WO2007007581A1 - Matériau d’électrode positive pour batterie secondaire au lithium, procédé de fabrication de celui-ci, et matériau secondaire au lithium fabriqué à l’aide de celui-ci - Google Patents

Matériau d’électrode positive pour batterie secondaire au lithium, procédé de fabrication de celui-ci, et matériau secondaire au lithium fabriqué à l’aide de celui-ci Download PDF

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WO2007007581A1
WO2007007581A1 PCT/JP2006/313259 JP2006313259W WO2007007581A1 WO 2007007581 A1 WO2007007581 A1 WO 2007007581A1 JP 2006313259 W JP2006313259 W JP 2006313259W WO 2007007581 A1 WO2007007581 A1 WO 2007007581A1
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lithium
positive electrode
secondary battery
lithium secondary
electrode material
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PCT/JP2006/313259
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English (en)
Japanese (ja)
Inventor
Junji Akimoto
Junji Awaka
Yasuhiko Takahashi
Norihito Kijima
Mitsuharu Tabuchi
Kuniaki Tatsumi
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National Institute Of Advanced Industrial Science And Technology
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Priority to JP2007524578A priority Critical patent/JP5051770B2/ja
Publication of WO2007007581A1 publication Critical patent/WO2007007581A1/fr

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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode material for a lithium secondary battery, a method for producing the same, and a lithium secondary battery containing the material as a positive electrode active material.
  • lithium secondary batteries are mounted on portable electronic devices such as mobile phones and laptop computers.
  • lithium secondary batteries are expected to be put into practical use as large batteries for electric vehicles and power load leveling systems in the future, and their importance is increasing.
  • This lithium secondary battery can absorb and release lithium, such as a positive electrode using a lithium-containing transition metal composite oxide as an active material, and lithium metal, a lithium alloy, a metal oxide, or carbon.
  • the main components are a negative electrode using a possible material as an active material and a separator or solid electrolyte containing a non-aqueous electrolyte.
  • those considered as positive electrode active materials include layered rock salt type lithium cobalt oxide (LiCoO), layered rock salt type lithium nickel oxide (LiNiO),
  • the layered rock salt type lithium cobalt oxide LiCoO is a secondary battery using this as a positive electrode.
  • Battery performance such as the operating voltage of the battery (difference between the oxidation-reduction potential of the transition metal in the positive electrode and the oxidation-reduction potential of the negative electrode element), charge / discharge capacity (positive-electrode force desorption 'the amount of lithium that can be inserted), etc. Future demand is expected to increase further as a positive electrode constituent material for secondary batteries.
  • this compound contains cobalt, which is a rare metal, as a main component, it is one of the high cost factors of lithium secondary batteries. Furthermore, considering that about 20% of the world's global cobalt production is already used in the battery industry! /, It is possible to meet future demand growth with only LiCoO-capable cathode materials. Power is unknown It is.
  • the layered rock-salt type lithium nickel oxides using nickel cheaper than cobalt Li NiO is advantageous in terms of cost and capacity, and is a promising alternative to lithium cobalt oxides.
  • spinel type lithium manganese oxide LiMn O is more than cobalt and nickel.
  • Na MnO that has a one-dimensional tunnel structure is used as a starting point.
  • the compound has two types of tunnels with different sizes, so it is considered that ion diffusion is easy. For example, it is attracting attention as a positive electrode material with high output (capable of rapid charge / discharge). (See non-patent documents 1 and 2)
  • Patent Document 1 A. R. Armstrong, H. Huang, R. A. Jennings, P. G. Bruce, J. Mater. Chem., 8, 255-259 (1998)
  • Non-Patent Document 2 MM Doeff, A. Anapolsky, L. Edman, TJ Richardson, LC De Jonghe, J. Electrochem. Soc., 148, A230—A236 (2001) [0010] Therefore, it is a positive electrode material that can replace LiCoO in current lithium secondary batteries.
