WO2016121947A1 - 組電池及び電池パック - Google Patents
組電池及び電池パック Download PDFInfo
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- WO2016121947A1 WO2016121947A1 PCT/JP2016/052708 JP2016052708W WO2016121947A1 WO 2016121947 A1 WO2016121947 A1 WO 2016121947A1 JP 2016052708 W JP2016052708 W JP 2016052708W WO 2016121947 A1 WO2016121947 A1 WO 2016121947A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
- B60L50/64—Constructional details of batteries specially adapted for electric vehicles
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- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
- B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
- B60L58/18—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries of two or more battery modules
- B60L58/21—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries of two or more battery modules having the same nominal voltage
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- 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
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- 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
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- H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
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- H01M50/249—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for aircraft or vehicles, e.g. cars or trains
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- Embodiments of the present invention relate to an assembled battery and a battery pack.
- Nonaqueous electrolyte batteries such as lithium ion secondary batteries have been actively promoted as high energy density batteries.
- Nonaqueous electrolyte batteries are expected to be used as power sources for hybrid vehicles, electric vehicles, and uninterruptible power supplies for mobile phone base stations. Therefore, in addition to high energy density, non-aqueous electrolyte batteries are also required to be excellent in other characteristics such as rapid charge / discharge characteristics and long-term reliability. For example, in a non-aqueous electrolyte battery capable of rapid charge and discharge, not only the charging time is significantly shortened, but also improvement of the motive power performance of a hybrid vehicle or the like and efficient recovery of motive power regenerative energy are possible.
- a battery using a metal composite oxide as a negative electrode instead of a carbonaceous material has been developed.
- a battery using titanium oxide as a negative electrode has the characteristics that stable rapid charge and discharge are possible, and the life is longer than that of a carbon-based negative electrode.
- titanium oxide has a high potential for metallic lithium, ie, noble, as compared with carbonaceous substances. Moreover, titanium oxide has a low capacity per weight. Therefore, a battery using titanium oxide as a negative electrode has a problem that the energy density is low. In particular, when a material having a high potential with respect to metallic lithium is used as the negative electrode material, the voltage is smaller than that of a battery using a conventional carbonaceous material, and therefore, a system requiring high voltage such as an electric car or a large scale power storage system There is a problem that the number of series connected batteries increases.
- the electrode potential of titanium oxide is about 1.5 V with respect to metallic lithium and is higher (noble) than the potential of the carbon-based negative electrode.
- the potential of titanium oxide is electrochemically restricted because it is due to the redox reaction between Ti 3+ and Ti 4+ in electrochemically absorbing and desorbing lithium . Therefore, it has been difficult to reduce the electrode potential to improve the energy density.
- An object of the present invention is to provide a battery pack capable of exhibiting excellent voltage compatibility with a battery pack including a lead-acid battery, and a battery pack provided with the battery pack.
- an assembled battery comprises five non-aqueous electrolyte batteries electrically connected in series with one another.
- Each of the five non-aqueous electrolyte batteries comprises a positive electrode, a negative electrode, and a non-aqueous electrolyte.
- the negative electrode contains an active material containing a titanium composite oxide.
- the titanium composite oxide contains Na and the metal element M in the crystal structure.
- the metal element M is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn and Al.
- a battery pack is provided.
- the battery pack includes the assembled battery according to the first embodiment.
- the block diagram which shows the electric circuit of the battery pack of FIG. X-ray diffraction diagrams of the products of Examples A-2, A-4, A-5, A-6 and A-9. Charge and discharge curves of Examples A-4 to A-6 and Reference Examples A-1 and A-6. Charge-discharge curve of the nonaqueous electrolyte battery of Example E. Charge-discharge curve of the assembled battery of Example F. The charging / discharging curve of the assembled battery of the reference example G.
- an assembled battery comprising five non-aqueous electrolyte batteries electrically connected in series with one another.
- Each of the five non-aqueous electrolyte batteries comprises a positive electrode, a negative electrode, and a non-aqueous electrolyte.
- the negative electrode contains an active material containing a titanium composite oxide.
- the titanium composite oxide contains Na and the metal element M in the crystal structure.
- the metal element M is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn and Al.
- the titanium composite oxide containing Na and the metal element M in the crystal structure has a weak overlap between the 2p band of oxygen O and the d band of Ti and the metal element M.
- the titanium composite oxide containing Na and the metal element M in the crystal structure can raise the Fermi level compared to oxides such as spinel type lithium titanate and titanium dioxide having various crystal structures. It becomes.
- This titanium complex oxide exhibits lower electrode potential (vs. Li + / Li) due to such difference in band structure as compared with the case of using titanium oxide such as spinel type lithium titanate and titanium dioxide Can be realized.
- an electrode containing a titanium composite oxide containing Na and metallic element M in the crystal structure has an electrode potential of 1.55 V (vs. Li + / Li) of an electrode containing spinel type lithium titanate.
- An electrode capable of showing such a low electrode potential is combined with any positive electrode material to realize a non-aqueous electrolyte battery having an average operating voltage of about 2.4 V to 2.8 V per battery. be able to.
- the assembled battery according to the first embodiment includes five such non-aqueous electrolyte batteries, and the five non-aqueous electrolyte batteries are electrically connected to one another in series. Therefore, the battery pack according to the first embodiment can exhibit an average operating voltage of 12V to 14V. The average operating voltage within this range is comparable to the average operating voltage of a 12 volt battery pack including lead acid batteries. Therefore, the battery pack capable of indicating such an average operating voltage can assist input / output of the lead storage battery when used in parallel with the 12V battery pack including the lead storage battery. As a result, it is possible to prevent charging due to overdischarge or excessive current which causes deterioration of the lead storage battery. Therefore, the assembled battery according to the first embodiment can exhibit excellent voltage compatibility with the assembled battery including the lead storage battery.
- the Fermi level of the titanium composite oxide containing Na and the metal element M in the crystal structure can be changed by changing the amount of Na.
- an electrode containing a titanium composite oxide containing Na and a metal element M in the crystal structure has an electrode potential of, for example, 1.25 V (vs. Li + / Li) to 1.45 V by changing the amount of Na. It can be arbitrarily changed in the range of (vs. Li + / Li). For example, by using an electrode having an electrode potential of 1.25 V (vs. Li + / Li), it is possible to achieve a high voltage of 0.3 V per battery as compared with the case of using an electrode containing spinel lithium titanate. Voltage can be achieved.
- the metal element M preferably contains Nb.
- a titanium composite oxide containing Na and Nb in the crystal structure is preferable because it can incorporate more Li ions into the crystal structure than a titanium composite oxide not containing Nb, and the electrode capacity is improved. . This is because Nb can be reduced in a divalent manner from pentavalent to trivalent when Li is occluded in the crystal structure of the titanium composite oxide.
- Ti can reduce only one monovalent component from tetravalent to trivalent at the time of Li storage in the crystal structure, and the amount of Li storage is restricted.
- the crystal structure of the titanium composite oxide containing Na and the metal element M in the crystal structure can have, for example, a symmetry belonging to the space group Cmca or Fmmm. These space groups will be described later.
- the titanium composite oxide containing Na and the metal element M in the crystal structure is, for example, a composite represented by the general formula Li 2 + a M (I) 2-b Ti 6-c M (II) d O 14 + ⁇ It is an oxide.
- M (I) is Na or Na and at least one selected from the group consisting of Sr, Ba, Ca, Mg, Cs and K.
- M (II) is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn and Al.
- a is in the range of 0 ⁇ a ⁇ 6.
- b is in the range of 0 ⁇ b ⁇ 2.
- c is in the range of 0 ⁇ c ⁇ 6.
- d is in the range of 0 ⁇ d ⁇ 6.
- ⁇ is in the range of ⁇ 0.5 ⁇ ⁇ ⁇ 0.5.
- the assembled battery according to the first embodiment includes five non-aqueous electrolyte batteries electrically connected in series with one another.
- Each of the five non-aqueous electrolyte batteries comprises a positive electrode, a negative electrode, and a non-aqueous electrolyte.
- Each non-aqueous electrolyte battery can further include a separator disposed between the positive electrode and the negative electrode.
- the positive electrode, the negative electrode, and the separator can constitute an electrode group.
- the non-aqueous electrolyte can be retained in the electrode group.
- each non-aqueous electrolyte battery can further include an electrode assembly and an exterior member for containing the non-aqueous electrolyte.
- each non-aqueous electrolyte battery can further include a positive electrode terminal electrically connected to the positive electrode and a negative electrode terminal electrically connected to the negative electrode. At least a portion of the positive electrode terminal and at least a portion of the negative electrode terminal may extend outside the exterior member.
- the assembled battery according to the first embodiment can further include a lead for electrically connecting five non-aqueous electrolyte batteries.
- the lead is preferably made of, for example, the same material as the terminal of the non-aqueous electrolyte battery in order to reduce the contact resistance with the terminal of the non-aqueous electrolyte battery connecting the lead.
- the negative electrode, the positive electrode, the non-aqueous electrolyte, the separator, the package member, the positive electrode terminal, and the negative electrode terminal that can be included in each of the non-aqueous electrolyte batteries included in the battery assembly according to the first embodiment will be described in more detail.
- the negative electrode can include a current collector and a negative electrode layer (a negative electrode active material-containing layer).
- the negative electrode layer can be formed on one side or both sides of the current collector.
- the negative electrode layer can contain a negative electrode active material, and optionally a conductive agent and a binder.
- the active material containing the titanium composite oxide containing Na and the metal element M in the crystal structure described above can be included in the negative electrode layer as a negative electrode active material. Specific examples of the titanium composite oxide containing Na and the metal element M in the crystal structure will be described later.
- the negative electrode may use the above active material alone as a negative electrode active material, but may use a mixture of this active material and another active material.
- active materials include lithium titanate having a ramsdellite structure (eg, Li 2 Ti 3 O 7 ), lithium titanate having a spinel structure (eg, Li 4 Ti 5 O 12 ), monoclinic titanium dioxide (TiO 2 (B)), anatase titanium dioxide, rutile titanium dioxide, hollandite titanium composite oxide, and monoclinic niobium titanium composite oxide (for example, Nb 2 TiO 7 ).
- the conductive agent is blended to enhance the current collection performance and to reduce the contact resistance between the negative electrode active material and the current collector.
- conductive agents include carbon materials such as vapor grown carbon fiber (VGCF), acetylene black, carbon black and graphite.
- the binder is blended to fill the gaps of the dispersed negative electrode active material and to bind the negative electrode active material and the current collector.
- the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, and styrene butadiene rubber, polyacrylic acid compounds, and imide compounds.
- the active material, the conductive agent, and the binder in the negative electrode layer may be compounded at a ratio of 68% by mass to 96% by mass, 2% by mass to 30% by mass, and 2% by mass to 30% by mass, respectively. preferable.
- the current collection performance of the negative electrode layer can be improved by setting the amount of the conductive agent to 2% by mass or more. Further, by setting the amount of the binder to 2% by mass or more, the binding property between the negative electrode layer and the current collector is sufficient, and excellent cycle characteristics can be expected.
- the conductive agent and the binder are preferably 28% by mass or less, respectively, in order to achieve high capacity.
- the current collector a material that is electrochemically stable at the storage and release potential of lithium of the negative electrode active material is used.
- the current collector is preferably made of copper, nickel, stainless steel or aluminum, or an aluminum alloy containing one or more elements selected from Mg, Ti, Zn, Mn, Fe, Cu and Si.
- the thickness of the current collector is preferably 5 to 20 ⁇ m. A current collector having such a thickness can balance the strength and weight reduction of the negative electrode.
- the density of the negative electrode layer (not including the current collector) is 1.8 g / cm 3 to 2.8 g / It can be in the range of 3 cm.
- the negative electrode having the density of the negative electrode layer in this range can exhibit excellent energy density and can exhibit excellent retention of the electrolyte solution. More preferably, the density of the negative electrode layer is 2.1 to 2.6 g / cm 3 .
- the negative electrode is prepared, for example, by suspending a negative electrode active material, a binder and a conductive agent in a widely used solvent to prepare a slurry, applying the slurry to a current collector and drying to form a negative electrode layer, It is produced by applying a press.
- the negative electrode may also be produced by forming a negative electrode active material, a binder and a conductive agent in the form of pellets to form a negative electrode layer, and arranging the negative electrode layer on a current collector.
- the positive electrode can include a current collector and a positive electrode layer (positive electrode active material-containing layer).
