WO2014181436A1 - Matériau actif d'électrode positive pour des batteries rechargeables, et batterie rechargeable qui utilise ce dernier - Google Patents

Matériau actif d'électrode positive pour des batteries rechargeables, et batterie rechargeable qui utilise ce dernier Download PDF

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WO2014181436A1
WO2014181436A1 PCT/JP2013/063073 JP2013063073W WO2014181436A1 WO 2014181436 A1 WO2014181436 A1 WO 2014181436A1 JP 2013063073 W JP2013063073 W JP 2013063073W WO 2014181436 A1 WO2014181436 A1 WO 2014181436A1
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positive electrode
active material
electrode active
secondary battery
lithium
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PCT/JP2013/063073
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Japanese (ja)
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裕介 浅利
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株式会社日立製作所
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/38—Condensed phosphates
    • C01B25/42—Pyrophosphates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 active material for a secondary battery (rechargeable battery) such as a lithium ion battery and a secondary battery using the same.
  • a non-aqueous electrolyte secondary battery using an alkali metal such as lithium or sodium, an alkaline earth metal such as magnesium, or an alloy or compound thereof as a negative electrode active material is used to insert or intercalate negative electrode metal ions into the positive electrode active material.
  • the positive electrode active material and the negative electrode active material are referred to as a host, and the movable metal ion that is inserted or intercalated into the host is referred to as a guest.
  • a typical example of such a host / guest type non-aqueous electrolyte secondary battery is a lithium ion secondary battery.
  • Lithium ion secondary batteries have a higher energy density than conventional secondary batteries, and it is important to ensure the safety of the batteries.
  • the thermal stability of the positive electrode active material is one of the factors that determine the safety of lithium ion secondary batteries. When the temperature rises due to external factors such as heating, crushing, and short circuit and exceeds the thermal decomposition temperature of the positive electrode active material, heat generation or oxygen release occurs. The released oxygen may react with the combustible organic electrolyte or the negative electrode active material, and the safety of the battery may be impaired.
  • the problem of thermal stability is particularly noticeable in the charged state.
  • lithium ions are accumulated in the negative electrode active material, and the positive electrode active material is delithiated.
  • the delithiated positive electrode active material is in a chemically high energy state, and the thermal decomposition temperature is lower than in the lithiated state. For this reason, the positive electrode active material is likely to be deteriorated during high temperature storage and may be thermally decomposed as the temperature rises.
  • the structural instability increases in an overcharged state, so the thermal decomposition temperature decreases, Specifically, a thermal decomposition reaction occurs at a temperature of 200 ° C. or higher, and oxygen may be released due to a phase transition to a more stable structure by self-heating.
  • the spinel type metal oxide LiMn 2 O 4 manganese is eluted in the electrolyte during storage at high temperature, and the eluted manganese clogs the separator or forms a film on the negative electrode, resulting in battery resistance. May increase and the battery capacity may be reduced (see Patent Document 1).
  • a protection circuit In a lithium ion secondary battery using the positive electrode group as described above, it is necessary to prevent overcharge by a protection circuit in order to ensure reliability and safety. Such protection circuits and mechanical mechanisms occupy a considerable volume of current battery packs.
  • the olivine type compound LiFePO 4 is known to have high thermal stability.
  • the charge phase of LiFePO 4 , FePO 4 (Heterosite) is extremely stable with respect to heating, and even when heated to 620 ° C. or higher, it only undergoes a phase transition to the Quartz phase, which is more thermodynamically stable. Does not release.
  • the reason for exhibiting such high thermal stability is that the olivine type compound has a phosphate skeleton.
  • phosphorus (P) and oxygen (O) are connected by a strong covalent bond. That is, oxygen is fixed by phosphorus, oxygen release due to heat generation is difficult to occur, and heat stability is high.
  • a positive electrode active material containing a phosphoric acid type structure (P x O y ) is referred to as a polyanion positive electrode group.
  • polyanion positive electrode active materials olivic acid compound LiMPO 4 (for example, see Non-Patent Document 1), pyrophosphate compound Li 2 MP 2 O 7 (for example, see Patent Document 2 and Non-Patent Document 2) and the like have been proposed. ing.
  • the olivic acid compound LiMPO 4 is known as a part of a series of positive electrode active material groups represented by a polyanion (chemical formula (XO 4 ) y ⁇ ).
