WO2013035222A1 - Matériau d'électrode positive de batterie secondaire et batterie secondaire l'utilisant - Google Patents

Matériau d'électrode positive de batterie secondaire et batterie secondaire l'utilisant Download PDF

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WO2013035222A1
WO2013035222A1 PCT/JP2012/003452 JP2012003452W WO2013035222A1 WO 2013035222 A1 WO2013035222 A1 WO 2013035222A1 JP 2012003452 W JP2012003452 W JP 2012003452W WO 2013035222 A1 WO2013035222 A1 WO 2013035222A1
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positive electrode
secondary battery
electrode material
lithium
site
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PCT/JP2012/003452
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Japanese (ja)
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裕介 浅利
雄二 諏訪
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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
    • 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 secondary battery (rechargeable battery) and a secondary battery using the same.
  • Non-aqueous electrolyte secondary batteries that use alkaline metals such as lithium and sodium, alkaline earth metals such as magnesium, or alloys and compounds thereof as negative electrode materials insert or intercalate negative electrode metal ions into the positive electrode material. As a result, the electric capacity and charge reversibility are ensured.
  • the positive electrode material and the negative electrode material are called hosts, and the movable metal ions that are inserted and intercalated with respect to the host are called guests.
  • a typical example of such a host / guest type non-aqueous electrolyte secondary battery is a lithium ion secondary battery. Secondary batteries are disclosed in, for example, Patent Documents 1 and 2 and Non-Patent Documents 1 to 5.
  • Lithium ion secondary batteries have a higher energy density than conventional secondary batteries, and it is important to ensure battery safety.
  • the thermal stability of the positive electrode material is one of the factors that determine the safety of lithium ion secondary batteries.
  • heat generation or oxygen release occurs.
  • the released oxygen may react with the combustible organic electrolyte or the negative electrode 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 material, and the positive electrode material is delithiated.
  • the delithiated cathode material is chemically high in energy and has a lower pyrolysis temperature. For this reason, the positive electrode material is likely to deteriorate during storage at high temperatures, and may be thermally decomposed as the temperature rises.
  • layered rock salt type LiMO 2 (where M is a transition metal) which is a metal oxide type positive electrode material
  • LiCoO 2 a metal oxide type positive electrode material
  • the instability of the structure increases in an overcharged state.
  • a thermal decomposition reaction occurs at a temperature of °C or higher and oxygen is released by self-heating of the positive electrode material.
  • the spinel type metal oxide LiMn 2 O 4 manganese is eluted in the electrolyte during storage at high temperature, and the eluted manganese causes clogging of the separator or forms a film on the negative electrode.
  • the material may be deteriorated (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. If a secondary battery can be constituted by using a positive electrode material having high thermal stability, it becomes possible to realize intrinsic safety, simplify the battery mechanism, and improve the effective energy density.
  • 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.
  • the covalent bond between phosphorus and oxygen is an effective means for ensuring the thermal stability of the positive electrode material.
  • a positive electrode material excellent in thermal stability a polyanion positive electrode group containing a phosphoric acid type structure (P x O y ) is considered optimal.
  • polyanion positive electrode materials olivic acid compound LiMPO 4 (for example, see Non-patent Documents 1 and 5), pyrophosphate compound Li 2 MP 2 O 7 (for example, refer to Non-Patent Documents 2 to 4) and the like have been proposed. Yes. The detail regarding said phosphoric acid type positive electrode material is described below.
  • the olivic acid compound LiMPO 4 is known as part of a series of positive electrode materials 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 iron phosphate Li x FePO 4 , 0 ⁇ x ⁇ 1, hereinafter referred to as olivine Fe
  • the olivine-type LiFePO 4 has one atom of lithium per chemical composition formula and a theoretical electric capacity of 160 mAh / g. In experiments, almost all of the theoretical electric capacity can be used.
  • the pyrophosphate compound Li 2 MP 2 O 7 is a positive electrode material using Fe, Mn, Co or the like as M.
