aqueous solution of 0.3 M MnSO4H2O to prepare a dispersion. Dispersion of the hollow nanofibrous carbon performed using an ultrasonic dispersion method and a high-pressure dispersion method. Subsequently, the dispersion was continuously flown and 0.15 M Na3PO412H2O was sprayed into a flow of the dispersion to form Mn3(PO4)2 and remove Na from the salt using a centrifuge. The reaction system was sufficiently stirred to a low speed within the reactor or ultrasonic waves were vibrated in the reaction system using Sonochemistry for 1 hour after adding 0.1M LiOH, 0.05M LiH2PO4, sucrose and an aqueous citric acid solution including LiMnPO4, citric acid and sucrose at a ratio of 1:0.3:0.05 in an aqueous Mn3(PO4)2 solution that is the Na-removed salt and stirring the mixture. A circulation type constant temperature oven was used to maintain temperature inside the reactor to 30° C., control the operation frequency and intensity to 200 kHz and 300 W respectively, and constantly pressurize pressure inside the reactor to 3 atm. Argon gas was used inside the reactor. The reactant was dried at 150° C. in the spray dryer after the reaction. After drying the reactant, the resulting material was calcined at 700° C. for 24 hours in a nitrogen atmosphere.
2 weight % of hollow nanofibrous carbon was uniformly dispersed into an aqueous solution of 0.15 M MnSO4H2O to prepare a dispersion. Dispersion of the hollow nanofibrous carbon performed using an ultrasonic dispersion method and a high-pressure dispersion method. Subsequently, the dispersion was continuously flown and 0.3 M NaOH was sprayed into a flow of the dispersion to form Mn(OH)2 and remove Na from the salt using a centrifuge. The reaction system was sufficiently stirred to a low speed within the reactor or ultrasonic waves were vibrated in the reaction system using Sonochemistry for 1 hour after adding 0.1M LiOH, 0.05M LiH2PO4, sucrose and an aqueous citric acid solution including LiMnPO4, citric acid and sucrose at a ratio of 1:0.3:0.05 in an aqueous Mn(OH)2 solution that is the Na-removed salt and stirring the mixture. The subsequent process is performed in the same manner as in the example 1.
The cathode active material precursor produced in the example 1, and lithium salt and carbon black were mixed and ball-milled. The mixed composite cathode active material was calcined at 750° C. for 24 hours in a nitrogen atmosphere.
The cathode active material precursor was produced in the same method as in the example 1 except that sucrose and citric acid were not included in the example 1.
The cathode active material precursor was produced in the same method as in the example 1 except that sucrose, citric acid and CNT were not included in the example 1.
An observation of the shape of particles of the composite cathode active material produced in the examples was performed by FE-SEM (Field Emission-Scanning Electron Microscope), and the observation resulting images were shown in
Referring to
Particle size analysis of materials was conducted using a laser diffraction particle size analyzer. The samples of the corresponding particle sizes were designated as d10, d50, and d90 respectively after particle sizes of samples were confirmed at points at which cumulative volumes reached 10%, 50% and 90% respectively from the results of cumulative particle size distributions. The results of the particle size analysis were shown in the following Table 1.
Tap densities were calculated by injecting 50 g of materials into cylinders and measuring volumes of the cylinders after conducting 2,000 times of tapping, and the calculation results were shown in Table 1. It can be seen that the tap densities are decreased such that a carbon substance and CNT are included in the composite cathode active material. However, performances of the batteries were increased in the evaluation of batteries when the carbon substance and CNT are included in the composite cathode active material. Electrical conductivity, a problem of manganese, is thought to be improved to obtain good results in the battery evaluation.
Battery evaluation was conducted using a mixture obtained by weighing and mixing composite cathode active material, conductive material and binder to the weight ratio of 85:8:7. Electrode plate were manufactured by drying the coated slurry at 120° C. for 8 hours after preparing a slurry from the mixture and coating an aluminum thin film with the slurry. The manufactured electrode plates were pressed. Li metal was used as an anode, 2030-type coin cells were produced, and electrodes were used after producing it by dissolving 1M-LiPF6 into EC-DEC to the volume ratio of 1:1. Charging and discharging were carried out at the charging condition of 4.4 V and discharging condition of 3.0 V. Charging and discharging were conducted at 0.1 C in order to confirm the initial capacity, and cycle characteristics were checked by 0.5 C charging and 1 C discharging.
Referring to
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2009-0119919 | Dec 2009 | KR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/KR2010/008674 | 12/6/2010 | WO | 00 | 6/1/2012 |