  • M Fe, Mn, Co, Ni or the like is used for the chemical composition formula LiMPO 4 .
  • olivine-type lithium-containing iron phosphate Li x FePO 4 , 0 ⁇ x ⁇ 1, hereinafter olivine Fe
  • the electric capacity when the pyrophosphate compound can use all the lithium ions for charging and discharging is called the theoretical electric capacity, which is 220 mAh / g.
  • the electrical capacity is summarized as follows.
  • the theoretical electric capacity of the olivine type positive electrode is 160 mAh / g, and the capacity can be used even in experiments.
  • the theoretical electric capacity of the pyrophosphate-type positive electrode is 220 mAh / g, but only 110 mAh / g, which is half of that, can be used in the experiment.
  • an electrochemical reaction for realizing a high capacity will be described with an olivine-type positive electrode active material LiFePO 4 as an example.
  • delithiation reaction is performed by applying a voltage to olivine-type LiFePO 4
  • FePO 4 is formed. Due to the electrical neutral principle, the system needs to maintain a state in which the sum of formal charges of all ionic species is zero through such a lithium elimination reaction.
  • the formal charge of each ion Lithium is ionized and the formal charge is a monovalent cation.
  • the phosphate group PO 4 is a trivalent anion. Therefore, Fe in LiFePO 4 is a divalent cation.
  • Fe in FePO 4 in a delithiated state is a trivalent cation.
  • the Fe ion is transitioned from a divalent cation to a trivalent cation by delithiation.
  • ions that change their valence in order to maintain the electrical neutral principle associated with lithium desorption are called redox centers and serve as a charge compensation mechanism in lithium batteries.
  • the present inventors have a problem, but as a positive electrode active material excellent in thermal stability, a polyanion positive electrode group containing a phosphoric acid type structure (P x O y ) is optimal.
  • a method for making M tetravalent in the pyrophosphate compound Li 2 MP 2 O 7 which is still expected to improve the discharge capacity, was studied.
  • Non-Patent Document 4 discloses a case where Fe is replaced with Mn. It is known that Mn is a multivalent ion. Specifically, the olivine-type positive electrode active material LiMnPO 4 is in a divalent cation state, the spinel structure Mn 3 O 4 is in a trivalent cation state, and the manganese dioxide MnO 2 is in a tetravalent state. It is in the state of cations. Therefore, Mn becomes a redox center in the elimination of lithium and is expected to be responsible for electrochemical reactions from divalent to tetravalent. However, in Non-Patent Document 4, as a result of experiments, Mn is not oxidized at all, and lithium is hardly desorbed. The reason why Mn does not work as a redox center is not known.
  • the transition metal element can change the valence from 2 to 4, the charge / discharge capacity can be increased.
  • a low-cost transition metal element can be used as the redox center, it can be a positive electrode material with high price competitiveness.
  • the pyrophosphate-type positive electrode active material can be charged and discharged using particles having a larger particle diameter (1 ⁇ m) than the olivine-type positive electrode material. That is, the micronization process can be omitted, and the restriction of the surface modification treatment is greatly relaxed, leading to a reduction in battery cost, ease of process management, and elimination of performance hindrance factors.
  • the conditions for the positive electrode active material that satisfies the requirements for safety and electric capacity are as follows: (1) Positive electrode active material having a pyrophosphoric acid type crystal structure with potentially large electric capacity (2) having a skeleton based on phosphoric acid with high thermal stability, and (3) being capable of detaching 1 mol or more of lithium.
  • Positive electrode active material having a pyrophosphoric acid type crystal structure with potentially large electric capacity (2) having a skeleton based on phosphoric acid with high thermal stability, and (3) being capable of detaching 1 mol or more of lithium.
  • pyrophosphate-type positive electrode active materials having these characteristics have not been realized yet.
  • the present invention has been proposed to improve the discharge capacity of a pyrophosphate-type positive electrode active material, and has an object of having a crystal structure having a pyroskeleton-type P 2 O 7 structure having a high thermal stability as a basic skeleton. It is another object of the present invention to provide a non-aqueous electrolyte positive electrode active material for a secondary battery with improved discharge capacity and a secondary battery using the same.
