WO2001078168A1 - Materiau d'electrode positive pour accumulateur au lithium, et accumulateur au lithium utilisant un tel materiau - Google Patents

Materiau d'electrode positive pour accumulateur au lithium, et accumulateur au lithium utilisant un tel materiau Download PDF

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Publication number
WO2001078168A1
WO2001078168A1 PCT/JP2001/001254 JP0101254W WO0178168A1 WO 2001078168 A1 WO2001078168 A1 WO 2001078168A1 JP 0101254 W JP0101254 W JP 0101254W WO 0178168 A1 WO0178168 A1 WO 0178168A1
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Prior art keywords
lithium
lithium secondary
positive electrode
manganese
less
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PCT/JP2001/001254
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English (en)
Japanese (ja)
Inventor
Tuyoshi Kinoshita
Keigi Suzuki
Ryuichi Nagase
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Japan Energy Corporation
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Publication of WO2001078168A1 publication Critical patent/WO2001078168A1/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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 having excellent high-temperature characteristics (high-temperature holding characteristics and high-temperature cycle characteristics) and excellent coating properties. It also relates to a lithium secondary battery having excellent battery characteristics.
  • the “lithium secondary battery” has a higher energy density compared to “Nikkol-dominium batteries” and “nickel-metal hydride batteries” and can further reduce the weight and extend the life of equipment. Is spreading rapidly.
  • this lithium secondary battery is formed by three basic elements: a “positive electrode”, a “negative electrode”, and an “electrolyte-retaining separator" interposed between the two electrodes.
  • the positive electrode and the negative electrode use a “slurry obtained by mixing and dispersing an active material, a conductive material, a binder, and, if necessary, a dispersant in a dispersion medium” to collect current such as a metal foil or a metal mesh. What is applied to the body is used.
  • lithium and cobalt complex oxide (UCoO,) have been mainly used.
  • the negative electrode active material a material capable of inserting and extracting lithium ions (for example, a carbon material such as coke-based carbon and graphite-based carbon) is used.
  • a carbon material such as coke-based carbon and graphite-based carbon
  • the conductive material a substance having electronic conductivity (eg, natural graphite, carbohydrate) Black, acetylene black, etc.), and fluorocarbon resins such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and hexafluoropropylene (HFP) as binders. These copolymers are used.
  • an organic solvent capable of dissolving the binder such as acetate, methylethylketone (MEK), tetrahydrofuran (THF), dimethylformamide, and dimethylacetamide , Tetramethylurea, trimethyl phosphate, N-methyl-2-pyrrolidone (NMP) and the like are used.
  • an organic solvent that can be replaced with an electrolyte after the slurry is applied to the current collector and formed into a film is appropriate.
  • an “organic solvent” that can be replaced with an electrolyte after the slurry is applied to the current collector and formed into a film is appropriate.
  • An “organic solvent” that can be replaced with an electrolyte after the slurry is applied to the current collector and formed into a film is appropriate.
  • An “organic solvent” that can be replaced with an electrolyte after the slurry is applied to the current collector and formed into a film is appropriate.
  • kind is preferred.
  • stainless steel, nickel, aluminum, titanium, copper perforated metal, and expanded metal are preferred, and these have been subjected to surface treatment. Materials can also be used.
  • the slurry required for coating is adjusted by kneading the above-mentioned active material, conductive material, binder, dispersion medium and plasticizer in a predetermined ratio.
  • Various coating methods such as gravure coating, blade coating, comma coating, and dip coating can be applied to the coating on the current collector.
  • liquid, polymer or solid electrolytes are known as electrolytes to be retained in the separator, but they are composed of a solvent and a lithium salt dissolved in the solvent.
  • Liquid type is often used.
  • the solvent in this case, polyethylene carbonate, ethylene carbonate, dimethyl sulfoxide, butyl lactone, sulfolane, 1,2-dimethoxy ethane, tetrahydrofuran, and getyl carbonate Bok, Mechiruechiruka Bone DOO, organic solvents such as dimethyl carbonate Natick bets are suitable, in the Matari lithium salt Li CF, S 0 ,, LiAsF LiCI 0 Li BF *, Li PF s And the like are preferred.