  • manganate-based positive electrode material that has a voltage flat part associated with trivalent and tetravalent oxidation-reduction reactions of manganese in the vicinity of 4 V, and that can be stably charged and discharged. Judgment criteria.
  • the present inventors can charge and discharge even in the 4V region and have a high capacity, a new lithium manganate, and a titanium substitution product (Li Mn Ti O (0.4 ⁇ x ⁇ 0.5, O ⁇ y ⁇ 0.56) was found and proposed earlier
  • the discharge capacity that can be realized with this material is about 60mAhZg in the initial discharge capacity and about 150mAhZg in the battery using the lithium negative electrode in the battery using the carbon negative electrode. In order to realize the theoretical capacity (193 mAhZg), further capacity improvement was necessary.
  • Patent Document 1 Japanese Patent Application No. 2004-065402
  • Patent Document 2 Japanese Patent Application No. 2004- 080970
  • Patent Document 3 Japanese Patent Application No. 2004 080971
  • a battery using lithium metal or a lithium alloy as a negative electrode material has been studied.
  • lithium metal or a lithium alloy as a negative electrode material
  • many studies have been conducted on “lithium polymer secondary batteries” using solid polymers as electrolytes.
  • a positive electrode material that can maximize its performance in the use of a lithium negative electrode, and the development of new materials with high voltage and high capacity is also being promoted.
  • the constituent elements of the positive electrode material oxide that can be used with various negative electrode materials are replaced with light elements with as low an atomic weight as possible for the purpose of reducing the weight of the battery itself. Development is also underway.
  • the above-mentioned spinel type lithium manganese oxide LiMn O is a battery using a lithium negative electrode.
  • the present invention solves the above-mentioned problems by using an inexpensive manganic acid raw material with less resource restrictions, and the above-described Li MnO type tunnel structure.
  • a new positive electrode material that can be charged and discharged stably with a high capacity in a working voltage range (about 4 V) equivalent to that of an existing practical positive electrode material, a manufacturing method thereof, and the positive electrode active material
  • the aim is to provide lithium secondary batteries using various negative electrode materials as substances.
  • the present invention provides a lithium manganese titanate positive electrode material, a production method thereof, and a lithium secondary battery using the same as shown in the following 1 to 6.
  • the chemical composition is expressed as Li Mn Ti O (0.5 ⁇ x ⁇ l, 0 ⁇ y ⁇ 0.56), and the crystal structure belongs to the orthorhombic system and has a tunnel structure occupied by lithium.
  • Lithium secondary battery positive electrode material that is also composed of lithium, mangan, titanium and oxygen power.
  • the lithium secondary battery according to 4 wherein a lithium or lithium alloy negative electrode is used as the negative electrode of the battery and can be stably charged and discharged in a voltage range of 4V.
  • an inexpensive raw material is used in a lithium secondary battery in a high operating voltage range (about 4V) equivalent to that of an existing lithium cobalt oxide-based positive electrode material.
  • a novel lithium manganese titanate positive electrode material can be obtained which can be charged and discharged stably and has a larger V and capacity than the existing positive electrode lithium manganate spinel.
  • the lithium secondary battery of the present invention using the above lithium manganese titanate positive electrode material has high voltage, high capacity, can exhibit excellent charge / discharge cycle characteristics, and is highly practical. Is.
  • FIG. 1 is a schematic diagram showing an example of a lithium secondary battery of the present invention.
  • FIG. 2 is an X-ray powder diffraction pattern of the positive electrode material of the present invention obtained in Examples 1 and 2.
  • FIG. 3 is a graph showing initial discharge characteristics of the batteries obtained in Example 1 and Comparative Example 1.
  • FIG. 4 is a graph showing initial discharge characteristics of the batteries obtained in Example 1 and Comparative Example 2.
  • FIG. 5 is a graph showing initial discharge characteristics of the batteries obtained in Example 3 and Comparative Examples 3 and 4.
  • FIG. 6 is a graph showing the discharge output characteristics of the battery obtained in Example 4.