  • the chemical composition formula is Li 2-x M A0.5 M B0.5 P 2 O 7 , and M A and M B are each a transition metal element,
  • the combination is (V, Ti), (V, Mn), (V, Fe), (Ni, Mn), or (V, Cu), and
  • x is the main component of a compound in the range of 0 ⁇ x ⁇ 2. It is set as the positive electrode active material for secondary batteries characterized by these.
  • a secondary battery is characterized in that the positive electrode active material for a secondary battery is used in a positive electrode molded body.
  • the present invention it is possible to provide a positive electrode active material for a secondary battery that has high thermal stability and can improve the discharge capacity, and a secondary battery using the same.
  • the present inventor has repeatedly examined the lithium desorption structure and the valence change of the redox center associated with the charge / discharge reaction of the pyrophosphate-type positive electrode active material. It was found that 1 mol or more of lithium can be eliminated by constructing a compound with the use of. For example, to replace the combination of 0.5 mole of 0.5 mole and M B of 1 mole of two kinds of elements M A transition metal element M.
  • the present invention was born based on this new knowledge, has based on this new knowledge, has a highly safe pyrophosphate-type crystal structure, and a positive electrode for a lithium ion secondary battery having an electric capacity higher than 110 mAh / g. An active material can be provided. Details of the positive electrode active material design that leads to an improvement in charge / discharge capacity will be described below.
  • the crystal structure of the pyrophosphate-type positive electrode active material is shown in FIG.
  • the crystal structure consists of an alternating layered structure of lithium layers and transition metal layers along the bc plane.
  • the transition metal M has an MO x polyhedral structure with oxygen atoms coordinated around it.
  • the dotted polyhedron 6 in FIG. 1 has an MO x structure.
  • Reference numeral 1 denotes a Li1 site
  • reference numeral 2 denotes a Li2 site
  • reference numeral 3 denotes a Li3 site
  • reference numeral 4 denotes a Li4 site
  • reference numeral 5 denotes a phosphor polyhedron
  • reference numeral 7 denotes a unit cell.
  • MO 6 and MO 5 There are two types of MO x polyhedral structures, MO 6 and MO 5 .
  • the transition metal element M (21, 22) is located at the center of the polyhedron, and oxygen 23 is coordinated around it.
  • a metal site coordinated with six oxygens 23 is M1
  • a metal site coordinated with five oxygens is M2.
  • the hexacoordinate polyhedron M1O 6 and the pentacoordinate polyhedron M2O 5 form a cluster by covalently bonding edges.
  • Reference numeral 24 indicates a chemical bond between the transition metal and oxygen.
  • a phosphoric acid structure P 2 O 7 is arranged between polyhedral clusters in which MO 6 and MO 5 are bonded, and the clusters are joined to each other. For this reason, the transition metal layer can maintain a layered structure during charging and discharging.
  • Reference numeral 41 denotes a lone electron paired oxygen ion
  • reference numeral 42 denotes an oxygen ion
  • reference numeral 43 denotes a phosphoric acid polyhedron
  • reference numeral 44 denotes an iron oxide polyhedron (transition metal oxide polyhedron).
  • Lithium forms a two-dimensional network structure as shown in FIG. 3, and can be desorbed and inserted from the active material through this network during charging and discharging.
  • Reference numeral 31 denotes a Li3 site
  • reference numeral 32 denotes a Li4 site
  • reference numeral 33 denotes a unit cell.
  • transition metal oxides often have an MO 6 structure in which oxygen is six-coordinated.
  • the transition metal in a rock salt type oxide structure, the transition metal has an octahedral structure in which oxygen is coordinated to six.
  • the structure is similar to the six-coordinate structure in the pyrophosphate-type positive electrode active material, but the symmetry is lower in the pyrophosphate-type positive electrode active material, and the bond length between the transition metal and oxygen varies. Therefore, even if it has the same topology as the six-coordinate structure, the stability of the transition metal is considered to be different.
  • the transition metal oxide is pentacoordinated
  • the ⁇ -phase V 2 O 5 is known to have a 5-coordinated MO 5 structure. Therefore, the stable coordination number and the stable coordination state are generally not unique depending on the type of transition metal.