  • lithium-nickel composite oxides LiNiO,
  • Lithium 'manganese composite oxide ⁇ Li, + x M - ⁇ 4 (0 ⁇ x ⁇ 0.20) ⁇ has a high discharge voltage and a large interest from thermal stability in a charged state that relatively high I'm getting bathed.
  • Lithium 'manganese composite oxide ⁇ Li i + xMn, - x0 4 (0 ⁇ X ⁇ 0.20) ⁇ is electrolytic manganese dioxide (EMD) or chemical dioxide manganese (CMD) Moshiku is by heat-treating them It is synthesized by mixing the obtained “manganese oxide” such as Mn! 0 ,, ⁇ , ⁇ , etc. and “lithium compound” such as lithium carbonate at a predetermined ratio, and subjecting it to heat treatment.
  • EMD electrolytic manganese dioxide
  • CMD chemical dioxide manganese
  • the present inventors have provided a cathode material exhibiting excellent characteristics (various battery characteristics such as high-temperature cycle characteristics) for a lithium secondary battery, and also used the cathode material with excellent battery characteristics. Research to realize a lithium secondary battery.
  • lithium-manganese composite oxide ⁇ ,, + ⁇ , ,, (0 ⁇ X ⁇ 0.20) ⁇ lithium-manganese composite oxide
  • Lithium for the positive electrode active material is a “lithium manganese composite oxide.”
  • lithium secondary batteries can be used. Characteristics can be improved.
  • lithium-manganese composite oxides which are fine particles with an average particle diameter of 10 ⁇ m or less and whose particle shape is spherical, have been tested in the following series of trials. It was achieved at the end.
  • Electrolytic manganese dioxide EMD
  • CMD chemical manganese dioxide
  • ⁇ ⁇ , ⁇ , ⁇ , ⁇ are considered to have good fluidity and high packing density, but have a large particle size (maximum particle size of 100 m or more, average particle size of 25 or more).
  • maximum particle size 100 m or more, average particle size of 25 or more.
  • the resulting composite oxides also become irregularly shaped particles having a large particle size, and the density is not sufficient, so that satisfactory battery characteristics cannot be exhibited.
  • the final reaction is accelerated, and the final density is high (the density of 1.8 g / cm : can be sufficiently achieved).
  • lithium fine particles having an average particle diameter of 10 m or less and having a spherical particle shape can be realized by a new method.
  • Lithium-manganese composite oxides composed of spherical particles of ⁇ m or less have poor coating properties when applied to a current collector as a positive electrode material for lithium secondary batteries, and electrodes with conventional compositions It is clear that coating irregularities occur frequently when attempting to coat the current collector with a film-forming slurry. I got it.
  • an object of the present invention is to provide a positive electrode material for lithium secondary batteries which is excellent not only in high-temperature characteristics (high-temperature holding characteristics and high-temperature cycle characteristics) but also in coating properties.
  • the aim was to realize a lithium secondary battery that could maintain excellent battery characteristics without being particularly affected by environmental temperature. Disclosure of the invention
  • the present inventors have conducted further research to achieve the above object, and as a result, have obtained the following new knowledge.
  • Lithium as a positive electrode material for lithium secondary batteries ⁇
  • manganese composite oxides require finer particles to improve battery characteristics, coating properties greatly affect their specific surface area, and lithium ⁇ manganese composites. Even if the oxide is very fine particles, if its specific surface area is large, agglomerates will be formed during coating, which tends to cause unevenness, but lithium-manganese composite oxides with a small specific surface area are excellent. Coatability is ensured.
  • the specific surface area of the lithium 'manganese composite oxide is also greatly affected by the characteristics maintenance performance (retention of the positive electrode active material, cycle characteristics) of the lithium secondary battery using the lithium' manganese composite oxide as the cathode material. If the specific surface area is large, the "dissolution of Mn" becomes remarkable when left at high temperature in the charged state, and the retention characteristics and cycle characteristics tend to deteriorate.