- the positive electrode layer can be formed on one side or both sides of the current collector.
- the positive electrode layer can contain a positive electrode active material and optionally a conductive agent and a binder.
- an oxide or a sulfide can be used as the positive electrode active material.
- oxides and sulfides are compounds capable of storing and releasing lithium, manganese dioxide (MnO 2 ), iron oxide, copper oxide, nickel oxide, lithium manganese composite oxide (eg Li x Mn) 2 O 4 or Li x MnO 2 ), lithium nickel complex oxide (eg Li x NiO 2 ), lithium cobalt complex oxide (eg Li x CoO 2 ), lithium nickel cobalt complex oxide (eg Li Ni 1-y Co y) O 2 ), lithium manganese cobalt complex oxide (eg Li x Mn y Co 1-y O 2 ), lithium manganese cobalt complex oxide (eg Li x Mn y Co 1-y O 2 ), lithium manganese nickel complex oxide having a spinel structure (eg Li x Mn 2-y Ni y O 4 ), olivine structure Lithium phosphate oxides (eg, Li x FePO 4 , Li x Fe 1-
- Examples of more preferable positive electrode active materials include lithium manganese complex oxide (eg, Li x Mn 2 O 4 ), lithium nickel complex oxide (eg, Li x NiO 2 ), lithium cobalt complex oxide (eg, Li x CoO 2 ), lithium nickel cobalt complex oxide (eg, LiNi 1-y Co y O 2 ), lithium manganese nickel complex oxide having a spinel structure (eg, Li x Mn 2-y Ni y O 4 ), lithium manganese cobalt Included are complex oxides (eg Li x Mn y Co 1 -yO 2 ), lithium iron phosphate (eg Li x FePO 4 ), and lithium nickel cobalt manganese complex oxides. In the above equation, 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1.
- Preferred examples of the positive electrode active material when using a normal temperature molten salt as the non-aqueous electrolyte of a battery include lithium iron phosphate, Li x VPO 4 F (0 ⁇ x ⁇ 1), lithium manganese composite oxide, lithium nickel composite oxide And lithium nickel cobalt composite oxide. Since these compounds have low reactivity with the normal temperature molten salt, the cycle life can be improved.
- the primary particle size of the positive electrode active material is preferably 100 nm or more and 1 ⁇ m or less.
- the positive electrode active material having a primary particle size of 100 nm or more is easy to handle in industrial production.
- a positive electrode active material having a primary particle size of 1 ⁇ m or less can smoothly diffuse lithium ions in the solid.
- the specific surface area of the positive electrode active material is preferably 0.1 m 2 / g or more and 10 m 2 / g or less.
- the positive electrode active material having a specific surface area of 0.1 m 2 / g or more can sufficiently secure lithium ion absorption / desorption sites.
- the positive electrode active material having a specific surface area of 10 m 2 / g or less can be easily handled in industrial production and can ensure good charge / discharge cycle performance.
- the binder is blended to bind the positive electrode active material and the current collector.
- the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, polyacrylic acid compound, and imide compound.
- the conductive agent is blended as necessary to enhance the current collection performance and to suppress the contact resistance between the positive electrode active material and the current collector.
- conductive agents include carbonaceous materials such as acetylene black, carbon black and graphite.
- the positive electrode active material and the binder are preferably blended in a proportion of 80% by mass or more and 98% by mass or less and 2% by mass or more and 20% by mass or less.
- the binder By setting the binder in an amount of 2% by mass or more, sufficient electrode strength can be obtained. Moreover, by setting it as 20 mass% or less, the compounding quantity of the insulator of an electrode can be reduced and internal resistance can be reduced.
- the positive electrode active material, the binder and the conductive agent are each 77% by mass or more and 95% by mass, 2% by mass or more and 20% by mass or less, and 3% by mass or more and 15% by mass or less It is preferable to blend in proportions.
- the conductive agent can exhibit the above-mentioned effects by setting it to 3% by mass or more. Further, by setting the content to 15% by mass or less, the decomposition of the non-aqueous electrolyte on the surface of the positive electrode conductive agent under high temperature storage can be reduced.
- the current collector is preferably an aluminum foil or an aluminum alloy foil containing one or more elements selected from Mg, Ti, Zn, Ni, Cr, Mn, Fe, Cu and Si.
- the thickness of the aluminum foil or aluminum alloy foil is desirably 5 ⁇ m or more and 20 ⁇ m or less, more preferably 15 ⁇ m or less.
- the purity of the aluminum foil is preferably 99% by mass or more.
- the content of transition metals such as iron, copper, nickel, and chromium contained in aluminum foil or aluminum alloy foil is preferably 1% by mass or less.
- the positive electrode is prepared, for example, by suspending a positive electrode active material, a binder and a conductive agent optionally mixed in an appropriate solvent to prepare a slurry, applying the slurry to a positive electrode current collector, and drying it. After forming a layer, it is produced by applying a press.
- the positive electrode may also be produced by forming the active material, the binder, and the conductive agent blended as necessary into a pellet to form a positive electrode layer, and arranging the positive electrode layer on the current collector.
- the nonaqueous electrolyte is, for example, a liquid nonaqueous electrolyte prepared by dissolving the electrolyte in an organic solvent, or a gel-like nonaqueous electrolyte in which a liquid electrolyte and a polymer material are complexed. Good.
- the liquid non-aqueous electrolyte is preferably one in which the electrolyte is dissolved in an organic solvent at a concentration of 0.5 mol / L to 2.5 mol / L.
- electrolytes examples include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium arsenic hexafluoride (LiAsF 6 ), trifluoromethane sulfone Lithium salts such as lithium acid (LiCF 3 SO 3 ), and bistrifluoromethylsulfonylimido lithium (LiN (CF 3 SO 2 ) 2 ), and mixtures thereof are included.
- the electrolyte is preferably one that is not easily oxidized even at high potential, and LiPF 6 is most preferable.
- organic solvent examples include propylene carbonate (PC), ethylene carbonate (EC), cyclic carbonate such as vinylene carbonate; linear carbonate such as diethyl carbonate (DEC), dimethyl carbonate (DMC) and methyl ethyl carbonate (MEC) Carbonates; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2 MeTHF), dioxolane (DOX); linear ethers such as dimethoxyethane (DME), diethoxyethane (DEE); ⁇ -butyrolactone (GBL), Acetonitrile (AN) and sulfolane (SL) are included.
- PC propylene carbonate
- EC ethylene carbonate
- cyclic carbonate such as vinylene carbonate
- linear carbonate such as diethyl carbonate (DEC), dimethyl carbonate (DMC) and methyl ethyl carbonate (MEC)
- cyclic ethers such as
- polymeric materials examples include polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), and polyethylene oxide (PEO).
- PVdF polyvinylidene fluoride
- PAN polyacrylonitrile
- PEO polyethylene oxide
- non-aqueous electrolyte a lithium ion-containing normal temperature molten salt (ionic melt), a solid polymer electrolyte, an inorganic solid electrolyte, or the like may be used.
- the normal temperature molten salt refers to a compound which can be present as a liquid at normal temperature (15 to 25 ° C.) among organic salts consisting of a combination of an organic cation and an anion.
- the room temperature molten salt includes a room temperature molten salt which is singly present as a liquid, a room temperature molten salt which becomes a liquid by mixing with an electrolyte, and a room temperature molten salt which becomes a liquid when dissolved in an organic solvent.
- the melting point of the room temperature molten salt used for the non-aqueous electrolyte battery is 25 ° C. or less.
- organic cations generally have a quaternary ammonium skeleton.
- a solid polymer electrolyte is prepared by dissolving an electrolyte in a polymer material and solidifying it.
- the inorganic solid electrolyte is a solid substance having lithium ion conductivity.
- the separator may be formed of, for example, a porous film containing polyethylene, polypropylene, cellulose, or polyvinylidene fluoride (PVdF), or a synthetic resin non-woven fabric.
- a porous film formed of polyethylene or polypropylene can be melted at a certain temperature to interrupt the current, so that the safety can be improved.
- Exterior member for example, a laminate film having a thickness of 0.5 mm or less or a metal container having a thickness of 1 mm or less can be used.
- the thickness of the laminate film is more preferably 0.2 mm or less.
- the thickness of the metal container is more preferably 0.5 mm or less, and further preferably 0.2 mm or less.
- the shape of the exterior member is not particularly limited, and may be flat (thin), rectangular, cylindrical, coin, button, or the like.
- the exterior member may be, for example, a small battery exterior member loaded on a portable electronic device or the like, or a large battery exterior member loaded on a two- or four-wheeled automobile or the like according to the battery size.
- a multilayer film including a resin layer and a metal layer interposed between these resin layers is used.
- the metal layer is preferably aluminum foil or aluminum alloy foil for weight reduction.
- the resin layer for example, polymeric materials such as polypropylene (PP), polyethylene (PE), nylon, and polyethylene terephthalate (PET) can be used.
- PP polypropylene
- PE polyethylene
- PET polyethylene terephthalate
- the laminated film can be molded into the shape of the exterior member by sealing by heat fusion.
- the metal container is made of, for example, aluminum or an aluminum alloy.
- the aluminum alloy is preferably an alloy containing an element such as magnesium, zinc or silicon.
- the alloy contains a transition metal such as iron, copper, nickel, or chromium, the content is preferably 1% by mass or less.
- Positive electrode terminal and negative electrode terminal The positive electrode terminal can be formed of, for example, a material having electrical stability and conductivity in the range of 3 V to 5 V with respect to the redox potential of lithium.
- the positive electrode terminal is formed of aluminum or an aluminum alloy containing an element such as Mg, Ti, Zn, Mn, Fe, Cu, or Si.
- the positive electrode terminal is preferably formed of the same material as the positive electrode current collector in order to reduce the contact resistance with the positive electrode current collector.
- the negative electrode terminal can be formed of a material that is electrochemically stable at the Li absorption and release potential of the above-described negative electrode active material and has conductivity.
- the material of the negative electrode terminal includes copper, nickel, stainless steel or aluminum.
- the negative electrode terminal is preferably formed of the same material as the negative electrode current collector in order to reduce the contact resistance with the negative electrode current collector.
- the battery active material containing the titanium composite oxide containing Na and the metal element M will be described as a first example and a second example.
- the active material containing the titanium composite oxide containing Na and the metal element M is not limited to the first and second examples described below.
- the active material of the first example has an orthorhombic crystal structure and contains a complex oxide represented by the general formula Li x M 1 1 y M 2 y Ti 6-z M 3 z O 14 + ⁇ It is a substance.
- M1 is at least one selected from the group consisting of Sr, Ba, Ca, and Mg.
- M2 is Na or contains Na and at least one selected from the group consisting of Cs and K.
- M3 is at least one selected from the group consisting of Al, Fe, Zr, Sn, V, Nb, Ta and Mo.
- x is in the range of 2 ⁇ x ⁇ 6.
- y is in the range of 0 ⁇ y ⁇ 1.
- z is in the range of 0 ⁇ z ⁇ 6.
- ⁇ is in the range of ⁇ 0.5 ⁇ ⁇ ⁇ 0.5.
- This complex oxide is a complex oxide having an orthorhombic crystal structure represented by the general formula Li x M 1 Ti 6 O 14 + ⁇ , in which a part of the M 1 site is substituted with a metal cation M 2 and one of the Ti sites is It is a substituted oxide in which a part is substituted by metal cation M3.
- the active material of the first example can have an average potential of lithium storage in the range of 0.5 V to 1.45 V (vs. Li / Li + ) with respect to the redox potential of metal lithium.
- a non-aqueous electrolyte battery using the active material of the first example as a negative electrode for example, uses a titanium composite oxide having a lithium storage potential of 1.55 V (vs. Li / Li + ) as a negative electrode. It can exhibit a higher battery voltage than an electrolyte battery.
- the active material of the first example can exhibit a gentle potential change in the potential range of 1.0 V to 1.45 V (vs. Li / Li + ).
- the active material of the first example can exhibit a gentle potential change.
- FIG. 1 shows the charge / discharge curve (broken line) of the complex oxide Li 2 SrTi 6 O 14 and the charge / discharge curve (solid line) of the complex oxide Li 2 (Sr 0.75 Na 0.25 ) Ti 5.75 Nb 0.25 O 14 .
- the complex oxide Li 2 (Sr 0.75 Na 0.25 ) Ti 5.75 Nb 0.25 O 14 whose potential change is indicated by a solid line is one having a rhombic crystal structure, and the active material of the first example includes Can be a complex oxide.