  • the pyrophosphate-type positive electrode active material Li 2 MP 2 O 7 since the same transition metal element M is assigned to the transition metal sites M1 and M2 having different coordination numbers, the two sites It is considered that the stability of M is different, and the ease of valence change is also different. That is, it is considered that there are combinations of transition metal sites and transition metal species that are difficult to change in valence due to differences in local structure.
  • the ionic radius of the transition metal element that becomes the oxidation-reduction center increases and decreases, so that the bond distance between the transition metal and oxygen ions increases and decreases, and the polyhedral structure changes.
  • the two types of polyhedrons MO 6 and MO 5 have edge covalent bonds, and the shape of the polyhedron is strongly bound to each other's geometric structure. In the case of having a polyhedral structure with such a strong constraint, it is considered that the structural change cannot sufficiently follow the valence change. That is, the present inventors considered that it is difficult for the MO x polyhedron to sufficiently relax the structure, and as a result, the valence cannot be changed with respect to lithium desorption.
  • the present inventors considered that there exist elements that are best suited to the respective coordination structures for the two types of transition metal sites, that is, M1 and M2, and that enable desired redox. Therefore, first, a crystal structure in which a transition metal element is applied to a transition metal site of (M1, M2) was searched by computer simulation. Specifically, six types of transition metals, Ti, V, Mn, Fe, Ni, and Cu, are considered and applied to the brute force (M1, M2) sites to improve the stability of the crystal structure with high accuracy. Theoretical prediction was made by using the one-principles density functional method.
  • the weight energy density is not disadvantageous when used as the positive electrode material of the lithium ion battery, so avoid heavy transition metal elements after Y, That is, among Sc to Zn, except for Sc that is not tetravalent, except for Cr that is expected to have a cost corresponding to environmental load, except for Co that is inferior in price competitiveness, and excluding Zn that is not expected to be redox with a stable element. is there.
  • the crystal structure of the chemical formula Li 2 M A0.5 M B0.5 P 2 O 7 prepared by applying the transition metal elements M A and M B to (M1 and M2), respectively, is theoretically predicted, and the result is obtained.
  • the crystal structure of a single type of transition metal element M A alone were prepared by applying the formula Li 2 M A P 2 O 7 with respect to (M1, M2) and theoretical predictions, the resulting total energy It is referred to as E a.
  • (M1, M2) with respect to only the crystal structure of Formula Li 2 M B P 2 O 7 created by applying the theory predicts single type of transition metal element M B, the resulting total energy Is EB .
  • the mixing energy defined in this way is obtained when Li 2 M A P 2 O 7 and Li 2 M B P 2 O 7 are separated and when Li 2 M A0.5 M B0.5 P 2 O 7 is present. It is a comparison of the energy when it exists. If E mix > 0, it indicates that it is more stable if it exists separately, and if E mix ⁇ 0, it indicates that it is more stable if it is mixed. .
  • (M1, M2) (Ti, Cu), (V, Ti), (V, Mn), (V, Fe), (Fe, Mn), (Ni, Mn), (Ni, Fe), ( It can be seen that a combination of (Cu, Ti) and (Cu, V) can be formed.
  • the present inventor investigated whether 1 mol or more of lithium can be extracted from the positive electrode material by a multi-electron reaction. Specifically, changes in the magnetic moment of transition metals were investigated using a high-accuracy first-principles density functional method. The reason why a multi-electron reaction is possible by this method is that the magnetic moment varies depending on the valence of the transition metal.
  • An oxidation reaction from Fe 2+ to Fe 3+ will be described as an example. Fe has 8 valence electrons, and its electron configuration is (4s) 2 (3d) 6 . When two electrons are desorbed from Fe to form a divalent cation, the electron configuration is (3d) 6 .
  • V the valence change of the transition metal element was examined with respect to the combination (V, Fe).
  • V the magnetic moment in the lithiated state Li 2 V 0.5 Fe 0.5 P 2 O 7 was examined.
  • V 3 ⁇ B
  • Fe was found to have become 4 ⁇ B. Since electron configuration of V is neutral state is (2s) 2 (3d) 3 , electron configuration by a divalent cation V 2+ (3d) 3, and the that the magnetic moment is 3.mu. B I understand. Therefore, in this state, V is a divalent cation. From the above discussion, it can be seen that Fe is a divalent cation like V.