  • 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 theoretical electric capacity of the olivine-type positive electrode is 160 mAh / g, and the capacity can be used in experiments.
  • the theoretical electric capacity of the pyrophosphate-type positive electrode is 220 mAh / g, but only 110 mAh / g, which is half that, can be used in the experiment.
  • olivine-type positive electrode material LiFePO 4 As an example, olivine-type LiFePO 4 generally has an experimental electric capacity much lower than the theoretical capacity, it is known that the electric capacity increases by making the particles of the positive electrode material finer and reducing the particle diameter. The fine particle size necessary to operate as an electrode is 200 nm or less. In order to achieve the theoretical capacity of 160 mAh / g of LiFePO 4 , it is essential to further refine the positive electrode material.
  • the reason for the increase in capacity due to such micronization is related to the movement distance of the inserted lithium ions. If the particle size is large, the movement distance of lithium ions in the particles of the positive electrode material is long. In such cases, various impurities such as impurities in the particles, atomic position exchange defects (antisite defects), trapping of ions due to atomic vacancies, blocking of ion diffusion paths caused by mismatched surfaces such as grain boundaries, etc. There is a high possibility that the movement of lithium ions will be hindered by factors.
  • LiFePO 4 is known to have a one-dimensional lithium diffusion path.
  • Such a one-dimensional diffusion path is susceptible to the above-described crystal defects. That is, in the one-dimensional network-like phosphoric acid compound, lithium ions move one-dimensionally through the network in the material, so that the network is easily interrupted by crystal defects. Even if one crystal defect such as an antisite defect exists in one lithium diffusion network, the utilization rate of the network hardly changes. The fact that the network utilization rate does not change means that the electric capacity does not decrease.
  • Non-Patent Document 5 when two or more crystal defects occur, the lithium storage site between the defects in the one-dimensional network cannot be used, the network utilization rate decreases, and the electric capacity decreases.
  • the number of one-dimensional networks having two or more crystal defects increases rapidly as the particle size increases. For example, even when assuming 0.1% antisite defects, a particle size of 100 nm is required to achieve 100% network utilization.
  • the theoretical value of the network utilization rate decreases to 50%, resulting in a significant decrease in electric capacity (Non-Patent Document 5).
  • Non-patent Document 2 a one-electron theoretical capacity is achieved even for particles having a large size of about 1 ⁇ m without controlling the particle size such as micronization (Non-patent Document 2). If large particle size control is not required and particle size control is possible, the micronization process can be omitted, the surface modification treatment restrictions are greatly relaxed, battery costs are reduced, and process management is simplified. This leads to the elimination of performance impediment factors. If surface modification treatment with a conductive material such as graphite, which is essential for the olivine cathode material, is unnecessary, there are many advantages such as cost reduction and ease of process, as well as ease of electrode binding.
  • a conductive material such as graphite
  • the pyrophosphate-type positive electrode can be a positive electrode active material that exceeds the olivine-type positive electrode not only in electric capacity but also in productivity.
  • the dimension of the diffusion network of lithium ions in the pyrophosphate cathode material Li 2 MP 2 O 7 is expected to be greater than 1. That is, in Li 2 MP 2 O 7 , lithium ions have a layered structure, and are alternately laminated with transition metal layers, and it is expected that a lithium diffusion network having a dimension different from the olivine type exists.
  • the lithium ion diffusion network has a higher dimension than one.
  • the conditions for the positive electrode material satisfying the requirements for safety and electric capacity are: (1) a positive electrode material having a potentially large electric capacity pyrophosphoric acid crystal structure, and (2) heat. It has a highly stable skeleton based on phosphoric acid, and (3) has an electric capacity higher than 110 mAh / g.
  • pyrophosphate-type positive electrode materials having these characteristics have not been realized yet.