- the complex oxide Li 2 SrTi 6 O 14 whose potential change is indicated by a broken line is a complex oxide having a orthorhombic crystal structure represented by a general formula Li x M 1 Ti 6 O 14 + ⁇ .
- the charge / discharge curve of the complex oxide Li 2 SrTi 6 O 14 has a potential flat portion in the potential range of about 1.4 V to 1.45 V (vs. Li / Li + ). However, when the potential falls below 1.4 V (vs. Li / Li + ), the potential drops sharply. That is, the charge / discharge curve of the complex oxide Li 2 SrTi 6 O 14 includes a step portion of the potential. In a non-aqueous electrolyte battery manufactured using a composite oxide exhibiting such a potential change as a negative electrode, voltage control is difficult because a rapid voltage change occurs at low SOC.
- the charge-discharge curve of the complex oxide Li 2 (Sr 0.75 Na 0.25 ) Ti 5.75 Nb 0.25 O 14 has a potential of approximately 1.0 V to 1.45 V (vs. Li / Li + ) In the range, a gentle potential change can be shown.
- a non-aqueous electrolyte battery manufactured using a composite oxide exhibiting such a potential change as a negative electrode can suppress a rapid voltage change at low SOC, and therefore, voltage management is easy.
- the compound oxide that the active material of the first example can contain can exhibit a smooth potential change in the potential range of 1.0 V to 1.45 V (vs. Li / Li + ) because of the uniformity of lithium It is possible to have an insertion site. The reason is described below.
- a composite oxide that can be included in the active material of the first example is represented by the general formula Li x M 1 1-y M 2 y Ti 6-z M 3 z O 14 + ⁇ .
- Li is present as a monovalent cation.
- M1 is a divalent cation that is at least one selected from the group consisting of Sr, Ba, Ca, and Mg.
- M2 is Na which is a monovalent cation, or contains Na and at least one type of monovalent cation selected from the group consisting of Cs and K.
- M3 is selected from the group consisting of Al and Fe as trivalent cations, Zr and Sn as tetravalent cations, V as pentavalent cations, Nb and Ta, and Mo as hexavalent cations It is at least one kind.
- the valence of the cation is the valence of each cation in the state where x is 2 in the above general formula, that is, in the discharge state.
- the sum of the valences of the cations corresponds to the sum of the valences of the oxide ions which are anions, and maintains charge neutrality.
- the sum of valences of lithium ions is x.
- the sum of the valences of M1 is 2 ⁇ (1-y).
- the sum of the valences of M2 is y.
- the sum of the valences of Ti is 4 ⁇ (6-z).
- the sum of the valences of these cations corresponds to the sum of the valences of the anions, oxide ions: ( ⁇ 2) ⁇ (14 + ⁇ ).
- the subscript ⁇ of the oxide ion can indicate a value within the range of -0.5 or more and 0.5 or less, and therefore, the sum of the valences of the cations shown here is the total valence of the oxide ions
- the same effect can be obtained by fluctuating within the range of ⁇ 1 value with respect to ⁇ 28 value. If this ⁇ is out of the range of ⁇ 0.5 ⁇ ⁇ ⁇ 0.5, the redox state of the cation may be out of the stable state, or lattice defects such as oxygen deficiency may occur. Not preferable because the battery performance is reduced.
- the complex oxide in which the charge neutrality is maintained is that a part of the M1 site is correctly substituted with the metal cation M2 and the Ti site is Is a substituted oxide in which part of the metal cation is correctly substituted by the metal cation M3.
- lithium ions are inserted by including a substituted oxide in which M2 and M3 are correctly substituted in the crystal structure of the complex oxide represented by the general formula Li x M 1 Ti 6 O 14 + ⁇ .
- the coordination environment of the oxide ion to the void site can be made uniform.
- the composite oxide that the active material of the first example can contain can exhibit a gentle potential change in the potential range of 1.0 V to 1.45 V (vs. Li / Li + ).
- the uniformity of the coordination environment of the oxide ion with respect to the void site is low, the charge / discharge curve of the composite oxide will show a step portion of the potential.
- the active material of the first example can be charged and discharged by virtue of including a substituted oxide in which M 2 and M 3 are correctly substituted within the crystal structure of the complex oxide represented by the general formula Li x M 1 Ti 6 O 14 + ⁇ .
- the present invention can provide a non-aqueous electrolyte battery that can exhibit high reversible capacity and excellent life characteristics.
- the active material of the first example can exhibit high energy density and high battery voltage, and can realize a non-aqueous electrolyte battery having excellent life characteristics and easy voltage management.
- the subscript x in the general formula Li x M 1 1-y M 2 y Ti 6-z M 3 z O 14 + ⁇ for the complex oxide varies between 2 ⁇ x ⁇ 6, depending on the charge state of the complex oxide obtain.
- a complex oxide in which the subscript x is 2 in the above general formula can be manufactured.
- a state in which the value of x has risen to a value within the range of more than 2 and 6 or less by incorporating the composite oxide having a subscript x of 2 as a negative electrode active material into a non-aqueous electrolyte battery and charging this non-aqueous electrolyte battery. become.
- the composite oxide can be synthesized with a raw material composition ratio such that the value of the subscript x is in the range of more than 2 and 6 or less before the first charge by the method described later.
- An active material containing a complex oxide in which the value of subscript x is in the range of 2 or more and 6 or less before the first charge suppresses that lithium ions are trapped in the structure during the first charge and discharge. As a result, the initial charge and discharge efficiency can be improved.
- the complex oxide as one example of such a preferred embodiment has an orthorhombic crystal structure belonging to the space group Cmca, and has an X-ray diffraction diagram obtained by powder X-ray diffraction using Cu-K ⁇ rays ( 112) plane and (021) and the intensity I L1 diffraction line towards intensity is large among diffracted rays respectively corresponding to the plane, (220) intensity ratio of the intensity I H1 of diffraction line corresponding to the plane I L1 / I H1 is in the range of 0.6 ⁇ IL1 / IR1 ⁇ 3.
- FIG. 2 shows a crystal structure diagram of Li 2 (Sr 0.75 Na 0.25 ) Ti 5.75 Nb 0.25 O 14 , which is an example of a complex oxide having a symmetry of space group Cmca.
- the position indicated by the smallest sphere 100 at the top of the polyhedron indicates the position of the oxide ion.
- the region A shows a void site having a channel in which lithium ions can move in three dimensions in the crystal structure, and this region A can occlude and release lithium ions.
- the region B has a polyhedral structure of oxide centering on Ti or Nb, which is a skeleton of the crystal structure.
- Region C is a site where lithium ions capable of occluding and releasing are present.
- the region D is a site where Sr, Na, or Li, which functions as a skeleton for stabilizing the crystal structure, is present.
- the crystallite grows in a preferable direction for absorption and release of lithium ions, and a void having a different coordination environment of oxide ions, which is one of the causes of the step-like charge / discharge curve. Insertion of lithium ions into the site can be suppressed.
- the active material containing the composite oxide of this example not only has a smooth charge / discharge curve but also has improved reversibility of lithium ions in charge / discharge, thereby increasing the effective capacity, and a non-aqueous electrolyte battery It is preferable because it can also improve the life performance of
- FIG. 3 shows a crystal structure diagram of Li 2 (Sr 0.25 Na 0.75 ) Ti 5.25 Nb 0.75 O 14 , which is an example of a complex oxide having a space group Fmmm symmetry.
- the smallest sphere 100 indicates the position of the oxide ion.
- the region A indicates a void site having a channel in which lithium ions can move in three dimensions in the crystal structure, and this region A can occlude and release lithium ions.
- the region B has a polyhedral structure of oxide centering on Ti or Nb, which is a skeleton of the crystal structure.
- Region C is a site where lithium ions capable of storage and release exist.
- the region D is a site where Sr, Na, or Li, which functions as a skeleton for stabilizing the crystal structure, is present.
- the crystallite grows in a preferable direction for absorption and release of lithium ions, and a void having a different coordination environment of oxide ions, which is one of the causes of the step-like charge / discharge curve. Insertion of lithium ions into the site can be suppressed.
- the active material containing the composite oxide of this example not only has a smooth charge / discharge curve but also has improved reversibility of lithium ions in charge / discharge, thereby increasing the effective capacity, and a non-aqueous electrolyte battery It is preferable because it can also improve the life performance of
- the active material of the first example may contain a complex oxide having a crystal structure in which crystal phases having Cmca or Fmmm symmetry exist, or a crystal structure similar to Cmca or Fmmm symmetry. Even if it has a composite oxide, it can obtain the same effect as an active material of an embodiment including a composite oxide having a symmetry of space group Cmca or a composite oxide having a symmetry of space group Fmmm. .
- Examples of symmetry similar to that of Cmca or Fmmm include Pmcm, Pmma and Cmma.
- the intensity ratio I L / I H to the intensity I H of the strongest diffraction line appearing in the range of 2 ° ⁇ 2 ⁇ ⁇ 19.5 ° be in the range of 0.6 ⁇ I L / I H ⁇ 3.
- the charge and discharge curve becomes gentle but also the reversibility of lithium ions in charge and discharge is improved, whereby the effective capacity can be increased and the life performance of the non-aqueous electrolyte battery can be improved.
- the subscript x is in the range of 2 ⁇ x ⁇ 6, depending on the charge state of the complex oxide represented by this general formula Change.
- the subscript y indicates the ratio of the substitution by the general formula Li x M1 1 Ti 6 O 14 + ⁇ cation M2 of sites of the composite oxide in the crystal structure of the cation M1 represented.
- the subscript y is in the range of 0 ⁇ y ⁇ 1, preferably in the range of 0.1 ⁇ y ⁇ 0.9, and more preferably in the range of 0.25 ⁇ y ⁇ 0.75.
- subscript z indicates the ratio of substitution of the site of Ti in the crystal structure of the complex oxide represented by the general formula Li x M 11 Ti 6 O 14 + ⁇ with the cation M 3.
- the subscript z is in the range of 0 ⁇ z ⁇ 6, preferably in the range of 0.1 ⁇ z ⁇ 0.9, and more preferably in the range of 0.25 ⁇ z ⁇ 0.75.
- the subscript ⁇ represents the oxygen deficiency of the complex oxide represented by this general formula, or the manufacturing process of the active material. It can be varied within the range of ⁇ 0.5 ⁇ ⁇ ⁇ 0.5 depending on the amount of oxygen inevitably mixed.
- the subscripts x, y, z and ⁇ can each take numerical values within a specific range as described above, but as described above, the general formula Li x M1 1-y M2 y Ti 6-z M3 z O 14+ In the complex oxide represented by ⁇ , the sum of the cation valences is equal to the sum of the anion valences.
- the composite oxide contained in the active material of the first example is represented by the general formula Li x Sr 1-y Na y Ti 6-z M3 z O 14 + ⁇ , where the M3 At least one selected from the group consisting of Al, Fe, Zr, Sn, V, Nb, Ta and Mo, x is in the range of 2 ⁇ x ⁇ 6, and y is in the range of 0 ⁇ y ⁇ 1 And z is in the range of 0 ⁇ z ⁇ 6, and ⁇ is in the range of ⁇ 0.5 ⁇ ⁇ ⁇ 0.5.
- the lattice constant of the crystal is obtained by substituting a part of the Sr site with Na whose ion radius is close to that of the Sr ion
- the lithium storage potential can be lowered without significantly changing the As a result, the energy density per unit weight or unit volume can be increased while maintaining the lattice volume in which lithium ions are easily stored and released.
- the cation M3 is Nb. That is, in this further preferred embodiment, the complex oxide contained in the active material of the first example is represented by the general formula Li x Sr 1-y Na y Ti 6-z Nb z O 14 + ⁇ . Since Nb can be divalently reduced from pentavalent to trivalent, the lithium storage capacity of the complex oxide can be obtained by substituting at least a part of Ti which can be univalently reduced from tetravalent to trivalent with Nb. Can be increased. Furthermore, Nb changes gently in a wide range of 1.5 V to 1.0 V with respect to the redox potential of metal lithium when storing Li.
- the composite oxide contained in the active material of the first example can be, for example, in the form of particles.
- the average particle size of the composite oxide contained in the active material of the first example is not particularly limited, and can be changed according to desired battery characteristics.
- the active material of the first example preferably contains particles of the composite oxide and a conductive material such as carbon coated on the surface thereof. Active materials of such preferred embodiments can exhibit improved rapid charge and discharge performance.