  • V 0.5 Fe 0.5 P 2 O 7 in which all 2 mol of lithium was desorbed from this positive electrode material was prepared, and the magnetic moment was examined. Then V is 0 ⁇ B, Fe was found to have become 5 ⁇ B. V of 0Myu B has means that all of the valence are eliminated, a pentavalent cation V 5+. It can also be seen that Fe is a trivalent cation Fe 3+ from the magnetic moment.
  • the compound which is the positive electrode active material can be produced using a known general method, and various methods can be adopted as the method. Specifically, for example, in the case of Li 2 V 0.5 Fe 0.5 P 2 O 7 , iron oxide (Fe 2 O 3 ), a lithium phosphate compound, and vanadium oxide (V 2 O 5 ) are mixed, Synthesized by firing in an inert gas atmosphere such as argon.
  • the lithium phosphate compound is one selected from the group consisting of Li 3 PO 4 , Li 4 P 2 O 7 and LiPO 3 , for example.
  • the active material When producing a positive electrode for a non-aqueous electrolyte secondary battery using the positive electrode active material, the active material may be usually used in the form of powder, and the average particle size may be about 0.1 to 1 ⁇ m.
  • the average particle diameter is a value measured by, for example, a laser diffraction particle size distribution measuring apparatus.
  • a binder binder
  • the usage-amount of a electrically conductive agent etc.
  • the above active material alone or a mixture with other conventionally known positive electrode active materials may be used.
  • a known positive electrode preparation method may be used except that the positive electrode active material is used.
  • a powder of the above active material may be added to a known binder (polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, ethylene propylene diene polymer, styrene butadiene rubber, acrylonitrile butadiene rubber, fluoro rubber, polyvinyl acetate as necessary.
  • the obtained mixed powder may be pressure-formed on a support made of stainless steel or filled in a metal container.
  • the above mixed powder is mixed with an organic solvent (N-methylpyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran.
  • Etc. can also be produced by a method such as applying a slurry obtained by mixing with a metal substrate such as aluminum, nickel, stainless steel or copper.
  • the negative electrode is formed by applying a negative electrode mixture to a current collector made of copper or the like.
  • the negative electrode mixture includes an active material, a conductive material, a binder, and the like.
  • the active material of the negative electrode metallic lithium, a carbon material, a material capable of inserting lithium or forming a compound can be used, and a carbon material is particularly preferable.
  • the carbon material include graphites such as natural graphite and artificial graphite, and amorphous carbon such as coal-based coke, coal-based pitch carbide, petroleum-based coke, petroleum-based pitch carbide, and pitch-coke carbide.
  • these carbon materials are subjected to various surface treatments. These carbon materials can be used not only in one kind but also in combination of two or more kinds.
  • Examples of the material capable of inserting lithium or forming a compound include metals such as aluminum, tin, silicon, indium, gallium, and magnesium, alloys containing these elements, and metal oxides containing tin, silicon, and the like. . Furthermore, the composite material of the above-mentioned metal, an alloy, a metal oxide, and the carbon material of a graphite type or an amorphous carbon is mentioned.
  • FIG. 5 is a longitudinal sectional view of a coin-type lithium secondary battery which is an example of a battery using the positive electrode active material.
  • a battery having a diameter of 6.8 mm and a thickness of 2.1 mm was produced.
  • a positive electrode can 51 also serves as a positive electrode terminal and is made of stainless steel having excellent corrosion resistance.
  • the negative electrode can 52 also serves as a negative electrode terminal and is made of stainless steel made of the same material as the positive electrode can 51.
  • the gasket 53 insulates the positive electrode can 51 and the negative electrode can 52 and is made of polypropylene. Pitch is applied to the contact surface between the positive electrode can 51 and the gasket 53 and the contact surface between the negative electrode can 52 and the gasket 53.
  • a separator 55 made of a nonwoven fabric made of polypropylene is disposed between the positive electrode molded body (pellet) 54 and the negative electrode molded body (pellet) 56.
  • the electrolyte solution is infiltrated when the separator 55 is installed.
  • the shape of the secondary battery is not limited to the coin type, but may be a cylindrical shape obtained by winding an electrode, for example, an 18650 type. Alternatively, the electrodes may be stacked to form a square shape.
  • the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
  • the battery was manufactured and measured in a dry box under an argon atmosphere. The battery started from discharging for the first time, and then charged and discharged.