  • Cathode material is the starting material Na Mn Ti l -y y 2 x l -y y
  • the ratio of titanium and titanium can be freely selected within the above composition range.
  • the Li Mn Ti O (0.5 ⁇ x ⁇ l, 0 ⁇ y ⁇ 0. 56) positive electrode material of the present invention is the above-mentioned prior application l -y y 2
  • the positive electrode material can be produced by subjecting the positive electrode material to a lithium insertion treatment.
  • the total amount of lithium in the positive electrode material can be 0.4 ⁇ x ⁇ l (however, X is larger than X in the starting material). It is preferable that 5 ⁇ x ⁇ l, especially 0.6 ⁇ x ⁇ l.
  • the positive electrode material of the present invention is capable of almost completely replacing sodium contained in the starting material with lithium by ion exchange treatment and lithium insertion treatment because of the crystal structure and the characteristics of the production process. It is characterized by that. However, it is generally known that such a method leaves significant or impure sodium. That is, the Li Mn Ti 2 O (0.5 ⁇ x ⁇ l, 0 ⁇ y ⁇ 0.56) positive electrode material of the present invention is
  • Impurity elements such as sodium may be contained within a range that does not impede the effect of the present invention, force S characterized by containing thium, manganese, titanium, and oxygen as main constituent elements.
  • the Li Mn Ti O (0.5 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.56) positive electrode material of the present invention includes manganese and titanium.
  • the amount of tongue can be freely selected within the range of 0 ⁇ y ⁇ 0.56. It has been confirmed in the prior application that replacing titanium has the effect of increasing the stability of the crystal structure and increasing the trivalent manganes that contribute to the charge / discharge reaction.
  • the amount of U and titanium is within the range of force 0 ⁇ y ⁇ 0.56, more preferably 0 ⁇ y ⁇ 0.4, which correlates with the amount of lithium in the structure.
  • the Li Mn Ti O (0.5 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.56) positive electrode material of the present invention is
  • the body has a Li MnO type tunnel structure, it hinders the effect of the present invention.
  • the Li Mn Ti O (0.5 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.56) positive electrode material of the present invention is the above-mentioned prior application.
  • lithium manganese titanium oxide Li Mn Ti O (0.40 ⁇ x ⁇ 0
  • Positive electrode material is sodium manganese titanium oxide Na Mn Ti O
  • the Na Mn Ti O (0.40 ⁇ x ⁇ 0.50, 0 ⁇ y ⁇ 0.56) compound is, for example, (1) sodium
  • the sodium raw material at least one of sodium (metallic sodium) and a sodium compound is used.
  • the sodium compound is not particularly limited as long as it contains sodium, for example, oxides such as Na 0 and Na O, salts such as Na CO and NaNO, NaO
  • manganese raw material at least one of manganese (metallic manganese) and a manganese compound is used.
  • Manganese compounds are not particularly limited as long as they contain manganese. For example, oxides such as MnO, MnO and MnO, salts such as MnCO and MnCl, M
  • hydroxides such as n (OH) and oxide hydroxides such as MnOOH.
  • n (OH) hydroxides
  • MnOOH oxide hydroxides
  • Mn 2 O, MnO and the like are preferable.
  • titanium raw material at least one of titanium (titanium metal) and a titanium compound is used.
  • the titanium compound is not particularly limited as long as it contains titanium, and examples thereof include oxides such as TiO, Ti 2 O, and TiO, and salts such as TiCl. Among these, special
  • TiO and the like are preferable.
  • the mixing ratio of the sodium raw material, the manganese raw material, and the titanium raw material is preferably such that the tunnel structure is formed. Specifically, Na Mn Ti O (0. 40 ⁇ x ⁇ 0. 50, 0 ⁇ y ⁇ 0.5.56)
  • the mixture may be such that the molar ratio of NaZ (Mn + Ti) is about 0.4 to 0.7, preferably 0.43 to 0.55.
  • the sodium contained in the product volatilizes and the amount of sodium in the product is often less than the charged composition. It is preferable to increase the amount charged.