- the above complex oxide has the property that the electronic conductivity increases as the lithium storage amount increases, since the storage and release of lithium occur due to the homogeneous solid state reaction. In such a complex oxide, the electron conductivity is relatively low in the region where the lithium storage amount is small. Therefore, by coating the surface of the composite oxide particles with a conductive substance such as carbon in advance, high rapid charge / discharge performance can be obtained regardless of the lithium storage amount.
- lithium titanate which exhibits electronic conductivity along with lithium storage
- lithium titanate coated on the surface of the composite oxide particles releases lithium at the time of an internal short circuit of the battery to insulate, and therefore can exhibit excellent safety.
- the BET specific surface area of the composite oxide contained in the active material of the first example is not particularly limited, but is preferably 5 m 2 / g or more and less than 200 m 2 / g. More preferably, it is 5 m 2 / g or more and 30 m 2 / g or less.
- the contact area with the electrolytic solution can be secured, good discharge rate characteristics can be easily obtained, and the charge time can be shortened.
- the BET specific surface area is less than 200 m 2 / g, the reactivity with the electrolytic solution is not too high, and the life characteristics can be improved.
- the BET specific surface area is set to 30 m 2 / g or less, the side reactivity with the electrolytic solution can be suppressed, and therefore, further prolonging of the life can be expected.
- the coatability of the slurry containing the active material, which is used for the production of an electrode described later can be made favorable.
- the measurement of the specific surface area uses a method of adsorbing a molecule whose adsorption occupied area is known on the powder particle surface at the temperature of liquid nitrogen and determining the specific surface area of the sample from the amount thereof.
- the most frequently used is the BET method based on low temperature and low humidity physical adsorption of inert gas, and the Langmuir theory, which is a monolayer adsorption theory, is extended to multilayer adsorption, and it is the most famous theory as a calculation method of specific surface area is there.
- the specific surface area thus determined is referred to as BET specific surface area.
- the active material of the first example can be synthesized by a solid phase reaction method as described below.
- the above salts are preferably salts which decompose at relatively low temperatures to form oxides, such as carbonates and nitrates.
- the resulting mixture is then ground and mixed as homogeneous as possible.
- this mixture is calcined. Pre-baking is performed in the air at a temperature range of 600 to 850 ° C. for a total of 1 to 3 hours. Next, the firing temperature is increased, and main firing is performed in the air at 900 to 1500 ° C.
- lithium which is a light element
- lithium may evaporate when it is fired at a temperature of 900 ° C. or more.
- the amount of transpiration of lithium under the calcination conditions is examined, and an excess amount of lithium raw material is added accordingly to compensate for the transpiration to obtain a sample of the correct composition.
- firing is performed under a high oxygen partial pressure such as in an oxygen atmosphere, or heat treatment (annealing) is performed at a temperature range of 400 to 1000 ° C. after firing in a normal atmosphere. It is preferable to repair oxygen deficiency. If the generation of lattice defects is not suppressed in this manner, the crystallinity may be low.
- the intensity ratio of the stronger one of the diffraction lines I L1 to the intensity I H1 of the diffraction line corresponding to the (220) plane which appears in the range of 18.5 ° ⁇ 2 ⁇ ⁇ 19.5 ° I L1 / I H1 becomes 0.6 ⁇ I L1 / I H1 ⁇ 3.
- the complex oxide obtained by the synthesis as described above has the symmetry based on the space group Fmmm
- the X-ray diffraction diagram obtained by the powder X-ray diffraction method using the Cu-K ⁇ ray 17.8 ° ⁇ 2 ⁇ ⁇ 18.5 °
- the intensity I L2 of the diffraction line corresponding to the (111) plane 17.8 ° ⁇ 2 ⁇ ⁇ 19.5 °
- the intensity ratio I L2 / I H2 to the diffraction line intensity I H2 corresponding to the surface is 0.6 ⁇ I L2 / I H2 ⁇ 3.
- the composite oxide whose subscript x is 2 in said general formula can be manufactured, for example.
- a state in which the value of x has risen to a value within the range of more than 2 and 6 or less by incorporating the composite oxide having a subscript x of 2 as a negative electrode active material into a non-aqueous electrolyte battery and charging this non-aqueous electrolyte battery. become.
- the value of x is larger than 2
- Complex oxides in the range of 6 or less can also be synthesized.
- the complex oxide can be obtained by immersing the complex oxide in an aqueous solution of lithium hydroxide or the like after the complex oxide is synthesized, in which the value of x is in the range of more than 2 and 6 or less.
- a composite oxide represented by orthorhombic has a crystal structure of Akiragata and general formula Li 2 + w Na 2-x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2 Containing active material.
- M ⁇ is at least one selected from the group consisting of Cs and K.
- M ⁇ is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn and Al.
- w is in the range of 0 ⁇ w ⁇ 4.
- x2 is in the range of 0 ⁇ x2 ⁇ 2.
- y2 is in the range of 0 ⁇ y2 ⁇ 2.
- z2 is in the range of 0 ⁇ z2 ⁇ 6.
- ⁇ 2 is in the range of ⁇ 0.5 ⁇ ⁇ ⁇ 0.5.
- this complex oxide a part of the Na site in the orthorhombic crystal structure of the complex oxide represented by the general formula Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 is substituted with the cation M ⁇ and / or the Na site It is a substituted complex oxide in which Na ion is removed from a part of Al to be vacancy, and part of Ti site is substituted by cation M ⁇ .
- a non-aqueous electrolyte battery using the active material of the second example as a negative electrode is, for example, a titanium composite oxide having an average potential of 1.55 V (vs. Li / Li + ) in the same operating potential range.
- the battery can exhibit a higher battery voltage than a non-aqueous electrolyt
- the vacancy can serve as a further site for insertion and desorption of Li ions. Therefore, the complex oxide containing such vacancies is easier to occlude and release Li ions than the complex oxide represented by the general formula Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2, and as a result, A high charge and discharge capacity can be realized.
- the active material of the second example has a general formula Li 2+ w Na 2 Ti 6 O in the potential range of 1.0 V (vs. Li / Li + ) to 1.45 V (vs. Li / Li + ).
- the correlation between the charge capacity and the battery voltage can be grasped more easily than the complex oxide represented by 14 + ⁇ 2 .
- the reason why the active material of the second example can easily grasp the correlation between the charge capacity and the battery voltage will be described below with reference to FIG.
- FIG. 4 shows the charge / discharge curve (broken line) of the complex oxide Li 2 Na 2 Ti 6 O 14 and the charge / discharge curve (solid line) of the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 .
- Composite oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 showing the potential change in the solid line are those having a crystal structure of orthorhombic Akiragata, composite oxides which can be the active material of the second embodiment includes It is.
- the complex oxide Li 2 Na 2 Ti 6 O 14 whose potential change is indicated by a broken line is a complex oxide having a orthorhombic crystal structure represented by the general formula Li 2 + w Na 2 Ti 6 O 14 + ⁇ 2 It is a thing.
- the Na cation is removed from a part of the Na site of the crystal structure of the complex oxide Li 2 Na 2 Ti 6 O 14 and the part becomes void. And it is a substituted oxide in which a part of Ti site is substituted by Nb.
- the charge curve and the discharge curve of the complex oxide Li 2 Na 2 Ti 6 O 14 have the amount of change in potential with the change in capacity as the majority excluding charge and discharge initial and final stages. Includes a small flat.
- the complex oxide Li 2 Na 2 Ti 6 O 14 has a potential of 1.20 V (vs. Li / Li + ) and a potential of 1. 20 V (vs. Li / Li + ) It can be seen that about 80 mAh / g is charged within the potential difference of only 0.15 V when being charged up to. This charge capacity corresponds to about 90% of the total charge capacity of the complex oxide Li 2 Na 2 Ti 6 O 14 .
- the complex oxide Li 2 Na 2 Ti 6 O 14 is 1.35 V (vs. Li / Li + ) from the potential of 1.20 V (vs. Li / Li + ) It can be seen that the capacity of about 90% of the total discharge capacity is discharged within the potential difference of only 0.15 V by being subjected to the discharge up to the potential of.
- the charge curve and the discharge curve of the complex oxide Li 2 Na 2 Ti 6 O 14 show almost no change in potential with changes in charge capacity and discharge capacity, that is, most of the area with a small potential gradient As included.
- a non-aqueous electrolyte battery manufactured using a composite oxide exhibiting such a potential change as a negative electrode is difficult to grasp the correlation between charge capacity and battery voltage, and SOC management during charge and discharge is difficult.
- the charge curve and the discharge curve of the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 have most of the potentials associated with the capacity change except for the initial and final stages of charge and discharge. It can be seen that there is a portion where the amount of change is large. Specifically, from the charge curve in the Li insertion direction, the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 starts charging from the potential of 1.50 V (vs. Li / Li + ) and the total capacity is It can be seen that when 90% is charged, the potential is about 1.15 V (vs. Li / Li + ).
- the composite oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 the potential during the charging is changed by about 0.35 V.
- the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 starts discharge from the potential of 1.15 V (vs. Li / Li + ), and 90% of the total capacity Is discharged to give a potential of about 1.50 V (vs. Li / Li + ), and it can be seen that the potential changes by about 0.35 V in this discharge.
- the charge-discharge curve of the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 is the potential associated with the change in capacitance relative to the potential flat portion included in the charge-discharge curve of the complex oxide Li 2 Na 2 Ti 6 O 14 Most of the change is large, that is, the part with the large gradient is included.
- the charge / discharge curve of the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 shows a potential step where the potential changes sharply at portions other than the initial and final stages of charge / discharge. Show a continuous potential change.
- a non-aqueous electrolyte battery manufactured using a composite oxide exhibiting such a potential change as a negative electrode can easily grasp the correlation between the charge and discharge capacity and the battery voltage, thereby facilitating SOC management of the battery.
- the complex oxide Li 2 Na 2 Ti 6 O 14 has a charge and discharge capacity of about 90 mAh / g.
- the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 has a charge / discharge capacity of 115.9 mAh / g, and exhibits a capacity higher than that of the complex oxide Li 2 Na 2 Ti 6 O 14 it can.
- the complex oxide that the active material of the second example can exhibit a continuous potential change without a potential step in the potential range of 1.0 V to 1.45 V (vs. Li / Li + )
- the reason is that it can have a uniform insertion site of lithium. The reason is described below.
- Composite oxides capable of active material of the second example is provided is represented by the general formula Li 2 + w Na 2-x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2.
- Li is present as a monovalent cation.
- M ⁇ is at least one monovalent cation selected from the group consisting of Cs and K.
- M ⁇ is trivalent cation Fe, Co, Mn and Al, tetravalent cation Zr and Sn, pentavalent cation V, Nb and Ta, and hexavalent cation Mo and W
- the valence of the cation is the valence of each cation in the state where w is 0 in the above general formula, that is, in the discharge state.
- the sum of the valences of the cations corresponds to the sum of the valences of the oxide ions which are anions, and maintains charge neutrality.
- the sum of the valences of lithium ions is 2 + w.
- the sum of valences of sodium ions is 2-x2.
- the sum of the valences of M1 is y2.
- the sum of valences of Ti is 4 ⁇ (6-z2).
- the sum of the valences of these cations corresponds to the sum of the valences of the anions, oxide ions: ( ⁇ 2) ⁇ (14 + ⁇ 2).
- the subscript ⁇ 2 of the oxide ion can indicate a value within the range of -0.5 or more and 0.5 or less, and therefore, the sum of the valences of the cations shown here is the total valence of the oxide ion
- the same effect can be obtained by fluctuating within the range of ⁇ 1 value with respect to ⁇ 28 value. If this ⁇ 2 is out of the range of ⁇ 0.5 ⁇ ⁇ 2 ⁇ 0.5, the redox state of the cation may be out of the stable state, or lattice defects such as oxygen deficiency may occur. Not preferable because the battery performance is reduced.
- Li 2 + w Na 2-x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2 is represented by the general formula Li 2 + w Na 2 Ti 6 O 14 + ⁇ 2 It is a substituted oxide in which a part of the Ti sites in the crystal structure of the complex oxide is correctly substituted by the cation M ⁇ .
- y is a large complex oxide than 0 Li 2 + w Na 2- x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2 of the general formula Li 2 + w Na 2 It is a substituted oxide in which part of the Na site in the crystal structure of the complex oxide represented by Ti 6 O 14 + ⁇ 2 is correctly substituted by the cation M ⁇ .