  • the present invention has been made based on the above findings and the like, and provides the following positive electrode material for lithium secondary batteries and lithium secondary batteries.
  • the chemical composition consists of an average particle diameter of 1 0 or smaller particles represented by U 4 (0 ⁇ x ⁇ 0.20), and a specific surface area of the feature to be less than 1 m z / g, a lithium secondary Positive electrode material for secondary batteries.
  • a lithium secondary battery characterized in that a material having a specific surface area of not less than 1 ⁇ m and a specific surface area of not more than 1 m 2 / g is applied to a positive electrode material.
  • the present invention provides a method for producing an “average particle size of 10 m or less and a specific surface area of
  • this lithium-manganese composite can be used by using it as a positive electrode material for lithium secondary batteries.
  • a major feature is that the high-temperature characteristics (high-temperature holding characteristics and high-temperature cycle characteristics) of oxide-based lithium secondary batteries can be improved.
  • FIG. 2 is a graph comparing the cycle test results of the lithium batteries produced in the example and the comparative example.
  • FIG. 3 is an electron micrograph (SEM) of the fine-grained lithium-manganese composite oxide obtained in the comparative example.
  • Lithium ⁇ manganese composite oxide according to the present invention Li, + ⁇ ⁇ 1 ⁇ Bok x the value of X in OJ
  • the reason for limiting the "0 ⁇ X ⁇ 0.20" the scan when the value of X is a negative value Pinel structure
  • the discharge capacity when used as the positive electrode active material of a lithium secondary battery becomes 100 mAh / g or less.
  • the average particle size of the lithium-manganese composite oxide ⁇ Li, + ⁇ ⁇ 2 ⁇ (, (0 ⁇ X ⁇ 0.20) ⁇ is less than 10 m.
  • the specific surface area is 1 m 2 / g or less
  • the specific surface area exceeds 1 m 2 / g, this is The coating properties of the positive electrode material when applied to the current collector are worse than those with a small specific surface area. This is because the frequency of the generation of coating unevenness increases and the product quality tends to become unstable.
  • the lithium-manganese composite oxide also has a positive effect on lithium secondary battery characteristics maintenance performance (retention and cycling characteristics of the positive electrode active material).
  • the ratio If the surface area is greater than 1 m '/ g, "leaching of Mn" becomes remarkable when left at high temperature in a charged state, and the retention characteristics and cycle characteristics tend to deteriorate.
  • the process of producing lithium ⁇ manganese composite oxide by the reaction between manganese oxide and lithium compound extremely fine primary particles of lithium 'manganese composite oxide are generated, and then these primary particles are mutually bonded. It is considered that the secondary abscission is formed and the reaction is completed by the parallel progress of the bonding and the nucleation and grain growth. Therefore, when observing the obtained lithium-manganese composite oxide particles, it is recognized that the primary particles of the fine particles adhere to the surface of the large-grown secondary particles to form an integrated structure.
  • the composition, particle size, and specific surface area of the lithium-manganese composite oxide greatly affect the characteristics as a positive electrode material for a lithium secondary battery.
  • the particle size of the above primary particles (observed as fine particles attached to the surface of the grown secondary particles) in the composite oxide also increases through the specific surface area of the lithium-manganese composite as a positive electrode material for lithium secondary batteries. It has also been found that lithium ⁇ manganese composite oxides, in which the primary particles have a particle size of 1 am or more, are preferable in terms of coatability and battery characteristics.
  • Lithium-manganese composite oxide with an average particle size of 10 m or less and a specific surface area of 1 m '/ g or less ⁇ Li, + x Mn 2 — x O 4 (0 ⁇ x ⁇ 0.20) ⁇ "
  • Particle size is 1 or more lithium ⁇ manganese composite oxide has an average particle diameter of 10 ⁇ m or less manganese oxide (Nln0 2, Mn 2 0! Or Mn 3 0 4) and Lithium compound (carbonate Lithium etc. ) Can be manufactured by mixing and firing at a predetermined ratio, but it is important to carefully select the firing reaction raw materials through preliminary tests.
  • the firing temperature in this case is suitably in the range of 450 to 900 ° C.