  • the ratio of manganese and titanium can be selected arbitrarily within the range of (0 ⁇ y ⁇ 0.56).
  • the mixing method is not particularly limited as long as they can be mixed uniformly.
  • a known mixer such as a mixer may be used to mix them in a wet or dry manner.
  • the calcination temperature can be appropriately set according to the composition of the mixture, etc., but is usually about 600 to 1200 ° C., preferably 800 to 1050 ° C.
  • the firing atmosphere is not particularly limited, but usually it may be carried out in an acidic atmosphere or air.
  • the firing time can be appropriately changed according to the firing temperature and the like.
  • the cooling method is not particularly limited! Usually, natural cooling (cooling in the furnace) or slow cooling is sufficient! ,.
  • the fired product may be pulverized by a known method, if necessary, and the above firing step may be further performed. That is, in the method of the present invention, it is preferable that the mixture is repeatedly fired, gradually cooled and pulverized twice or more. The degree of grinding depends on the firing temperature. You can adjust it accordingly.
  • pulverized ⁇ ⁇ ⁇ ⁇ Ti O (0.40 ⁇ x ⁇ 0.50, 0 ⁇ y ⁇ 0.56) is dispersed in the molten salt containing the lithium-containing compound.
  • the molten salt a molten salt containing at least one of the salts that are melted at a low temperature such as lithium nitrate, lithium chloride, lithium bromide, and lithium iodide can be used.
  • a lithium compound and a powder of Na Mn Ti O fired product are mixed well.
  • the mixing ratio is usually 2 to 40, preferably 10 to 30 in terms of the molar ratio of Na in LiZNa Mn Ti 2 O in the molten salt.
  • the ion exchange temperature is 260 ° C to 330 ° C. If the ion exchange temperature is lower than 260 ° C, it is not completely exchanged for sodium potassium in Na Mn Ti O (0.40 x 0, 50, 0 ⁇ v ⁇ 0.56). A considerable amount of sodium remains in the product. On the other hand, when the ion exchange temperature is higher than 330 ° C, a part of the ion exchange temperature changes to a spinel structure, so that a uniform crystal structure cannot be obtained.
  • the treatment time is usually 2 to 20 hours, preferably 5 to 15 hours.
  • an ion exchange treatment method a treatment method in an organic solvent or an aqueous solution in which a lithium compound is dissolved is also suitable.
  • powdered Na Mn Ti O (0.40 ⁇ x ⁇ 0.50, 0 ⁇ y ⁇ 0.56) is put into an organic solvent in which a lithium-containing compound is dissolved, and the boiling point of the organic solvent Process at the following temperatures.
  • the treatment temperature is usually 30 ° C to 200 ° C, preferably 60 ° C to 180 ° C.
  • the treatment time is not particularly limited, but it is usually 5 to 50 hours, preferably 10 to 20 hours because a reaction time is required at a low temperature.
  • lithium-containing compound used in the present invention hydroxide, carbonate, acetate, nitrate, oxalate, halide, butyllithium and the like are preferable. Used in combination of two or more as required.
  • organic solvent used in the present invention higher alcohols such as hexanol and ethoxyethanol, ethers such as diethylene glycol monoethyl ether, or organic solvents having a boiling point of 140 ° C. or higher have good workability. It is preferable at this point. These may be used alone or in combination of two or more as required.
  • the concentration of the lithium-containing compound in the organic solvent or aqueous solution is usually 3 to 10 mol%, preferably 5 to 8 mol%.
  • the dispersion concentration of Na Mn Ti O in the organic solvent or aqueous solution is not particularly limited, but is 1 to 20 weight from the viewpoint of operability and economy.
  • the obtained product is washed thoroughly with distilled water, washed with methanol and ethanol, and then dried to obtain the target Li Mn Ti O (0.40 x
  • the washing method and drying method are not particularly limited, and a normal method may be used, or natural drying in a desiccator may be used.