- Li 2 + w Na 2-x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2 is represented by the general formula Li 2 + w Na 2 Ti 6 O 14 + ⁇ 2
- a portion corresponding to a part of Na site in the crystal structure of the complex oxide can be stably present as a vacancy in the crystal structure.
- the active material of the second example includes lithium ion by including the cation M ⁇ correctly substituted in the crystal structure of the complex oxide to be mixed and / or the substitution oxide containing the vacancy that can be stably present.
- the coordination environment of the oxide ion to the void site where is inserted can be made uniform. This is the reason why the composite oxide that the active material of the second example can contain can exhibit a continuous potential change in the potential range of 1.0 V to 1.45 V (vs. Li / Li + ). .
- the charge / discharge curve shows a step portion of the potential, that is, a portion where the potential change is steep.
- the cation M ⁇ is correctly substituted within the crystal structure of the complex oxide represented by the general formula Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 , and is represented by the general formula Li 2 + w Na 2 Ti 6 O 14 + ⁇ 2
- the active material of the second example can be used in charge and discharge thanks to the fact that it contains a cation M ⁇ correctly substituted in the crystal structure of the complex oxide and / or a substitution oxide containing vacancies that can be stably present.
- a non-aqueous electrolyte battery can be provided which can exhibit high reversible capacity and excellent life characteristics.
- a substituted oxide in which a part of the Na site of the complex oxide Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 is replaced with a vacancy stably exists is a charge repulsion of a site that can be a Li ion host. Higher reversible capacity can be realized.
- the active material of the second example can exhibit high energy density and high battery voltage, and can realize a non-aqueous electrolyte battery having excellent life characteristics and easy voltage management.
- a complex oxide in which the subscript w is 0 in the above general formula can be manufactured.
- a state in which the value of w +2 is increased to a value in the range of more than 2 and 6 or less by incorporating a composite oxide having a subscript w of 0 as a negative electrode active material into a non-aqueous electrolyte battery and charging this non-aqueous electrolyte battery. become.
- the composite oxide may be synthesized with a raw material composition ratio such that the value of the amount w + 2 of Li in the formula is in the range of more than 2 and 6 or less before the first charge by a method described later. it can.
- the active material containing the complex oxide in a state where the value of Li amount w + 2 is in the range of 6 or more and 2 or less before the first charge suppresses that lithium ions are trapped in the structure during the first charge and discharge. As a result, the initial charge and discharge efficiency can be improved.
- Subscript x in the general formula Li 2 + w Na 2-x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2 for composite oxide represents the Na content in the crystal structure of the composite oxide.
- the active material of the second example changes the average working potential of the electrode containing this active material by changing the amount of Na in the crystal structure, that is, by changing the value of the subscript x, and the redox potential of metallic lithium To 1.2 V (vs. Li / Li + ) to 1.5 V (vs. Li / Li + ). This facilitates the design of the operating potential of the battery.
- the subscript x is a part of the site corresponding to the Na site of the complex oxide Li 2 + w Na 2 Ti 6 O 14 + ⁇ 2 in the substituted complex oxide, which is substituted for the cation M 1 or the vacancy. It is an indicator that shows the ratio.
- the subscript x2 is such that x2 is in the range of 0 ⁇ x2 ⁇ 2, preferably in the range of 0.1 ⁇ x2 ⁇ 0.9, and more preferably in the range of 0.25 ⁇ x2 ⁇ 0.75. is there.
- Formula Li 2 + w Na 2-x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 subscripts in O 14 + ⁇ 2 y2 indicates the amount of cationic m.alpha contained in the crystal structure of the complex oxide represented by the general formula ing.
- the cation M ⁇ is a part of the Na site of the complex oxide Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 . Therefore, the combination of the subscript x2 and the subscript y2 indicates the ratio of the part corresponding to the Na site of the complex oxide Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 in the substituted complex oxide, which is substituted by the cation M ⁇ . It is an index. Therefore, the value of the subscript y2 is less than or equal to the value of the subscript x2.
- This subscript y2 is in the range of 0 ⁇ y2 ⁇ 2. Therefore, the value of the subscript y2 may be zero. In other words, the general formula Li 2 + w Na composite oxide represented by the 2-x2 M ⁇ y2 Ti 6- z2 M ⁇ z2 O 14 + ⁇ 2 may not contain a cation m.alpha. If the value of the subscript y2 is 0, complex oxide active material of the second embodiment includes is represented by the general formula Li 2 + w Na 2-x2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2. In this complex oxide, a portion corresponding to a part of the Na site of the complex oxide Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2, that is, a portion with a ratio represented by the subscript x 2 is void.
- Charge neutrality can be maintained by substituting the pentavalent cation M ⁇ 5 or the hexavalent cation M ⁇ 6 as M ⁇ .
- Such substitution while maintaining the crystal structure of the complex oxide Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 , reduces the Na ion which interferes with lithium ion conduction, and the vacancy which becomes the host site of Li ion It can be increased. Thereby, it is possible to obtain a substituted complex oxide that can realize the improved charge and discharge capacity.
- the subscript y2 is preferably in the range of 0 ⁇ y2 ⁇ 1, and more preferably 0.
- the subscript z2 is in the range of 0 ⁇ z2 ⁇ 6, preferably in the range of 0.1 ⁇ z2 ⁇ 0.9, and more preferably in the range of 0.25 ⁇ z2 ⁇ 0.75.
- the subscripts w, x2, y2, z2 and ⁇ 2 can each take numerical values within a specific range as described above, but as described above, the general formula Li 2+ w Na 2-x 2 M ⁇ y 2 Ti 6- z 2 M ⁇ In the complex oxide represented by z 2 O 14 + ⁇ 2 , the sum of the cation valences is equal to the sum of the anion valences.
- Formula Li 2 + w Na composite oxide represented by the 2-x2 M ⁇ y2 Ti 6- z2 M ⁇ z2 O 14 + ⁇ 2 is obtained by powder X-ray diffraction method using a Cu-K [alpha line for this composite oxide
- the intensity I L20 of the most intense diffraction line appearing in the range 17 ⁇ 2 ⁇ ⁇ 18.5 ° and the intensity of the most intense diffraction line appearing in the range 18.5 ° ⁇ 2 ⁇ ⁇ 19.5 ° intensity ratio I L20 / I H20 and I H20 is preferably in the range of 2.25 ⁇ I L20 / I H20 ⁇ 3.5.
- the intensity ratio I L20 / I H20 is in the range of 2.25 ⁇ I L20 / I H20 ⁇ 3.5 in an X-ray diffraction pattern obtained by powder X-ray diffraction for a composite oxide
- the complex oxide of is a complex oxide having an orthorhombic crystal structure belonging to the space group Fmmm.
- Such a complex oxide has an intensity I L 21 of the diffraction line corresponding to the (111) plane in the X-ray diffraction diagram obtained by powder X-ray diffraction using Cu-K ⁇ radiation for this complex oxide and (202
- the intensity ratio I L21 / I H21 of the intensity I H21 of the diffraction line corresponding to the) surface is in the range of 2.25 ⁇ I L21 / I H21 ⁇ 3.5.
- Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 which is an example of a complex oxide having a space group Fm mm symmetry, can have a crystal structure similar to that shown in FIG. Specifically, it is as follows.
- the crystal structure of the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 includes a region corresponding to the region A shown in FIG. This region is a void site having a channel in which lithium ions can move in three dimensions in the crystal structure, and can occlude and release lithium ions.
- the crystal structure of the complex oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 includes a region corresponding to the region B shown in FIG. This region has a polyhedral structure of oxide centering on Ti or Nb, which is a skeleton of the crystal structure.
- the crystal structure of the composite oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 includes a region corresponding to the region C shown in FIG.
- this region is a site where there is a lithium ion capable of occluding and releasing.
- the crystal structure of the composite oxide Li 2 Na 1.75 Ti 5.75 Nb 0.25 O 14 has an area corresponding to the area D shown in FIG. 3, this region serves as a scaffold for stabilizing the crystal structure Na And Li, and a site where a void is present.
- coordination of the oxide ion is one of the causes of the crystallite growing in a direction preferable for insertion and extraction of lithium ion, and the charge / discharge curve includes steps of potential. Insertion of lithium ions into void sites in different environments can be suppressed.
- the active material containing the composite oxide of this example can suppress the appearance of the step portion of the potential in the charge and discharge curve, and the reversibility of lithium ions in charge and discharge improves, whereby the effective capacity And the life performance of the non-aqueous electrolyte battery can be improved.
- the active material of the second example contains a complex oxide having a crystal structure in which crystal phases having symmetries other than Fmmm are mixed, or a complex oxide having a crystal structure similar to the symmetry of Fmmm Even if it contains an object, the same effect as the active material of the aspect containing the complex oxide having the symmetry of space group Fmmm can be obtained.
- Specific examples of the symmetry similar to the symmetry of Fmmm include Cmca, F222, Pmcm, Pmma and Cmma.
- a complex oxide having a crystal structure having these symmetries has an intensity I L20 of the most intense diffraction line appearing in the range of 17 ° ⁇ 2 ⁇ ⁇ 18.5 °, and 18.5 ° ⁇ regardless of the crystal plane index. It is preferable that the intensity ratio I L20 / I H20 to the intensity I H20 of the strongest diffraction line appearing in the range of 2 ⁇ ⁇ 19.5 ° be in the range of 2.25 ⁇ I L20 / I H20 ⁇ 3.5. In this case, not only the charge and discharge curve becomes gentle but also the reversibility of lithium ions in charge and discharge is improved, whereby the effective capacity can be increased and the life performance of the non-aqueous electrolyte battery can be improved.
- the active material of the second embodiment comprises a composite oxide represented by the general formula Li 2 + w Na 2-x2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ .
- M ⁇ is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn and Al, and w is in the range of 0 ⁇ w ⁇ 4.
- X2 is in the range of 0 ⁇ x2 ⁇ 2
- z2 is in the range of 0 ⁇ z2 ⁇ 6, and ⁇ 2 is in the range of ⁇ 0.5 ⁇ ⁇ 2 ⁇ 0.5.
- the orthorhombic crystal structure of the complex oxide represented by the general formula Li 2+ w Na 2 Ti 6 O 14 reducing part of the Na site to constitute a vacancy site serving as a Li ion host Can.
- the energy density per unit weight or unit volume can be increased while maintaining the lattice volume in which lithium ions are easily stored and released.
- the average operating potential of the electrode can be changed. This facilitates the potential design of the battery.
- the cation M ⁇ is Nb. That is, in this further preferred embodiment, the complex oxide contained in the active material of the second example is represented by the general formula Li 2+ w Na 2 -x 2 Ti 6 -z 2 Nb z 2 O 14 + ⁇ 2 . Since Nb can be divalently reduced from pentavalent to trivalent, at least a portion of Ti capable of being monovalently reduced from tetravalent to trivalent is replaced with Nb, while vacancy sites are formed at the Na site. By the formation, the lithium storage capacity of the complex oxide can be increased.
- the potential with respect to the oxidation-reduction potential of metal lithium at the time of storing Li changes continuously in a wide range of 1.5 V to 1.0 V. Therefore, by replacing at least a part of Ti with Nb, it is possible not only to increase the charge and discharge capacity but also to include in the charge and discharge curve a portion where the amount of change in potential with the change in capacity is large.
- a complex oxide capable of showing such a charge / discharge curve can easily be correlated with the charge / discharge potential and the charge state, and the battery charge state (SOC) management can be facilitated.
- the complex oxide contained in the active material of the second example is a complex oxide of Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 corresponding to the Ti site of two or more types having different valences. Contains elements.
- Such a composite oxide is preferable because the potential gradient during charge and discharge becomes larger.
- the reason why the potential gradient is larger is, for example, that the electronic correlation with the oxide ion differs from each other at the site corresponding to the titanium site in the crystal structure of the complex oxide Li 2+ w Na 2 Ti 6 O 14 + ⁇ 2 2 This is because the existence of elements of the type or more causes a plurality of sites having different electronic correlations between Li ions and oxide ions at this site.
- the higher valence element contained in this site tends to attract more electron clouds of oxide ions, while the lower valence element of oxide ions and electron clouds
- the correlation tends to be weak. This causes a difference in the electronic state of the oxide ion in the vicinity of the lithium host site, and as a result, the electronic correlation that the lithium ion receives from the lithium host site also becomes different. Thus, the amount of change in potential caused by insertion and desorption of lithium ions is increased.