  • lithium carbonate Li 2 CO 3
  • ammonium dihydrogen phosphate NH 4 H 2 PO 4
  • iron oxide Fe 2 O 3 and vanadium oxide (V 2 O 5 )
  • a pyrophosphate positive electrode active material Li 2 V producing 0.5 Fe 0.5 P 2 O 7
  • citric acid In place of citric acid, other organic acids such as malic acid, tartaric acid, succinic acid and the like can be used.
  • the organic acid may be a mixture of a plurality of organic acids among citric acid, malic acid, tartaric acid, succinic acid, and the like.
  • the fired sample was pulverized for 1 hour using a meteor type ball mill (FRITSCH, Planetary micromill pulverisette 7). Thereafter, coarse particles of 50 ⁇ m or more are removed by sieving.
  • FRITSCH meteor type ball mill
  • the positive electrode active material for a secondary battery of a nonaqueous electrolyte having a crystal structure having a pyroskeleton-type P 2 O 7 structure with high thermal stability as a basic skeleton and improved discharge capacity can be provided.
  • Li 3 PO 4 , copper oxide (CuO), and vanadium oxide (V 2 O 5 ) are used as raw materials for preparing the positive electrode active material.
  • Li: Cu: V: P is 4: 1: 1: 4 in the raw material ratio, and wet pulverize and mix with a pulverizer.
  • the powder is dried and fired at 650 ° C. under an argon stream. It can be confirmed that the obtained sample is Li 2 V 0.5 Cu 0.5 P 2 O 7 .
  • V is trivalent in the lithiated state Li 2 V 0.5 Cu 0.5 P 2 O 7 . It was found to be a cation, and Cu was a monovalent cation. Further, in V 0.5 Cu 0.5 P 2 O 7 from which 2 mol of lithium has been eliminated from this crystal, V is a pentavalent cation, and Cu is a divalent cation. I understood. That is, it is expected that the capacity will be equivalent to 1.5 mol since charge compensation is possible up to 1.5 mol of electrons with 2 mol of lithium desorption.
  • the positive electrode active material for a secondary battery of a nonaqueous electrolyte having a crystal structure having a pyroskeleton-type P 2 O 7 structure with high thermal stability as a basic skeleton and improved discharge capacity can be provided.
  • Li 3 PO 4 , titanium oxide (TiO 2 ), and vanadium oxide (V 2 O 5 ) are used as raw materials for preparing the positive electrode active material.
  • Li: Ti: V: P is 4: 1: 1: 4 in the raw material ratio, and wet pulverize and mix with a pulverizer.
  • the powder is dried and fired at 700 ° C. under an argon stream. It can be confirmed that the obtained sample is Li 2 V 0.5 Ti 0.5 P 2 O 7 .
  • a discharge capacity of 170 mAh / g can be confirmed.
  • the positive electrode active material for a secondary battery of a nonaqueous electrolyte having a crystal structure having a pyroskeleton-type P 2 O 7 structure with high thermal stability as a basic skeleton and improved discharge capacity can be provided.
  • Li 3 PO 4 , manganese (III) (Mn 2 O 3 ), and vanadium oxide (V 2 O 5 ) are used as raw materials for preparing the positive electrode active material.
  • Li: Mn: V: P is 4: 1: 1: 4 in the raw material ratio, and wet pulverize and mix with a pulverizer.
  • the powder is dried and fired at 650 ° C. under an argon stream. It can be confirmed that the obtained sample is Li 2 V 0.5 Mn 0.5 P 2 O 7 .
  • a discharge capacity of 130 mAh / g can be confirmed.
  • the positive electrode active material for a secondary battery of a nonaqueous electrolyte having a crystal structure having a pyroskeleton-type P 2 O 7 structure with high thermal stability as a basic skeleton and improved discharge capacity can be provided.
  • Li 3 PO 4 , nickel oxide, and manganese (III) oxide (Mn 2 O 3 ) are used as raw materials for preparing the positive electrode active material.
  • Li: Ni: Mn: P is 4: 1: 1: 4 in the raw material ratio, and wet pulverize and mix with a pulverizer.
  • the powder is dried and fired at 700 ° C. under an argon stream. It can be confirmed that the obtained sample is Li 2 Ni 0.5 Mn 0.5 P 2 O 7 .