  • Li Mn Ti O (0.40 ⁇ x ⁇ 0.50, 0 ⁇ y) produced by ion exchange treatment
  • ⁇ 0. 56 is further subjected to ion insertion treatment in a molten salt containing a lithium compound, or in an organic solvent or an aqueous solution, so that it has a Li MnO type crystal structure and has a chemical composition formula Li Mn Ti A compound represented by O (0. 5 ⁇ x ⁇ l, 0 ⁇ y ⁇ 0. 56) is obtained.
  • Li Mn Ti 2 O (0.40 ⁇ x ⁇ 0.50, 0 ⁇ y ⁇ 0.56) prepared in advance is dispersed in the molten salt containing the lithium-containing compound. It is preferable to apply a lithium insertion treatment.
  • the molten salt lithium nitrate is used, and as additives, lithium hydroxide, lithium iodide, lithium bromide, lithium oxide, lithium peroxide, lithium carbonate, lithium chloride, etc. I ’m going to give you this.
  • the additive and Li Mn Ti O powder are mixed well.
  • the mixing ratio is usually 0.01 to 10, preferably 0.1 to 3, in terms of the molar ratio of the additive ZLi Mn Ti 2 O in the molten salt.
  • the temperature of the lithium insertion treatment is 260 ° C to 330 ° C.
  • the processing temperature is higher than 330 ° C, a part of the processing temperature changes to a spinel structure, so that a uniform crystal structure cannot be obtained.
  • the treatment time is usually 2 to 20 hours, preferably 5 to 15 hours. Insert process several times, It is more effective to repeat 2 to 3 times.
  • a method for lithium insertion treatment a method of treating in an organic solvent or an aqueous solution in which a lithium compound is dissolved is also suitable.
  • Li Mn Ti O (0.40 ⁇ x ⁇ 0.50, 0 ⁇ y) previously ion-exchanged in an organic solvent in which a lithium-containing compound is dissolved.
  • the treatment temperature is usually 30 ° C to 200 ° C, preferably 60 ° C to 180 ° C.
  • the treatment time is not particularly limited, but is usually 5 to 50 hours, preferably 10 to 20 hours, because the reaction time is required at low temperatures.
  • the lithium-containing compound used in the present invention is preferably a hydroxide, oxide, peroxide, carbonate, acetate, nitrate, oxalate, halide, butyllithium, or the like. These are used alone or in combination of two or more as required.
  • organic solvent used in the present invention higher alcohols such as hexanol and ethoxyethanol, ethers such as diethylene alcohol monoethyl ether, or organic solvents having a boiling point of 140 ° C. or higher have workability. It is preferable at the point which is favorable. These may be used alone or in combination of two or more as required.
  • the concentration of the lithium-containing compound in the organic solvent or aqueous solution is usually 3 to 10 mol%, preferably 5 to 8 mol%. Also, Li Mn Ti in organic solvent or aqueous solution
  • the dispersion concentration of O is not particularly limited, but is 1 to 20 weight from the viewpoint of operability and economy.
  • the obtained product is washed thoroughly with distilled water, washed with methanol and ethanol, and then dried to obtain the target Li Mn Ti O (0.5 ⁇ x
  • the washing method and the drying method are not particularly limited, and a normal method may be used, or natural drying in a desiccator may be used.
  • the lithium secondary battery of the present invention uses the positive electrode material for a lithium secondary battery. That is, the battery element of a known lithium secondary battery (coin type, button type, cylindrical type, etc.) is used as it is, except that the lithium manganese titanate of the present invention is used as the positive electrode material. Can be adopted.
  • FIG. 1 is a schematic view showing an example in which the lithium secondary battery of the present invention is applied to a button type battery.
  • the button-type battery 1 includes a negative electrode terminal 2, a negative electrode 3, (separator + electrolyte) 4, insulating knocking 5, a positive electrode 6, and a positive electrode can 7.
  • a positive electrode mixture is prepared by blending the above-described lithium manganese titanate salt of the present invention with a conductive agent, a binder or the like as necessary, and this is used as a current collector.