- the composite oxide contained in the active material of the second example can be, for example, in the form of particles.
- the average particle size of the composite oxide contained in the active material of the second example is not particularly limited, and can be changed according to the desired battery characteristics.
- the active material of the second example preferably contains particles of the composite oxide and a conductive material such as carbon coated on the surface thereof. Active materials of such preferred embodiments can exhibit improved rapid charge and discharge performance.
- the above complex oxide has the property that the electronic conductivity increases as the lithium storage amount increases, since the storage and release of lithium occur due to the homogeneous solid state reaction. In such a complex oxide, the electron conductivity is relatively low in the region where the lithium storage amount is small. Therefore, by coating the surface of the composite oxide particles with a conductive substance such as carbon in advance, high rapid charge / discharge performance can be obtained regardless of the lithium storage amount.
- lithium titanate which exhibits electronic conductivity along with lithium storage
- lithium titanate coated on the surface of the composite oxide particles releases lithium at the time of an internal short circuit of the battery to insulate, and therefore can exhibit excellent safety.
- the BET specific surface area of the composite oxide contained in the active material of the second example is not particularly limited, but is preferably 5 m 2 / g or more and less than 200 m 2 / g. More preferably, it is 5 m 2 / g or more and 30 m 2 / g or less.
- the contact area with the electrolytic solution can be secured, good discharge rate characteristics can be easily obtained, and the charge time can be shortened.
- the BET specific surface area is less than 200 m 2 / g, the reactivity with the electrolytic solution is not too high, and the life characteristics can be improved.
- the BET specific surface area is set to 30 m 2 / g or less, the side reactivity with the electrolytic solution can be suppressed, and therefore, further prolonging of the life can be expected.
- the coatability of the slurry containing the active material, which is used for the production of an electrode described later can be made favorable.
- the measurement of the specific surface area can use the same method as the active material of the first example.
- the active material of the second example can be synthesized by, for example, a solid phase reaction method as described below.
- the above salts are preferably salts which decompose at relatively low temperatures to form oxides, such as carbonates and nitrates.
- the resulting mixture is then ground and mixed as homogeneous as possible.
- this mixture is calcined. Pre-baking is performed in the air at a temperature range of 600 to 850 ° C. for a total of 1 to 3 hours. Next, the firing temperature is increased, and main firing is performed in the air at 900 to 1500 ° C.
- lithium which is a light element
- lithium may evaporate when it is fired at a temperature of 900 ° C. or more.
- the amount of transpiration of lithium under the calcination conditions is examined, and an excess amount of lithium raw material is added accordingly to compensate for the transpiration to obtain a sample of the correct composition.
- firing is performed under a high oxygen partial pressure such as in an oxygen atmosphere, or heat treatment (annealing) is performed at a temperature range of 400 to 1000 ° C. after firing in a normal atmosphere. It is preferable to repair oxygen deficiency. If the generation of lattice defects is not suppressed in this manner, the crystallinity may be low.
- the complex oxide obtained in the powder X-ray diffraction method using Cu-K ⁇ ray has 17 In the range of 8 ° ⁇ 2 ⁇ ⁇ 18.5 °, the intensity I L21 of the diffraction line corresponding to the (111) plane and in the range of 18.5 ° ⁇ 2 ⁇ ⁇ 19.5 °, on the (202) plane
- the intensity ratio I L21 / I H21 to the corresponding diffraction line intensity I H21 is 2.25 ⁇ I L21 / I H21 ⁇ 3.5.
- the composite oxide which the subscript w is 0 in the said general formula can be manufactured, for example.
- the value of Li amount w + 2 in the formula is in the range of more than 2 and 6 or less. It has risen to the value.
- the composite oxide can be obtained by immersing the composite oxide in an aqueous solution of lithium hydroxide or the like, so that the value of w + 2 is in the range of more than 2 and 6 or less. .
- pretreatment is performed as follows.
- the battery is disassembled in an argon-filled glove box and the electrode is taken out.
- the removed electrode is washed with an appropriate solvent and dried under reduced pressure.
- an appropriate solvent for example, ethyl methyl carbonate can be used. After washing and drying, make sure that there are no white precipitates such as lithium salt on the surface.
- the cleaned electrode When used for powder X-ray diffraction measurement, the cleaned electrode is cut into an area substantially the same as the area of the holder of the powder X-ray diffraction apparatus, and used as a measurement sample.
- the active material is taken out from the washed electrode, and the analysis is performed on the taken out active material.
- the target sample is crushed until the average particle size becomes about 5 ⁇ m. Even when the average particle size is originally smaller than 5 ⁇ m, it is preferable to carry out grinding treatment with a mortar or the like in order to grind agglomerates.
- the average particle size can be determined by laser diffraction.
- the crushed sample is loaded into a 0.5 mm deep holder portion formed on a glass sample plate.
- a glass sample plate a glass sample plate manufactured by Rigaku Corporation is used. At this time, care should be taken so that the sample is sufficiently filled in the holder portion. In addition, care should be taken not to cause cracks and voids due to insufficient filling of the sample. Then, using another glass plate from the outside, the sample is sufficiently pressed and smoothed.
- the glass plate filled with the sample is placed in a powder X-ray diffractometer, and a diffraction pattern (XRD (X-ray diffraction) pattern) is acquired using Cu-K ⁇ radiation.
- XRD X-ray diffraction
- the position of the peak may be shifted or the peak may be changed depending on the method of filling the sample.
- the intensity ratio may change.
- Such highly oriented samples are measured using a capillary (cylindrical glass capillary). Specifically, a sample is inserted into a capillary, and the capillary is placed on a rotary sample table and measured while being rotated. By such a measuring method, the result of relaxing the orientation can be obtained.
- the X-ray diffraction (XRD) pattern acquired here should be applicable to Rietveld analysis.
- XRD X-ray diffraction
- measure as appropriate so that the step width is 1/3 to 1/5 of the minimum half width of the diffraction peak and the intensity at the peak position of the maximum intensity reflection is 5000 cps or more Adjust time or x-ray intensity.
- the XRD pattern obtained as described above is analyzed by the Rietveld method.
- a diffraction pattern is calculated from a crystal structure model estimated in advance.
- parameters such as lattice constants, atomic coordinates, occupancy rates, etc.
- S the degree of agreement between the observed strength and the calculated strength in Rietveld analysis. It is necessary to analyze such that S is smaller than 1.8.
- the standard deviation ⁇ j should be taken into consideration.
- the fitting parameter S and the standard deviation ⁇ j defined here are estimated by the mathematical formulas described in “The Actual Condition of Powder X-ray Analysis” edited by the Japan Society for the Analysis of Chemical Analysis, X-ray Analysis Research Committee, edited by Izumi Nakai and Izumi Fujio It shall be.
- the above method information on the crystal structure of the active material to be measured can be obtained.
- the active material of the first example is measured as described above, it can be seen that the active material to be measured has a composite oxide having an orthorhombic crystal structure.
- the symmetry of the crystal structure to be measured such as the space groups Cmca and Fmmm, can be examined.
- the powder measured under the above conditions Use raw data without processing X-ray diffraction results. Strongest diffraction line peak top appearing in the range of 17.0 ° ⁇ 2 ⁇ ⁇ 18.5 °, i.e. the maximum intensity is defined as I L. On the other hand, the peak top of the strongest diffraction line appearing in the range of 18.5 ° ⁇ 2 ⁇ ⁇ 19.5 °, that is, the maximum intensity is defined as I H. Then, the intensity ratio I L / I H can be obtained by dividing the intensity numerical value (count number cps per unit time) of the intensity I L by the intensity numerical value (cps) of the intensity I H.
- the diffraction line intensities IL20 and IL20 ( IL21 and IL21 ) of the complex oxide contained in the active material of the second example
- powder X-ray diffraction results measured under the conditions described above Use raw data without processing
- the peak top of the strongest diffraction line appearing in the range of 17 ° ⁇ 2 ⁇ ⁇ 18.5 °, that is, the maximum intensity is defined as IL20 .
- the peak top of the maximum intensity diffraction line of the diffraction line appearing in the range of 18.5 ° ⁇ 2 ⁇ ⁇ 19.5 °, that is, the maximum intensity is defined as I H20 .
- the intensity ratio I L20 / I H20 can be obtained by dividing the intensity numerical value (count number cps per unit time) of the intensity I L20 by the intensity numerical value (cps) of the intensity I H20 .
- the electrode material of the non-aqueous electrolyte battery When the active material to be measured is contained in the electrode material of the non-aqueous electrolyte battery, first, the electrode is taken out of the non-aqueous electrolyte battery, taken out and washed according to the procedure described above, and the powder X-ray diffraction is performed. It is cut into approximately the same area as the area of the holder of the device to make a measurement sample.
- the obtained measurement sample is directly attached to a glass holder for measurement.
- the position of the peak derived from the electrode substrate such as metal foil is measured in advance.
- peaks of other components such as a conductive agent and a binder are also measured in advance.
- the layer containing the active material for example, an active material layer described later
- the active material layer can be peeled off by irradiating the electrode substrate with ultrasonic waves in a solvent.
- the active material layer is sealed in a capillary, placed on a rotating sample table, and measured.
- the composition of the active material can be analyzed using, for example, Inductively Coupled Plasma (ICP) emission spectroscopy.
- ICP Inductively Coupled Plasma
- the abundance ratio of each element depends on the sensitivity of the analyzer used. Therefore, for example, when the composition of the active material of the first example is analyzed using ICP emission spectroscopy, the numerical value may deviate from the element ratio described above by an error of the measuring apparatus. However, even if the measurement results deviate as described above within the error range of the analyzer, the active material of the first example can sufficiently exhibit the effects described above.
- the electrode containing the active material to be measured is taken out of the non-aqueous electrolyte battery and washed.
- the washed electrode body is placed in a suitable solvent and irradiated with ultrasonic waves.
- the electrode layer can be peeled from the current collector substrate by placing the electrode body in ethyl methyl carbonate placed in a glass beaker and vibrating in an ultrasonic cleaner.
- drying under reduced pressure is performed, and the peeled electrode layer is dried.
- a powder containing the target active material, a conductive auxiliary, a binder, and the like is obtained.
- a liquid sample containing an active material can be prepared.
- hydrochloric acid, nitric acid, sulfuric acid, hydrogen fluoride or the like can be used as the acid.
- the composition of the active material can be known by subjecting the liquid sample to ICP emission spectrometry.
- FIG. 5 is a schematic perspective view of an example assembled battery according to the first embodiment.
- the assembled battery 23 shown in FIG. 5 includes a non-aqueous electrolyte battery which is five single batteries 21.
- the battery assembly 23 shown in FIG. 5 further includes four leads 40.
- One lead 40 connects the negative electrode terminal 6 of one unit cell 21 and the positive electrode terminal 7 of another unit cell 21.
- the five unit cells 21 are electrically connected in series to one another by the four leads 40. That is, the battery assembly 23 of FIG. 5 is a 5-series battery assembly.
- the positive electrode terminal 7 of one of the five single cells 21 is connected to the positive electrode side lead 28 for external connection.
- the negative electrode terminal 6 of one of the five single cells 21 is connected to the negative electrode side lead 30 for external connection.
- the battery assembly including the rectangular non-aqueous electrolyte battery 21 has been described as an example, but the structure of the non-aqueous electrolyte battery included in the battery assembly according to the first embodiment is not particularly limited.
- the battery assembly according to the first embodiment can also include, for example, the non-aqueous electrolyte battery shown in FIGS. 6 and 7 described below.
- FIG. 6 is a schematic cross-sectional view of an example nonaqueous electrolyte battery that can be included in the battery assembly according to the first embodiment.
- 7 is an enlarged cross-sectional view of a portion A of FIG.
- the nonaqueous electrolyte battery 21 shown in FIGS. 6 and 7 includes the bag-like exterior member 2 shown in FIG. 6, the electrode group 1 shown in FIGS. 6 and 7, and a nonaqueous electrolyte not shown.
- the electrode group 1 and the non-aqueous electrolyte are accommodated in the exterior member 2.
- the non-aqueous electrolyte is held by the electrode group 1.
- the bag-like exterior member 2 is made of a laminate film including two resin layers and a metal layer interposed therebetween.
- the electrode group 1 is a flat wound electrode group.
- the flat wound electrode group 1 is formed by spirally winding a laminate obtained by laminating the negative electrode 3, the separator 4, the positive electrode 5, and the separator 4 in this order from the outside, and press-molding the laminate. It is formed.