  • a charge / discharge test is performed using this active material, a discharge capacity of 130 mAh / g can be confirmed.
  • the positive electrode active material for a secondary battery of a nonaqueous electrolyte having a crystal structure having a pyroskeleton-type P 2 O 7 structure with high thermal stability as a basic skeleton and improved discharge capacity can be provided.

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Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à fournir un matériau actif d'électrode positive pour des batteries rechargeables qui présente une structure cristalline qui comprend une structure P2O7 de type pyrophosphate qui présente une stabilité thermique élevée comme squelette de base, et qui présente une meilleure capacité de décharge, ainsi qu'une batterie rechargeable qui utilise le matériau actif d'électrode positive pour des batteries rechargeables. La solution proposée consiste en un matériau actif d'électrode positive pour des batteries rechargeables qui contient Li2-xMA0,5MB0,5P2O7 (où 0 ≤ x ≤ 2) comme composant principal, ledit matériau étant configuré de telle sorte que MA et MB soient des métaux de transition, qui sont, de façon précise, (V et Ti), (V et Mn), (V et Fe), (Ni et Mn) ou (V et Cu).
PCT/JP2013/063073 2013-05-09 2013-05-09 Matériau actif d'électrode positive pour des batteries rechargeables, et batterie rechargeable qui utilise ce dernier WO2014181436A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017073367A (ja) * 2015-10-09 2017-04-13 富士通株式会社 二次電池用正極材料、及びその製造方法、並びにリチウムイオン二次電池
WO2019159262A1 (fr) * 2018-02-14 2019-08-22 富士通株式会社 Matériau d'électrode positive et son procédé de fabrication, pile utilisant ledit matériau d'électrode positive et son procédé de fabrication et équipement électronique utilisant une telle pile

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006523930A (ja) * 2003-04-08 2006-10-19 ヴァレンス　テクノロジー　インコーポレーテッド オリゴリン酸塩をベースとした電極活物質およびその製造方法
WO2011068255A1 (fr) * 2009-12-04 2011-06-09 国立大学法人 東京大学 Composé pyrophosphate et son procédé de production
WO2012164751A1 (fr) * 2011-06-03 2012-12-06 株式会社日立製作所 Substance d'anode pour accumulateur électrique, et accumulateur électrique utilisant cette substance
WO2013035222A1 (fr) * 2011-09-09 2013-03-14 株式会社日立製作所 Matériau d'électrode positive de batterie secondaire et batterie secondaire l'utilisant
WO2013035572A1 (fr) * 2011-09-05 2013-03-14 国立大学法人 東京大学 Procédé pour produire un composé d'oxoate contenant du lithium ou du sodium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006523930A (ja) * 2003-04-08 2006-10-19 ヴァレンス　テクノロジー　インコーポレーテッド オリゴリン酸塩をベースとした電極活物質およびその製造方法
WO2011068255A1 (fr) * 2009-12-04 2011-06-09 国立大学法人 東京大学 Composé pyrophosphate et son procédé de production
WO2012164751A1 (fr) * 2011-06-03 2012-12-06 株式会社日立製作所 Substance d'anode pour accumulateur électrique, et accumulateur électrique utilisant cette substance
WO2013035572A1 (fr) * 2011-09-05 2013-03-14 国立大学法人 東京大学 Procédé pour produire un composé d'oxoate contenant du lithium ou du sodium
WO2013035222A1 (fr) * 2011-09-09 2013-03-14 株式会社日立製作所 Matériau d'électrode positive de batterie secondaire et batterie secondaire l'utilisant

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017073367A (ja) * 2015-10-09 2017-04-13 富士通株式会社 二次電池用正極材料、及びその製造方法、並びにリチウムイオン二次電池
WO2019159262A1 (fr) * 2018-02-14 2019-08-22 富士通株式会社 Matériau d'électrode positive et son procédé de fabrication, pile utilisant ledit matériau d'électrode positive et son procédé de fabrication et équipement électronique utilisant une telle pile
JPWO2019159262A1 (ja) * 2018-02-14 2021-03-04 富士通株式会社 正極材料、及びその製造方法、前記正極材料を用いた電池及びその製造方法、並びに前記電池を用いた電子機器

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