  • the present invention has been proposed to improve the discharge capacity of pyrophosphate-type positive electrode materials, and the object thereof is to have a crystal structure having a pyroskeleton-type P 2 O 7 structure having high thermal stability as a basic skeleton. Another object of the present invention is to provide a positive electrode material for a secondary battery capable of obtaining a high discharge capacity and a secondary battery using the same.
  • a positive electrode material for a secondary battery having a chemical composition formula of A 2-x MP 2 O 7- ⁇ Z ⁇ as a main component, wherein A is selected from alkali metals At least one element, M is at least one element selected from transition metals that can be a divalent or higher valent ion, Z is at least one element selected from halogen elements, and x is 0 ⁇ x ⁇ 2 and ⁇ is in a range of 0 ⁇ ⁇ 1.47.
  • the positive electrode material for the secondary battery is used for the positive electrode.
  • the positive electrode has a crystal structure having a pyrophosphate-type P 2 O 7 structure as a basic skeleton, and oxygen constituting the pyrophosphate-type P 2 O 7 structure
  • a part of oxygen constituting the pyrophosphate-type P 2 O 7 structure is substituted with a halogen element in a crystal structure having a pyroskeleton-type P 2 O 7 structure having a high thermal stability as a basic skeleton.
  • the present inventors have repeatedly studied lithium desorption and crystal structure change accompanying the charge / discharge reaction of the pyrophosphate-type positive electrode material.
  • the cause of the difficulty in desorption of lithium is the presence of single-bonded oxygen, and the instability of the crystal structure is reduced by substituting single-bonded oxygen with a different element, resulting in a higher charge / discharge capacity.
  • the positive electrode material design that leads to an improvement in charge / discharge capacity will be described below. Since lithium is the most practical, lithium will be described as an example, but any alkali metal can be used.
  • the crystal structure of the pyrophosphate-type positive electrode material is shown in FIG.
  • the crystal structure is a lithium layer and a transition metal layer along the bc plane (especially, transition metals that can be multivalent ions having two or more valences; V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, W
  • the transition metal M has an MO x polyhedral structure (corresponding to reference numeral 6) with oxygen atoms coordinated around it.
  • MO x polyhedron structures MO 6 and MO 5 , which take a cluster shape in which edges are covalently connected.
  • a phosphoric acid structure (polyhedron) P 2 O 7 (corresponding to reference numeral 5) 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.
  • the crystallographically independent lithium sites are the Li1 site 1, the Li2 site 2, the Li3 site 3 and the Li4 site 4, the lithium layer consisting only of the Li1 site 1 and the Li2 site 2, and only the LI3 site 3 and the Li4 site 4 Divided into lithium layers.
  • a lithium layer composed of the Li1 site 1 and the Li2 site 2 is defined as an A layer
  • a lithium layer composed of the Li3 site 3 and the Li4 site 4 is defined as a C layer.
  • the number of lithium sites contained in the A layer and the C layer is 8 in each unit cell 7, and the lithium density is equal.
  • the arrangement of lithium sites (lithium diffusion network shape) is different.
  • a lithium diffusion network of layer A is shown in FIG.
  • Reference numeral 21 denotes a Li1 site
  • reference numeral 22 denotes a Li2 site
  • reference numeral 23 denotes a unit cell.
  • Each lithium site is adjacent to the other three lithium sites.
  • the elementary process of lithium diffusion in the positive electrode is considered to be ion hopping from one lithium site to another adjacent lithium site. Therefore, the dimension of the lithium ion diffusion network can be determined by the number of adjacent sites. For example, in the well-known olivine-type positive electrode material LiFePO 4 , the number of adjacent lithium sites is 2, so it can be said that the lithium ion diffusion network has a one-dimensional topology.
  • the topology of the lithium ion diffusion network is considered to be two-dimensional.
  • the lithium diffusion path network of the C layer is shown in FIG.
  • Reference numeral 31 denotes a Li3 site
  • reference numeral 32 denotes a Li4 site
  • reference numeral 33 denotes a unit cell.