- the negative electrode 3 includes a negative electrode current collector 3a and a negative electrode layer 3b.
- the negative electrode 3 has a configuration in which the negative electrode layer 3 b is formed only on one side of the inner surface of the negative electrode current collector 3 a as shown in FIG. 7 in the outermost part. In the other part of the negative electrode 3, the negative electrode layer 3 b is formed on both sides of the negative electrode current collector 3 a.
- the positive electrode 5 includes a positive electrode current collector 5a and a positive electrode layer 5b formed on both sides thereof.
- the negative electrode terminal 6 is connected to the negative electrode current collector 3a of the outermost negative electrode 3 and the positive electrode terminal 7 is a positive electrode current collection of the inner positive electrode 5. Connected to the body 5a.
- the negative electrode terminal 6 and the positive electrode terminal 7 are extended from the opening of the bag-like exterior member 2 to the outside.
- the non-aqueous electrolyte battery 21 shown in FIGS. 6 and 7 can be manufactured, for example, by the following procedure. First, the electrode group 1 is manufactured. Then, the electrode group 1 is enclosed in the bag-like exterior member 2. At this time, one end of each of the negative electrode terminal 6 and the positive electrode terminal 7 is protruded to the outside of the package member 2. Next, the periphery of the exterior member 2 is heat sealed leaving a part. Next, for example, a liquid non-aqueous electrolyte is injected from the opening of the bag-like exterior member 2 which has not been heat-sealed. Finally, the wound electrode group 1 and the liquid non-aqueous electrolyte are sealed by heat sealing the opening.
- the battery assembly according to the first embodiment can also include, for example, a battery having the configuration shown in FIGS. 8 and 9.
- FIG. 8 is a partial cutaway perspective view schematically showing another example of the non-aqueous electrolyte battery that can be included in the battery assembly according to the first embodiment.
- FIG. 9 is an enlarged cross-sectional view of a portion B of FIG.
- the non-aqueous electrolyte battery 21 shown in FIGS. 8 and 9 includes the electrode group 11 shown in FIGS. 8 and 9, the exterior member 12 shown in FIG. 8, and a non-aqueous electrolyte not shown.
- the electrode group 11 and the non-aqueous electrolyte are accommodated in the exterior member 12.
- the non-aqueous electrolyte is held by the electrode group 11.
- the exterior member 12 is made of a laminate film including two resin layers and a metal layer interposed therebetween.
- the electrode group 11 is a laminated electrode group as shown in FIG. As shown in FIG. 9, the stacked electrode group 11 has a structure in which the positive electrode 13 and the negative electrode 14 are alternately stacked with the separator 15 interposed therebetween.
- the electrode group 11 includes a plurality of positive electrodes 13. Each of the plurality of positive electrodes 13 includes a positive electrode current collector 13a and a positive electrode layer 13b supported on both sides of the current collector 13a. Further, the electrode group 11 includes a plurality of negative electrodes 14. Each of the plurality of negative electrodes 14 includes a negative electrode current collector 14 a and a negative electrode layer 14 b supported on both sides of the negative electrode current collector 14 a. One side of the negative electrode current collector 14 a of each negative electrode 14 protrudes from the negative electrode 14. The protruding negative electrode current collector 14 a is electrically connected to the strip-shaped negative electrode terminal 16. The tip of the strip-like negative electrode terminal 16 is pulled out of the exterior member 12 to the outside.
- the side of the positive electrode current collector 13 a of the positive electrode 13 opposite to the protruding side of the negative electrode current collector 14 a protrudes from the positive electrode 13.
- the positive electrode current collector 13 a protruding from the positive electrode 13 is electrically connected to the strip-like positive electrode terminal 17.
- the tip of the strip-like positive electrode terminal 17 is located on the opposite side to the negative electrode terminal 16 and is drawn out from the side of the exterior member 12.
- the assembled battery according to the first embodiment includes five non-aqueous electrolyte batteries electrically connected in series with one another.
- Each non-aqueous electrolyte battery comprises a negative electrode containing an active material containing a titanium composite oxide.
- This titanium composite oxide contains Na and the metal element M in the crystal structure.
- the metal element M is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn and Al.
- This battery assembly can exhibit an average operating voltage similar to that of a 12V battery assembly including a lead storage battery. Therefore, the assembled battery according to the first embodiment can exhibit excellent voltage compatibility with the assembled battery including the lead storage battery.
- a battery pack is provided.
- the battery pack includes the assembled battery according to the first embodiment.
- FIG. 10 is an exploded perspective view of an example battery pack according to the second embodiment.
- FIG. 11 is a block diagram showing an electric circuit of the battery pack of FIG.
- the battery pack 20 shown in FIGS. 10 and 11 includes five single cells 21.
- the five unit cells 21 are the flat non-aqueous electrolyte battery 10 described with reference to FIGS. 6 and 7.
- the plurality of unit cells 21 are stacked such that the negative electrode terminal 6 and the positive electrode terminal 7 extended to the outside are aligned in the same direction, and are assembled with the adhesive tape 22 to configure the assembled battery 23. These single cells 21 are electrically connected in series with each other as shown in FIG. That is, the battery pack shown in FIG. 10 is equipped with the battery pack of one example according to the first embodiment.
- the printed wiring board 24 is disposed to face the side surface of the assembled battery 23 from which the negative electrode terminal 6 and the positive electrode terminal 7 extend.
- a thermistor 25 On the printed wiring board 24, as shown in FIG. 11, a thermistor 25, a protection circuit 26, and a terminal 27 for energizing to an external device are mounted.
- An insulating plate (not shown) is attached to the surface of the printed wiring board 24 facing the battery assembly 23 in order to avoid unnecessary connection with the wiring of the battery assembly 23.
- the positive electrode side lead 28 is connected to the positive electrode terminal 7 located in the lowermost layer of the assembled battery 23, and the tip thereof is inserted into the positive electrode side connector 29 of the printed wiring board 24 and is electrically connected.
- the negative electrode lead 30 is connected to the negative electrode terminal 6 located in the uppermost layer of the assembled battery 23, and the tip thereof is inserted into the negative electrode connector 31 of the printed wiring board 24 and is electrically connected.
- the thermistor 25 detects the temperature of the unit cell 21, and the detection signal is transmitted to the protection circuit 26.
- the protection circuit 26 can cut off the plus side wiring 34 a and the minus side wiring 34 b between the protection circuit 26 and the energizing terminal 27 to the external device under predetermined conditions.
- the predetermined condition is, for example, when the temperature detected by the thermistor 25 becomes equal to or higher than a predetermined temperature.
- another example of the predetermined condition is a case where overcharge, overdischarge, over current, and the like of the single battery 21 are detected. The detection of the overcharge and the like is performed on the individual single cells 21 or the entire assembled battery 23.
- the battery voltage When detecting each single battery 21, the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected. In the latter case, a lithium electrode used as a reference electrode is inserted into each single battery 21.
- wires 35 for voltage detection are connected to each of the single cells 21, and a detection signal is transmitted to the protection circuit 26 through the wires 35.
- Protective sheets 36 made of rubber or resin are respectively disposed on the three side surfaces of the assembled battery 23 except the side surfaces from which the positive electrode terminal 7 and the negative electrode terminal 6 protrude.
- the battery assembly 23 is stored in the storage container 37 together with the protective sheets 36 and the printed wiring board 24. That is, the protective sheet 36 is disposed on both the inner side in the long side direction of the storage container 37 and the inner side in the short side direction, and the printed wiring board 24 is disposed on the inner side opposite to the short side.
- the battery assembly 23 is located in a space surrounded by the protective sheet 36 and the printed wiring board 24.
- the lid 38 is attached to the upper surface of the storage container 37.
- a heat shrink tape may be used in place of the adhesive tape 22 for fixing the battery assembly 23.
- protective sheets are disposed on both sides of the battery pack, and the heat shrinkable tape is circulated, and then the heat shrinkable tape is heat shrunk to bind the battery pack.
- the battery pack having one battery pack has been described as an example, but the battery pack according to the second embodiment can also have a plurality of battery packs.
- the plurality of battery packs can be electrically connected in series and / or in parallel with one another.
- the battery pack according to the second embodiment includes the first assembled battery according to the first embodiment and a lead-acid battery operating at 12 V, and is electrically paralleled through the first assembled battery and a regulator circuit or the like. And a second assembled battery connected to the As described above, the battery pack according to the first embodiment can exhibit the same average operating voltage as the average operating voltage of the lead-acid battery operating at 12 V, and has excellent life performance and rapid charge / discharge performance. Have. Therefore, the battery pack of this example can assist the input / output characteristics of the lead storage battery, and can prevent charging due to overdischarge or large current that causes deterioration. Therefore, the load on the lead-acid battery can be reduced, and thus excellent life characteristics can be exhibited.
- the battery pack of this example can exhibit excellent life characteristics and can be manufactured at lower cost than a battery pack requiring six non-aqueous electrolyte batteries.
- the battery pack according to the second embodiment is suitably used in applications where excellent cycle characteristics are required when taking out a large current. Specifically, it is used as a power source of a digital camera or as an on-vehicle battery of, for example, a two- or four-wheel hybrid electric vehicle, a two- or four-wheel electric vehicle, or an assist bicycle. In particular, it is suitably used as a vehicle-mounted battery.
- the battery pack according to the second embodiment includes the battery assembly according to the first embodiment, it can exhibit excellent voltage compatibility with a battery assembly including a lead storage battery.
- Example A Examples A-1 to A-12
- the products of Examples A-1 to A-12 were synthesized by the following procedure.
- the target compositions of each of Examples A-1 to A-12 are shown in Table 1 below.
- the starting materials prepared as described above were mixed, and this mixture was charged into a ball mill agate pod (volume 300 ml).
- Agate balls made of 10 mm and 5 mm in diameter, respectively, were placed in the pod at a volume of 1: 1 and 1/3 of the pod volume.
- 50 ml of ethanol was added to the pod and wet mixed at 120 rpm for 60 minutes to obtain a mixture. Since the raw materials are uniformly mixed by such wet mixing, a single phase of the target crystal phase can be obtained.
- the mixture thus obtained was subsequently subjected to a first baking at a temperature of 900 ° C. for 6 hours. After firing, the fired powder was taken out of the furnace, and the fired powder was remixed.
- the recombined fired powder was placed in a furnace and subjected to a second firing for 6 hours at a temperature of 900 ° C. in an air atmosphere. After this, the temperature in the electric furnace was maintained at 400 ° C. for 2 hours and then cooled rapidly to room temperature. Then, the fired powder was taken out of the furnace, and the fired powder was remixed.
- the powders obtained after the second firing ie, as a result of firing for a total of 12 hours at a temperature of 900 ° C., were the products of Examples A-1 to A-12.
- Example A-13 In Example A-13, the procedure is the same as that of Example A-6 except that firing is performed in a reducing atmosphere while flowing the inside of the electric furnace with nitrogen gas containing 3% hydrogen. 13 products were synthesized.
- Reference Examples A-1 to A-7 the compound Li 2 SrTi 6 O 14 was synthesized by the solid phase reaction method described in Non-Patent Document 1. Starting materials and molar ratios were as described in Table 1 above.
- Reference Examples A-4 to A-6 the compounds listed in Table 1 above were synthesized in the same manner as Reference Example A-1 except that the starting materials and molar ratios were as described in Table 1 above.
- Reference Example A-7 the starting materials and molar ratios were as described in Table 1 above, and synthesis was performed in the same manner as Reference Example A-1 except that the temperature at the time of main firing was 1100 ° C.
- Example A-13 had an oxygen subscript of 13.5 in the composition formula. That is, the product of Example A-13 was slightly oxygen deficient relative to Example A-6.
- Powder X-ray diffraction measurement was performed on the products of Examples A-1 to A-13 and the products of Reference Examples A-1 to A-7 according to the procedure described above.
- FIG. 12 shows X-ray charts of Examples A-2, A-4, A-5, A-6 and A-2 as representative X-ray charts.
- Example A-14 In Example A-14, the product of Example A-14 was synthesized by the following procedure.
- Example A-6 a portion of the product of Example A-6 was immersed in an aqueous sucrose solution adjusted to a concentration of 10 wt%. The sucrose solution was then filtered. The filter residue was then heated at 700 ° C. for 2 hours in a nitrogen atmosphere. The product obtained by this heating was taken as the product of Example A-14.