  • the positive electrode can be produced by pressure bonding.
  • a stainless mesh, aluminum foil or the like can be preferably used.
  • acetylene black, ketjen black or the like can be preferably used.
  • the binder tetrafluoroethylene, polyvinylidene fluoride, or the like can be preferably used.
  • the composition of the lithium manganese titanate, the conductive agent, the binder, etc. in the positive electrode mixture is not particularly limited, but usually the conductive agent is about 1 to 30% by weight (preferably 5 to 25% by weight). ), About 0 to 30% by weight (preferably 3 to: LO% by weight) of the binder, and the remainder being lithium manganese titanate.
  • examples of the counter electrode with respect to the positive electrode include carbon-based materials such as black lead and MCMB (mesocarbon microbeads), alloy-based materials such as tin-based materials, lithium metal, and lithium alloys.
  • carbon-based materials such as black lead and MCMB (mesocarbon microbeads)
  • alloy-based materials such as tin-based materials, lithium metal, and lithium alloys.
  • a known material capable of occluding lithium can be used.
  • electrolytes can be used.
  • an electrolyte such as lithium perchlorate or lithium hexafluorophosphate was dissolved in a solvent such as ethylene carbonate (EC), dimethyl carbonate (DMC), propylene carbonate (PC), or jetyl carbonate (DEC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • PC propylene carbonate
  • DEC jetyl carbonate
  • An ion exchange treatment was performed for a treatment time of 10 hours, and the obtained solid was washed with distilled water, methanol, ethanol, etc. and dried to obtain a sample.
  • the amount of sodium remaining in the chemical formula is appropriate in the chemical formula of 22), and the molar ratio of NaZLi was 0.005.
  • the Li MnO-type orthorhombic tunnel was investigated by X-ray powder diffraction.
  • each lg shown in Table 1 was mixed well with 22 g of lithium nitrate and lg of lithium hydroxide, and then heated in air at 300 ° C for 10 hours to perform lithium insertion treatment. .
  • the obtained solid was washed with distilled water, methanol, ethanol or the like and dried to obtain a sample.
  • the amount of lithium X was about 0.59 ⁇ x ⁇ 0.72, confirming the insertion reaction.
  • the remaining sodium content is below the ICP detection limit (0.01 wt%), and the lithium insertion treatment further reduces the residual sodium content. It was confirmed that it is also effective in reducing this.
  • Sara Miko of the prepared samples, Li MnO
  • Table 2 shows the calculated lattice constants assuming 2 0. 44 2 structure. The change of lattice constant became clear due to the lithium insertion process compared to the original Li Mn Ti O (0.43 ⁇ x ⁇ 0.44).
  • a positive electrode was prepared by mixing 20 mg of a sample with 5 mg of acetylene black as a conductive agent and 0.5 mg of tetrafluoroethylene as a binder, lithium metal as the negative electrode material, and lithium hexafluorophosphate as ethylene carbonate (EC ) And jetyl carbonate (DEC) in a mixed solvent (volume ratio 1: 1) to produce a lithium secondary battery (coin-type cell) having the structure shown in FIG. The charge / discharge characteristics were measured.
  • the battery was produced according to a known cell configuration method.
  • the obtained lithium secondary battery was subjected to a charge / discharge test under a temperature condition of 30 ° C with a current density of 30mAZg (equivalent to 0.2C at C rate) and a cutoff potential of 4.8V-2.5V.
  • a current density of 30mAZg equivalent to 0.2C at C rate
  • a cutoff potential of 4.8V-2.5V As a result, it was found that an average discharge voltage of 3.55-3.64 V and an initial discharge capacity of 173 to 184 mAhZg can be stably charged and discharged.
  • the C rate is the discharge rate, that is, the magnitude of the discharge current
  • 1C is the amount of current that can be discharged in one hour, and is called the one-hour rate.
  • 1Ah 1C means 1A.