  • the number of adjacent lithium sites in the Li3 site 31 is 4, and the number of adjacent lithium sites in the Li4 site 32 is 3.
  • the topology of the lithium diffusion network is considered to be two-dimensional like the A layer.
  • the present inventors used a computer numerical analysis technique based on the first-principles calculation theory to determine pyrophosphoric acid.
  • the binding energy of lithium in was calculated.
  • the binding energy is an index of stabilization due to the binding of lithium to the lithium site, and 0 eV was used as a reference point in a negative electrode state (lithium ions intercalated with graphite).
  • the calculation results are shown in FIG.
  • the binding energy was 4.40 eV, 3.93 eV, 3.80 eV, and 3.61 eV. The higher the binding energy, the more difficult it is to extract lithium ions.
  • lithium ions in the A layer are difficult to extract, and lithium ions in the C layer are easy to extract. Since the number of lithium ions contained in the A layer and the C layer is the same, it is suggested that the one-electron reaction that has been confirmed at present is lithium desorption into the C layer.
  • the energy difference between the Li1 site 21 and the Li2 site 22 is 0.47 eV.
  • the lithium diffusion network FIG. 2
  • the lithium ions must pass through both the Li1 site 21 and the Li2 site 22 in order to diffuse. That is, at least 0.47 eV or more is required for the diffusion of lithium ions. This suggests that lithium ions cannot diffuse in the A layer unless they have high energy. It also means that the site related to the rate limiting of lithium ions in the A layer is the Li1 site 21.
  • the energy difference between the Li3 site 31 and the Li4 site 32 is 0.19 eV, which is much smaller than the energy difference in the A layer. That is, it is suggested that lithium ions are much more mobile in the C layer than in the A layer. This energy difference confirms that the one-electron reaction confirmed in the pyrophosphoric acid charging / discharging experiment occurs in the C layer.
  • the mechanism by which the Li1 site 21 controls the lithium ion diffusion in the A layer will be examined.
  • oxygen is coordinated to lithium.
  • four oxygen atoms were coordinated at the Li1 site 21, four oxygen atoms were coordinated at the Li2 site 22, five oxygen atoms were coordinated at the Li3 site 31, and four oxygen atoms were coordinated at the Li4 site 32.
  • Oxygen is responsible for adsorbing and immobilizing lithium.
  • the number of oxygen surrounding the lithium site is at most 4 or 5 at any site, and there is no significant difference. Therefore, the factor determining the adsorption energy of lithium ions is not the number of coordinated oxygen atoms but the chemical nature of the oxygen atoms.
  • Reference numeral 41 is an oxygen ion with a lone electron pair
  • reference numeral 42 is an oxygen ion
  • reference numeral 43 is a phosphoric acid (PO 4 ) polyhedron
  • reference numeral 44 is an iron oxide polyhedron (MOx polyhedron).
  • Oxygen occupies the apex position of the polyhedral structure.
  • oxygen atoms that are not coordinated to either MO 6 or MO 5 (corresponding to reference numeral 44).
  • Such an oxygen atom has only a single bond with phosphorus, and is considered to be extremely unstable during lithium desorption (charged state).
  • oxygen with lone pairs oxygen with lone pairs.
  • the lone pair of electrons not only affects the diffusion of lithium ions, but also affects the deterioration of the crystal structure.
  • the lone pair In the delithiated state, the lone pair is in a chemically unstable state, so it tries to stabilize by coordinating with surrounding iron ions.
  • MO 5 polyhedron MO 5 in which five oxygen atoms are coordinated with the transition metal
  • MO 6 is obtained , and the entire crystal structure is stabilized.
  • Stable spontaneously by changing the crystal structure without adsorbing lithium means that the positive electrode material has deteriorated.
  • the polyhedron becomes MO 6 in this way, lithium cannot be adsorbed when the battery is discharged, causing irreversible capacity. Therefore, in order to suppress the crystal structure deterioration, it is necessary to suppress the reactivity of the lone pair of electrons.