  • the desired fine particle lithium ⁇ manganese composite oxide ⁇ Li, + ⁇ ⁇ ⁇ ⁇ ⁇ , (0 ⁇ x ⁇ 0.20) ⁇ in order to obtain the tap density as the oxidizing manganese is preferably calcined material 1.8 It is preferable to use those having a g / cm 5 or more, more preferably those having a spherical particle shape.
  • Manganese oxide as sintering raw material (Mn0 2, Mn z 0 5 , n, 0 4) is a fine ⁇ manganese can be made viable by heat treatment at in air 3 0 0 ° C or higher,
  • a more preferable manganese oxide raw material is to heat-treat manganese carbonate having a spherical particle shape in an atmosphere having an oxygen concentration of less than 15% (preferably in a nitrogen atmosphere) at a high temperature of 600 to 900 ° C.
  • second heat treatment at a lower temperature of 530 to 800 ° C in an atmosphere with an oxygen concentration of 15% or more.
  • This treatment method obtains fine particles Mn, 0, which are suitable for the production of lithium manganese composite oxides having a small specific surface area and a small specific surface area, and porous MnO 2 is generated by the first stage heat treatment.
  • manganese oxides of low oxidation state is generated without, this atmosphere of oxygen concentration when is generated MnO z multi porous and is 1 5% or more, preferably lithium ⁇ manganese composite oxide synthesis Hara There is no charge. If the heat treatment temperature at this time is lower than 600 ° C., a manganese oxide in a low oxidation state cannot be obtained effectively. When the temperature exceeds ° C, the formed manganese oxide is remarkably agglomerated and irregular particles increase, so that fine manganese oxide suitable as a raw material for lithium and manganese composite oxides for lithium secondary batteries cannot be obtained.
  • manganese oxide with a high density is generated, but it takes a long time to form ⁇ , ,, and a single phase at low oxygen concentration.
  • the second-stage heat treatment is performed to shorten the time Mns C converts Mn z O, the. If the treatment temperature in the second stage heat treatment is lower than 530 ° C or the oxygen concentration in the heat treatment atmosphere is lower than 15%, ⁇ ⁇ , ⁇ , contained ⁇ ⁇ , ⁇ , It may not be converted quickly to a long time, and it may take a long time to process or deteriorate the performance of the product.
  • the treatment temperature in the second stage heat treatment is greater than 8 0 0 ° C
  • manganese oxide high evening-up density can not be obtained by also obtained oxide agglutination significantly Do connexion fine manganese (here
  • the switching of the heat treatment temperature for converting ⁇ ⁇ , ⁇ , to ⁇ ⁇ ⁇ , ⁇ , may be performed at the same time as the generation of manganese oxide in a low oxidation state, and the oxygen concentration in the heat treatment atmosphere is not less than 15%. need not be a time of enhanced.
  • carbonated manganese raw material spherical applied to the method for producing manganese oxide are "manganese sulfate solution and bicarbonate Anmoniumu also is properly bicarbonate Na dissolved bets method of mixing Li um "and" Anmoniu ⁇ solution manganese metal containing ions, a method for venting a C 0 2 gas after a predetermined manganese concentration (No. 3 0 3 2 9 7 5 No.)) Can be built.
  • the chemical composition is Li, + x Mn 2 -x O, (0 ⁇ X ⁇ 0.20), the average particle size is 10; the particles are less than m, and the specific surface area is 1 m '/ g or less. Or lithium whose primary particles have a particle size of 1 m or more.
  • lithium-manganese composite oxide it is possible to realize a relatively inexpensive lithium secondary battery having excellent battery characteristics including the characteristic maintenance performance.
  • spherical manganese carbonate having an average particle size of 6.9 m was produced by dissolving metallic manganese in ammonium sulfate and introducing carbon dioxide gas into the solution to precipitate manganese carbonate.