  • Fig. 3 (a) and (b) The initial discharge characteristics are shown in Fig. 3 (a) and (b).
  • Fig. 3 (c) the battery shown in Fig. 3 (c), which uses Li MnO before Li insertion as the positive electrode material, was similarly manufactured.
  • a positive electrode was produced in the same manner as in Example 1.
  • a lithium secondary battery was produced in the same manner as in Example 1 and a charge / discharge test was conducted.
  • the average discharge voltage was 3.54-3.60 V, the initial discharge capacity. It was confirmed that charging and discharging can be stably performed at 168 to 176 mAhZg.
  • Table 5 shows the initial charge capacity, initial discharge capacity, and average initial discharge voltage of each sample.
  • the sample was used as it is as a positive electrode material without being subjected to lithium insertion treatment, and a lithium secondary battery was produced and charged / discharged in the same manner as in Example 1. Both samples had an average discharge voltage of 3.48 to 3.54 V. The initial discharge capacity was about 141 to 156 mAhZg. For comparison, the initial discharge curve for Li MnO is shown in Fig. 3 (c).
  • the existing positive electrode lithium manganese spinel Li A lithium secondary battery was prepared in the same manner as in Example 1 using MnO as the positive electrode material.
  • the battery using this positive electrode material showed a large two-stage discharge curve characteristic of the spinel type.
  • the battery using Li MnO of the present invention obtained in Example 1 of the present invention as the positive electrode material has a voltage 'capacitance, as shown in Fig. 4 (a).
  • the superiority to the spinel material was confirmed from the viewpoint of energy density.
  • a positive electrode was prepared in the same manner as in Example 1, carbon (MCMB) as the negative electrode material, lithium hexafluorophosphate as ethylene carbonate (EC) and jetyl carbonate (D EC).
  • MCMB carbon
  • EC ethylene carbonate
  • D EC jetyl carbonate
  • a lithium ion secondary battery (coin-type cell) having the structure shown in FIG. 1 was prepared using a 1M solution dissolved in the above mixed solvent (volume ratio 1: 1) as an electrolytic solution, and its charge / discharge characteristics were measured.
  • the battery was produced according to a known cell configuration'assembly method.
  • the current density was 30mAZg under the temperature condition of 30 ° C.
  • Table 6 shows the initial charge capacity, initial discharge capacity, and average initial discharge voltage of each sample. The initial discharge characteristics of Li MnO
  • a positive electrode was prepared, and a lithium secondary battery was prepared and charged and discharged in the same manner as in Example 3. All of these batteries were stable at an average discharge voltage of 3.7 to 3.8 V and an initial discharge capacity of 100 to 119 mAhZg. It was confirmed that charging / discharging was possible. Table 7 shows the initial charge capacity, initial discharge capacity, and average initial discharge voltage of each sample.
  • the sample was used as it is as a positive electrode material without being subjected to lithium insertion treatment, and a lithium secondary battery was produced and charged / discharged in the same manner as in Example 3. Both samples had an average discharge voltage of 3.8 to 3.9 V. The initial discharge capacity was about 50-60mAhZg. For comparison, the initial discharge curve for Li MnO is shown in FIG. 5 (b).
  • Example 3 In order to clarify the characteristics of the lithium secondary battery using the novel lithium manganese titanate according to the present invention as the positive electrode material, the same as in Example 3 using the existing positive electrode lithium manganese spinel Li Mn O as the positive electrode material A lithium secondary battery was fabricated in the same conditions.
  • a positive electrode component similar to that in Example 1 was diluted with N-methyl 2-pyrrolidone (NMP) to form a slurry, and a coated electrode was produced according to a conventional method.
  • Table 8 shows the electrode physical properties of the produced positive electrode.
  • the positive electrode thus obtained MCMB as the negative electrode, polyethylene microporous membrane as the separator, and lithium secondary battery using lithium hexafluorophosphate electrolyte as in Example 1 (single layer aluminum laminate cell)
  • the output characteristics were measured.