  • the present inventors have replaced the oxygen with lone pair (two hands) with a halogen element (one hand) to reduce the reactivity.
  • a halogen element one hand
  • the reactivity of the lone pair is suppressed, and the diffusibility of lithium ions
  • Z is a halogen element
  • fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and the like are suitable.
  • fluorine or chlorine is preferable as the ion having a size that does not destroy the crystal structure.
  • the amount of the halogen element Z to be added is ⁇ and the chemical composition formula of the pyrophosphate positive electrode substituted with the halogen element Z is expressed as Li 2 ⁇ x MP 2 O 7 ⁇ Z ⁇ , 0 ⁇ ⁇ 1. 47.
  • ⁇ is preferably 0.5 or less.
  • the compound which is the positive electrode material according to the present embodiment can be manufactured using a known general method, and various methods can be adopted as the method. Specifically, for example, in the case of Li 2 FeP 2 O 7- ⁇ F ⁇ , iron oxide (Fe 2 O 3 ), a lithium phosphate compound, and a lithium monofluorophosphate compound (Li 2 PO 3 F) are mixed. It is 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 material When producing a positive electrode for a secondary battery of a non-aqueous electrolyte using the positive electrode material according to the present embodiment, the material may be usually used in the form of powder, and the average particle diameter is about 0.1 to 1 ⁇ m. That's fine.
  • 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 material alone or a mixture with other conventionally known positive electrode materials may be used as long as predetermined positive electrode characteristics can be obtained as the positive electrode material.
  • the production of the positive electrode of the secondary battery according to the present embodiment may be performed in accordance with a known method for producing a positive electrode except that the positive electrode material is used.
  • powders of the above materials may be combined with known binders (polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, ethylene propylene diene polymer, styrene butadiene rubber, acrylonitrile butadiene rubber, fluoro rubber, polyvinyl acetate, Polymethylmethacrylate, polyethylene, nitrocellulose, etc.) and further mixed with known conductive materials (acetylene black, carbon, graphite, natural graphite, artificial graphite, needle coke, carbon nanotube, carbon nanohorn, graphene nanosheet, etc.) if necessary Thereafter, the obtained mixed powder may be pressure-formed on a support made of stainless steel or filled into a metal container.
  • the 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.
  • organic solvent N-methylpyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran.
  • the electrode of the secondary battery according to this embodiment can also be manufactured 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 a material, a conductive material, a binder, and the like.
  • metallic lithium, a carbon material, a material capable of inserting lithium or forming a compound can be used, and a carbon material is particularly suitable.
  • 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 a specific example of the secondary battery according to the present embodiment.
  • a battery having a diameter of 6.8 mm and a thickness of 2.1 mm was manufactured.
  • 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 ), and iron oxide Fe 2 O 3 were mixed in a 2: 2: 1 predetermined molar ratio as raw materials, and then , 0.1 mole ratio lithium monofluorophosphate compound is added, and citric acid is added and mixed as a chelating agent. Thereafter, the water is evaporated while heating and stirring. After the evaporation of moisture, the remaining substance was recovered to be a precursor, and this precursor was subjected to a heat treatment in a firing atmosphere at 800 ° C. for 4 hours using an atmosphere furnace (argon gas stream) to obtain a fluoropyrophosphate positive electrode material (Li 2 FeP 2 O 7- ⁇ F ⁇ ) is prepared.
  • a fluoropyrophosphate positive electrode material Li 2 FeP 2 O 7- ⁇ F ⁇
  • 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 calcined sample was pulverized for 1 hour using a meteor-type ball mill (manufactured by FRITSCH, Planetary mill pulverisete 7). Thereafter, coarse particles of 50 ⁇ m or more are removed by sieving.
  • a part of oxygen in pyrophosphate type P 2 O 7 is substituted with a halogen element, so that the crystal structure having the pyrophosphate type P 2 O 7 structure with high thermal stability as a basic skeleton is obtained.