  • the obtained manganese carbonate was used as a starting material, and this was subjected to a heat treatment at 800 ° C. for 1 hour in nitrogen, and oxygen was subsequently introduced into the atmosphere to reduce the oxygen concentration in the atmosphere to 20%. %, And heat treatment was further performed at 65 ° C. for 1 hour in this atmosphere to obtain ⁇ , ⁇ with an average particle size of 7 ⁇ m. After mixing 12 g of the fine particles ⁇ : 0, with 3.17 g of lithium carbonate, the mixture was fired in air at 750 ° C. for 10 hours.
  • the obtained powder of the compound was measured powder X-ray diffraction, Li, + x Mn 2 - was confirmed to be x O ⁇ single phase (0 ⁇ x ⁇ 0.20).
  • the lithium-manganese composite oxide (Li i + xMn! X O, (0 ⁇ X ⁇
  • the applicability was evaluated using the obtained lithium ⁇ manganese composite oxide as the positive electrode active material at 85 wt%, polyvinylidene fluoride as the binder 7 wt%, and acetylene black as the conductive material 8 wt%. It was weighed and added with acetone as a dispersion medium to form a slurry, which was then applied to an aluminum foil with a hand and iron to observe the applied state. As a result, a coating film having a uniform thickness was formed without generation of coating streaks, and it was confirmed that the positive electrode material of the present invention had excellent coatability.
  • the amount of Mn eluted was investigated by a method of measuring the amount of Mn eluted by inductively coupled plasma (ICP) after immersing the lithium-manganese composite oxide in an electrolyte solution at 55 ° C for 1 week.
  • ICP inductively coupled plasma
  • the measured amount of Mn eluted was 0.3 mg per 1 g of lithium ⁇ manganese composite oxide, which is remarkably improved compared to about 1 mg per 1 g of lithium ⁇ manganese composite oxide of the conventional material. It was confirmed that in the cathode material of the present invention, deterioration of high-temperature characteristics (elution of Mn into the electrolyte at a high temperature), which is the most concerned about Mn-based cathode materials, was remarkably suppressed.
  • lithium secondary batteries using the obtained lithium-manganese composite oxide as the positive electrode active material were also investigated.
  • the obtained lithium ⁇ manganese composite oxide 85% by weight of ⁇ Li ,, (0 ⁇ x ⁇ 0.20) ⁇ as active material, 8% by weight of acetylene black as conductive material, and 7 v »t% of polyvinylidene fluoride as binder Each was weighed, and acetonitrile was added as a dispersion medium to form a slurry. The slurry was applied on an aluminum foil, and then the solvent was evaporated to prepare a positive electrode of a lithium battery.
  • the lithium battery that satisfies the specified conditions of the present invention using lithium-manganese composite oxide as the positive electrode active material has high cycle characteristics at high temperature (55 ° C). It is clear that it is excellent, and it can also be confirmed that it has excellent retention characteristics in combination with the result of the above-mentioned Mn elution amount investigation.
  • the spherical fine-grained manganese carbonate having an average particle size of 6.9 m produced in the above example was used as a starting material, and this was subjected to a heat treatment at 650 X) in nitrogen for 1 hour, and subsequently into an atmosphere. Oxygen was introduced to change the oxygen concentration in the atmosphere to 20%, and heat treatment was further performed in the atmosphere at the same temperature of 65 ° C. for 1 hour to obtain Mn 20 , having an average particle size of 7 ⁇ m. Obtained.
  • the powder of the obtained compound was subjected to powder X-ray diffraction measurement. As a result, it was confirmed that L + ⁇ ⁇ ⁇ 2 - ⁇ , was a single phase (0 ⁇ x ⁇ 0.20).
  • the particle size of the primary particles was found to be less than 1 ⁇ m.
  • FIG. 3 is a SEM photograph of the lithium-manganese composite oxide obtained by this comparative example.
  • the coating properties were not sufficient, such as streaks in the coating film due to agglomerated particles during coating, and it was evaluated that there were difficulties in stably producing a coating film having a uniform thickness.
  • This low evaluation of the coating property is considered to be due to the formation of aggregated particles due to the large specific surface area of the lithium-manganese composite oxide.
  • the amount of Mn eluted at a high temperature in the obtained lithium-manganese composite oxide was measured by the same method as in the above-mentioned Example.