  • the battery was produced according to a known cell configuration method.
  • the obtained lithium secondary battery was charged to 4.8 V at a constant current of 30 mAZg (equivalent to 0.2 C at C rate) at 25 ° C, and discharged at 30 mAZg and 60 mA / g, respectively.
  • 150 mAZg, 300 mAZg, 450 mA / g, 750 mA / g, 900 mA / g, and 1050 mA / g were used at constant currents up to 2.5 V to evaluate the output characteristics of each sample.
  • Figure 6 compares the capacity retention at each rate for Li MnO and Li MnO.
  • the capacity retention rate was about 40% at 1050mAZg equivalent to 7C.
  • Li MnO was found to have a high capacity retention of over 70%. From this

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L’invention concerne un nouveau matériau d’électrode positive que l’on peut obtenir une matière première d’oxyde de manganèse peu coûteuse de ressources peu limitées, qui possède une structure tunnel de type Li0,44MnO2, et que l’on charger et décharger en toute stabilité en grande quantité dans la fourchette de tension de fonctionnement équivalente à celle d’un matériau d’électrode positive pratique déjà existant (environ 4 V). Elle concerne aussi un processus de fabrication du matériau d’électrode positive. Elle concerne également une batterie secondaire au lithium comprenant le matériau comme matériau actif d’électrode positive et l'un quelconque des divers matériaux d’électrode négative. Elle porte sur un matériau d’électrode positive à utiliser dans une batterie secondaire au lithium, composé de lithium, de manganèse, de titane et d’oxygène et représenté par la composition chimique suivante : LixMn1-yTiYO2 (0,5 ≤ x ≤ 1, 0 ≤ y ≤ 0,56), ayant une structure cristalline orthorhombique, et possédant une structure de tunnel occupée par le lithium. Le matériau peut servir à construire une batterie secondaire au lithium.
PCT/JP2006/313259 2005-07-08 2006-07-04 Matériau d’électrode positive pour batterie secondaire au lithium, procédé de fabrication de celui-ci, et matériau secondaire au lithium fabriqué à l’aide de celui-ci WO2007007581A1 (fr)

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EP1837937A1 (fr) * 2006-03-20 2007-09-26 National Institute of Advanced Industrial Science and Technology Oxyde composite à base de manganèse au lithium et son procédé de préparation
WO2009066639A1 (fr) * 2007-11-22 2009-05-28 Sumitomo Chemical Company, Limited Oxyde métallique complexe sodium-manganèse, procédé pour sa fabrication, et batterie secondaire au sodium
JP2009227505A (ja) * 2008-03-21 2009-10-08 National Institute Of Advanced Industrial & Technology マンガン酸化物、電池用電極活物質、及びそれらの製造方法、並びに電池用電極活物質を用いた二次電池
JP2009227506A (ja) * 2008-03-21 2009-10-08 National Institute Of Advanced Industrial & Technology マンガン酸化物、二次電池用電極活物質、及びそれらの製造方法、並びに二次電池用電極活物質を用いたリチウム二次電池
JP2009242121A (ja) * 2008-03-28 2009-10-22 National Institute Of Advanced Industrial & Technology リチウムマンガン酸化物粉体粒子及びその製造方法、並びにそれを正極活物質として用いたリチウム二次電池

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EP1837937A1 (fr) * 2006-03-20 2007-09-26 National Institute of Advanced Industrial Science and Technology Oxyde composite à base de manganèse au lithium et son procédé de préparation
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JP2009227506A (ja) * 2008-03-21 2009-10-08 National Institute Of Advanced Industrial & Technology マンガン酸化物、二次電池用電極活物質、及びそれらの製造方法、並びに二次電池用電極活物質を用いたリチウム二次電池
JP2009242121A (ja) * 2008-03-28 2009-10-22 National Institute Of Advanced Industrial & Technology リチウムマンガン酸化物粉体粒子及びその製造方法、並びにそれを正極活物質として用いたリチウム二次電池

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