  • a positive electrode material for a secondary battery having a high discharge capacity and a secondary battery using the same can be provided.
  • Li 3 PO 4 and manganese (III) oxide are used as raw materials for preparing the positive electrode material.
  • Li 3 PO 4 and manganese (III) oxide (Mn 2 O 3 ) are used as raw materials for preparing the positive electrode material.
  • Li 3 PO 4 lithium monofluorophosphate
  • Li 2 PO 3 F lithium monofluorophosphate
  • Li: Mn: P is 2: 1: 2 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 MnP 2 O 7- ⁇ F ⁇ .
  • ⁇ 0.04.
  • a part of oxygen in pyrophosphate type P 2 O 7 is substituted with a halogen element, so that the crystal structure having the pyrophosphate type P 2 O 7 structure with high thermal stability as a basic skeleton is obtained.
  • a positive electrode material for a secondary battery having a high discharge capacity and a secondary battery using the same can be provided.
  • a higher discharge capacity can be obtained by using Mn.
  • lithium carbonate, Li 3 PO 4 , cobalt dioxide, and nickel oxide are used as the raw material for producing the positive electrode material, and Li: Co: Ni is 4.01: 0.34: 0.66 in the raw material ratio.
  • Li: Co: Ni is 4.01: 0.34: 0.66 in the raw material ratio.
  • Li 2 PO 3 F lithium monofluorophosphate
  • the obtained positive electrode material is Li 2 Co 1/3 Ni 2/3 P 2 O 7- ⁇ F ⁇ .
  • ⁇ 0.03.
  • a discharge capacity of 120 mAh / g can be confirmed.
  • the average particle size was 1 ⁇ m (the average radius was 0.5 ⁇ m).
  • a part of oxygen in pyrophosphate type P 2 O 7 is substituted with a halogen element, so that the crystal structure having the pyrophosphate type P 2 O 7 structure with high thermal stability as a basic skeleton is obtained.
  • a positive electrode material for a secondary battery having a high discharge capacity and a secondary battery using the same can be provided.
  • ion exchange from lithium ions to sodium ions is performed by a quantum simulation technique based on first-principles calculations.
  • a simulation was performed.
  • the ion exchange is reproduced on a computer, and by using a generalized density gradient approximation that takes into account the density functional theory and short-range Hubbard correlation terms, Na 2 FeP 2 O 7 - ⁇ F ⁇ crystal structure optimization calculation was performed.
  • Na 2 FeP 2 O 7 having a crystal structure equal to Li 2 FeP 2 O 7- ⁇ F ⁇ - ⁇ F ⁇ was obtained.
  • Unit cell volume of Na 2 FeP 2 O 7- ⁇ F ⁇ is 1127.7 ⁇ 3, was about 6% greater than the Li 2 FeP 2 O 7- ⁇ F ⁇ .
  • This result can be explained by the fact that sodium ions have a larger ionic radius than lithium ions, and shows that Na 2 FeP 2 O 7- ⁇ F ⁇ can be created experimentally.
  • the discharge capacity of 120 mAh / g can be confirmed.
  • a part of oxygen in pyrophosphate type P 2 O 7 is substituted with a halogen element, so that the crystal structure having the pyrophosphate type P 2 O 7 structure with high thermal stability as a basic skeleton is obtained.
  • a positive electrode material for a secondary battery having a high discharge capacity and a secondary battery using the same can be provided.
  • this invention is not limited to the above-mentioned Example, Various modifications are included.
  • the above-described embodiments have been described in detail for easy understanding of the present invention, and are not necessarily limited to those having all the configurations described.