  • the measured elution amount of Mn was 0.7 mg per 1 g of lithium ⁇ manganese composite oxide, deteriorating the high-temperature characteristics of Mn-based cathode materials (Mn elution into electrolyte at high temperatures) was found to occur.
  • a lithium cell a lithium battery
  • a coin cell CR2032
  • the lithium secondary battery using the lithium ⁇ manganese composite oxide obtained in this comparative example as a positive electrode active material also has a specific surface area in terms of high-temperature retention characteristics. It is evident that it will be inferior to those using a lithium manganese composite oxide of 1 m 2 / g or less as the positive electrode active material.
  • the present invention it is possible to provide a cathode material for a lithium secondary battery having excellent coatability and excellent high-temperature characteristics, and realize a relatively inexpensive lithium secondary battery having excellent battery characteristics. It has an extremely useful effect on industry, such as enabling

Abstract

L'invention concerne un matériau d'électrode positive pour un accumulateur au lithium, caractérisé en ce qu'il comprend des particules possédant une composition chimique représentée par Li1+xMn2-xO4 (0 ≤ x ≤ 0,2), un diamètre de particule inférieur ou égal à 10 νm et une surface spécifique inférieure ou égale à 1 m2/g . Ce matériau peut aussi être caractérisé en ce qu'il comprend des particules qui, en plus de ce qui est mentionné ci-dessus, possèdent un diamètre de particules primaires constituant les particules ci-dessus égal ou supérieur à 1νm. Cette invention concerne également un accumulateur au lithium utilisant ce matériau d'électrode positive. Ce matériau d'électrode positive possède d'excellentes caractéristiques à haute température et d'applicabilité, et ainsi il peut être utilisé pour produire un accumulateur au lithium capable de conserver d'excellentes caractéristiques d'accumulation sans être affecté de manière significative par la température ambiante.
PCT/JP2001/001254 2000-04-11 2001-02-21 Materiau d'electrode positive pour accumulateur au lithium, et accumulateur au lithium utilisant un tel materiau WO2001078168A1 (fr)

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JP2000/115777 2000-04-11
JP2000115777A JP2001297767A (ja) 2000-04-11 2000-04-11 リチウム二次電池用正極材料及びリチウム二次電池

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JP4940530B2 (ja) * 2003-02-05 2012-05-30 日亜化学工業株式会社 非水電解液二次電池用正極活物質
JP2005221842A (ja) * 2004-02-06 2005-08-18 Lintec Corp マスクフィルム用部材、それを用いたマスクフィルムの製造方法及び感光性樹脂印刷版の製造方法

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JPH10218662A (ja) * 1997-02-03 1998-08-18 Toray Ind Inc ジルコニア焼結体の製造方法
JPH10321227A (ja) * 1997-05-23 1998-12-04 Asahi Chem Ind Co Ltd 非水電解質二次電池
JPH11121006A (ja) * 1997-10-17 1999-04-30 Toyota Central Res & Dev Lab Inc リチウム二次電池用正極活物質
JP2000012031A (ja) * 1997-06-13 2000-01-14 Hitachi Maxell Ltd 非水電解液二次電池用正極活物質およびその製造方法ならびに上記正極活物質を用いた非水電解液二次電池
JP2000090982A (ja) * 1998-07-14 2000-03-31 Denso Corp 非水電解質二次電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10218662A (ja) * 1997-02-03 1998-08-18 Toray Ind Inc ジルコニア焼結体の製造方法
JPH10321227A (ja) * 1997-05-23 1998-12-04 Asahi Chem Ind Co Ltd 非水電解質二次電池
JP2000012031A (ja) * 1997-06-13 2000-01-14 Hitachi Maxell Ltd 非水電解液二次電池用正極活物質およびその製造方法ならびに上記正極活物質を用いた非水電解液二次電池
JPH11121006A (ja) * 1997-10-17 1999-04-30 Toyota Central Res & Dev Lab Inc リチウム二次電池用正極活物質
JP2000090982A (ja) * 1998-07-14 2000-03-31 Denso Corp 非水電解質二次電池

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