  • a part of the configuration of a certain embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of a certain embodiment.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

De manière à produire un matériau d'électrode positive de batterie secondaire ayant une structure cristalline comprenant une structure d'acide pyrophosphorique P2O7 très stable thermiquement à titre de squelette fondamental et apte à obtenir une capacité de décharge élevée, et également à produire une batterie secondaire utilisant le matériau d'électrode positive de batterie secondaire, la configuration suivante est utilisée selon l'invention. Le matériau d'électrode positive de batterie secondaire est principalement constitué d'une formule de composition chimique A2-xMP2O7-הZה, dans laquelle : A est un métal alcalin (1 à 4) tel que, par exemple, le lithium; M est un métal de transition tel que, par exemple, le fer qui est apte à former un ion divalent ou davantage multivalent; Z est un halogène tel que, par exemple, le fluor; x est égal à 0 ou plus et inférieur à 2; et ה est supérieur à 0 et inférieur ou égal à 1,47. Une batterie secondaire utilisant ce matériau d'électrode positive est également décrite.
PCT/JP2012/003452 2011-09-09 2012-05-28 Matériau d'électrode positive de batterie secondaire et batterie secondaire l'utilisant WO2013035222A1 (fr)

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JP2014535126A (ja) * 2011-09-30 2014-12-25 ファラディオン リミテッド 凝縮ポリアニオン電極
JP2016038996A (ja) * 2014-08-06 2016-03-22 Fdk株式会社 リチウム二次電池用正極活物質およびリチウム二次電池
JP2017182949A (ja) * 2016-03-29 2017-10-05 Fdk株式会社 全固体電池用正極活物質材料の製造方法、全固体電池用正極活物質材料
WO2018003071A1 (fr) * 2016-06-30 2018-01-04 富士通株式会社 Matériau actif d'électrode positive pour batteries secondaires, son procédé de fabrication et batterie secondaire au lithium-ion
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WO2020031690A1 (fr) * 2018-08-10 2020-02-13 日本化学工業株式会社 Procédé de production de pyrophosphate de lithium-cobalt et procédé de production de complexe pyrophosphate de lithium-cobalt-carbone
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JP2014535126A (ja) * 2011-09-30 2014-12-25 ファラディオン リミテッド 凝縮ポリアニオン電極
WO2014181436A1 (fr) * 2013-05-09 2014-11-13 株式会社日立製作所 Matériau actif d'électrode positive pour des batteries rechargeables, et batterie rechargeable qui utilise ce dernier
JP2016038996A (ja) * 2014-08-06 2016-03-22 Fdk株式会社 リチウム二次電池用正極活物質およびリチウム二次電池
JP2017182949A (ja) * 2016-03-29 2017-10-05 Fdk株式会社 全固体電池用正極活物質材料の製造方法、全固体電池用正極活物質材料
WO2018003071A1 (fr) * 2016-06-30 2018-01-04 富士通株式会社 Matériau actif d'électrode positive pour batteries secondaires, son procédé de fabrication et batterie secondaire au lithium-ion
JPWO2018003071A1 (ja) * 2016-06-30 2019-01-24 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
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JP2018002560A (ja) * 2016-07-05 2018-01-11 住友金属鉱山株式会社 複合タングステン酸化物の置換元素の選択方法、複合タングステン酸化物の製造方法
CN109980186A (zh) * 2017-12-27 2019-07-05 中国电子科技集团公司第十八研究所 一种掺杂改性型金属焦磷酸盐正极材料
CN109980186B (zh) * 2017-12-27 2021-12-03 中国电子科技集团公司第十八研究所 一种掺杂改性型金属焦磷酸盐正极材料
CN112313006A (zh) * 2018-04-23 2021-02-02 株式会社Posco 锂吸附成型体及其制造方法
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JPWO2020031690A1 (ja) * 2018-08-10 2021-04-01 日本化学工業株式会社 ピロリン酸コバルトリチウムの製造方法及びピロリン酸コバルトリチウム炭素複合体の製造方法
KR20230083343A (ko) * 2021-01-21 2023-06-12 울산대학교 산학협력단 리튬 금속 피로인산염의 산소의 일부가 할로겐 원소로 치환된 전극 재료 및 이의 제조방법
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