- Example A-14 The product of Example A-14 was analyzed by TEM-EDX (Transmission Electron Microscopy and Energy Dispersive X-ray Spectroscopy), as a result of Example A-6. It was found that the surface of the particles of the product was coated with carbon.
- TEM-EDX Transmission Electron Microscopy and Energy Dispersive X-ray Spectroscopy
- Example A-15 In Example A-15, the surface of the product of Example A-6 is coated with lithium titanate Li 4 Ti 5 O 12 using a tumbling fluidized bed apparatus according to the following procedure, Example A-15 The product of was synthesized.
- Example A-15 The product of Example A-15 was analyzed by TEM-EDX (transmission electron microscopy and energy dispersive X-ray spectroscopy) and electron diffraction to show that the spinel type was on the surface of the particles of the product of Example A-6. It was found that a layer of lithium titanate Li 4 Ti 5 O 12 was coated.
- Example B In Examples B-1 to B-11, Examples A-1 to A-12 and Example A-1 to A-12 were used except that the starting materials shown in Table 4 were used to obtain products of the target composition shown in Table 4 below. Similarly, the products of Examples B-1 to B-11 were obtained. The molar ratio of the starting materials was made to be the ratio shown in Table 4 below.
- Example B-1 to B-11 were subjected to compositional analysis and powder X-ray diffraction measurement in the same manner as in Example A series. The results are shown in Tables 5 and 6 below, respectively.
- Example C In Reference Examples C-1 to C-4, Examples C-5 and C-6, and Reference Example C-7, in order to obtain the products of the target composition shown in Table 7 below, starting shown in Table 7 Products of Reference Examples C-1 to C-4, Examples C-5 and C-6, and Reference Example C-7 in the same manner as in Examples A-1 to A-12 except that the raw materials were used. I got The molar ratio of the starting materials was made to be the ratio shown in Table 7 below.
- Example D In Examples D-1 to D-16, Examples A-1 to A-12 were used except that the starting materials shown in Table 10 were used to obtain products of the target compositions shown in Table 10 below. The products of Examples D-1 to D-16 were obtained in the same manner as in. The molar ratio of the starting materials was made to be the ratio shown in Table 10 below.
- Example D-1 to D-16 were subjected to compositional analysis and powder X-ray diffraction measurement in the same manner as in Example A series. The results are shown in Tables 11 and 12 below, respectively.
- Electrochemical measurement The electrochemical measurement was performed in the following procedures about each product obtained by the said Example and the reference example. In addition, although the example using the product of Example A-1 is demonstrated below, also about each product of another Example and a reference example, an electrochemical measurement is carried out similarly to the product of Example A-1. went.
- particles of the product of Example A-1 were pulverized to an average particle size of 5 ⁇ m or less to obtain a pulverized product.
- acetylene black was mixed as a conductive agent at a ratio of 10 parts by mass with respect to the active material to obtain a mixture.
- this mixture was dispersed in NMP (N-methyl-2-pyrrolidone) to obtain a dispersion.
- NMP N-methyl-2-pyrrolidone
- PVdF polyvinylidene fluoride
- This slurry was applied onto a current collector made of aluminum foil using a blade. After drying this at 130 ° C. under vacuum for 12 hours, rolling was performed so that the density of the electrode layer (excluding the current collector) was 2.2 g / cm 3 , to obtain an electrode.
- the electrochemical measurement cell of Example A-1 was produced using this electrode, metallic lithium foil as a counter electrode, and a non-aqueous electrolyte.
- a non-aqueous electrolyte one in which lithium hexafluorophosphate (LiPF 6 ) was dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) was used.
- Example A-1 For the electrochemical measurement cell of Example A-1, a charge / discharge test was performed at room temperature. The charge and discharge test was performed with a charge and discharge current value of 0.2 C (time discharge rate) in a potential range of 1.0 V to 3.0 V based on the metal lithium electrode. The initial Li insertion amount in this test was taken as the initial charge capacity, and the Li release amount was taken as the initial discharge capacity. At this time, the value obtained by dividing the initial discharge capacity by the initial charge capacity and multiplying by 100 (initial discharge capacity / initial charge capacity ⁇ 100) was defined as the initial charge / discharge efficiency.
- Example A-1 the electrochemical measurement cell of Example A-1 was repeatedly subjected to 50 cycles of charging and discharging.
- One cycle consisted of one charge and one discharge.
- the charge and discharge were performed at room temperature with a current value of 1 C (hourly discharge rate) in a potential range of 1.0 V to 3.0 V based on the metal lithium electrode.
- Example A-1 In order to confirm the discharge capacity retention rate after 50 cycles, the electrochemical measurement cell of Example A-1 is charged and discharged again at 0.2 C (hourly discharge rate) to set the initial discharge capacity to 100%. Calculated.
- Example A-1 0.2 C discharge capacity and 10.0 C discharge capacity were measured for the electrochemical measurement cell of Example A-1.
- the discharge rate as an index of rate performance was calculated by dividing the 10.0 C discharge capacity obtained by the measurement by the 0.2 C capacity obtained by the measurement as well.
- FIG. 13 the solid curve with the symbol (1) shows the potential change of the electrode containing the orthorhombic oxide of Example A-4.
- the solid curve with the symbol (2) shows the potential change of the orthorhombic oxide-containing electrode of Example A-5.
- the solid curve labeled (3) indicates the change in potential of the orthorhombic oxide-containing electrode of Example A-6.
- the dotted curve with the symbol (4) shows the potential change of the electrode containing the orthorhombic oxide of Reference Example A-1.
- the dotted curve with the symbol (5) shows the potential change of the electrode containing the orthorhombic oxide of Reference Example A-6.
- the electrochemical measurement cell in the range of 1.0 V (vs. Li / Li + ) to 2.0 V (vs. Li / Li + ) which is the effective potential range of the negative electrode keep potential
- the charge-discharge curves of example a-1 is a 1.4V (vs.Li/Li +) and around 1.2V (vs.Li/Li +) respectively to the vicinity of the flat potential part It became a step-like charge and discharge curve.
- the product of Reference Example A-1 exhibiting such a charge-discharge curve is not preferable in practice.
- the product of Reference Example A-2 has a potential flat portion with a wide charge / discharge curve, so that the correlation between the capacity and the potential is difficult to obtain, and the reversible capacity (Li release capacity) is 100 mAh / g. It is understood that less and less.
- the charge-discharge curves of Examples A-4, A-5 and A-6 are 1.0 V (vs. Li / Li + ) to 1.6 V (vs. Li). It has a continuous potential gradient over the range of (Li + ).
- the state of charge (remaining capacity) of the battery For rechargeable batteries, by examining the battery voltage, it is possible to estimate the state of charge (remaining capacity) of the battery. That is, the continuous potential gradient that the products of Examples A-4 to A-6 can exhibit is useful for charge and discharge control of the battery.
- the electrode capacities of Examples A-4 to A-6 are higher than those of Reference Examples A-1 and A-2. Thus, the products of Examples A-4 to A-6 can provide batteries with high energy density.
- Examples A-1 to A-3, Examples A-7 to A-15, Examples B-1 to B-11, Reference Examples C-1 to C-4, and Example C were the same as in Examples A-4 to At the battery voltage of the electrochemical measurement cell in the range of 0 V (vs. Li / Li + ) to 2.0 V (vs. Li / Li + ), the potential curve of the electrode is smaller than that of Reference Example A-1. There were few step-like charge and discharge curves, and they had continuous potential gradients. Furthermore, the electrode capacities of these examples were also higher than those of Reference Examples A-1 and A-2.
- Example E a non-aqueous electrolyte battery was produced by the following procedure.
- a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) was prepared as a mixed solvent.
- Lithium hexafluorophosphate (LiPF 6 ) was dissolved in this solvent at a concentration of 1M.
- a non-aqueous electrolyte was prepared.
- the non-aqueous electrolyte battery of Example E was produced using the electrode group produced as described above and the non-aqueous electrolyte.
- the charge / discharge curve of the nonaqueous electrolyte battery of Example E is shown in FIG.
- the operating voltage range is higher than that in the case where spinel type lithium titanate (Li 4 Ti 5 O 12 ) is used for the negative electrode, ie, 13.8 V to 10.8 V
- spinel type lithium titanate Li 4 Ti 5 O 12
- Example F In Example F, the assembled battery of Example F was produced according to the following procedure.
- Example F Five manufactured non-aqueous electrolyte batteries were electrically connected in series with one another. Thus, the assembled battery of Example F was produced.
- the charge / discharge curve of the battery assembly of Example F is shown in FIG. As is clear from FIG. 15, the battery pack of Example F had a smooth and continuous voltage fluctuation in the voltage range of 11.5 V to 9.0 V. That is, it was found that the assembled battery of Example F operated at 11.5 V to 9.0 V.
- Example E By using the non-aqueous electrolyte battery of Example E using the product of Example A-5, it is possible to obtain an assembled battery in which the voltage fluctuates gently in the voltage range of 11.5 V to 9.0 V. It was possible.
- This operating voltage is slightly lower than that of the automotive lead storage battery.
- the battery pack capable of showing this operating voltage is used in parallel with the lead storage battery through the regulator circuit, thereby enabling the lead storage battery to start up when the cell motor is started due to the rapid load generated in the lead storage battery or the engine start in cold regions. Can play a role in protecting the battery from overdischarge.
- FIG. 16 shows the charge / discharge curve of the battery pack of Reference Example G.
- the voltage fluctuated gently in the voltage range of 13.8V to 10.8V. That is, it was found that the battery pack of Reference Example G operated at 13.8 V to 10.8 V.
- the non-aqueous electrolyte battery of Example E using the product of Example A-5, it is possible to obtain an assembled battery in which the voltage fluctuates gently in the voltage range of 13.8 V to 10.8 V. It was possible.
- This operating voltage is slightly higher than that of the automotive lead storage battery.
- the assembled battery of the reference example G capable of showing an operating voltage higher than the operating voltage of the lead storage battery is connected to the lead storage battery through a regulator circuit in a vehicle equipped with an idling stop system or a vehicle equipped with a hybrid mechanism by a traveling motor.
- the load on the lead storage battery can be reduced when performing a large current discharge or regenerative input, and the life of the lead storage battery can be extended by avoiding deep charge and discharge.
- Example A2 Examples A2-1 to A2-13
- the products of Examples A2-1 to A2-13 were synthesized by the following procedure.
- the respective target compositions of Examples A2-1 to A2-13 are shown in Table 17 below.
- the starting materials prepared as described above were mixed, and this mixture was charged into a ball mill agate pod (volume 300 ml).
- Agate balls made of 10 mm and 5 mm in diameter, respectively, were placed in the pod at a volume of 1: 1 and 1/3 of the pod volume.
- 50 ml of ethanol was added to the pod and wet mixed at 120 rpm for 60 minutes to obtain a mixture. Since the raw materials are uniformly mixed by such wet mixing, a single phase of the target crystal phase can be obtained.
- the mixture thus obtained was subsequently subjected to a first baking at a temperature of 900 ° C. for 6 hours. After firing, the fired powder was taken out of the furnace, and the fired powder was remixed.
- the recombined fired powder was placed in a furnace and subjected to a second firing for 6 hours at a temperature of 900 ° C. in an air atmosphere. After this, the temperature in the electric furnace was maintained at 400 ° C. for 2 hours and then cooled rapidly to room temperature. Then, the fired powder was taken out of the furnace, and the fired powder was remixed.
- the powders obtained after the second firing ie, as a result of firing for a total of 12 hours at a temperature of 900 ° C., were the products of Examples A2-1 to A2-13.
- Example A2-14 In Example A2-14, the procedure of Example A2-5 is repeated except that firing is performed in a reducing atmosphere while flowing nitrogen gas containing 3% of hydrogen in the electric furnace. Fourteen products were synthesized.
- Reference Example A2-1 the compound Li 2 Na 2 Ti 6 O 14 is used as a target composition under the two different conditions to show that the intensity ratio of the powder X-ray diffraction pattern differs depending on the synthesis conditions.
- the products of A2-1b were synthesized respectively.
- Reference Example A2-1a as shown in Table 17, except that the starting material containing no M ⁇ source was used, and that the calcining was continued for 24 hours at 1000 ° C. without considering the amount of Li evaporation during the calcining
- the product of Reference Example A2-1a was synthesized in the same manner as in Example A2-1.
- Reference Example A2-1b as shown in Table 17, the product of Reference Example A2-1b was synthesized in the same manner as Example A2-1 except that the starting material containing no M ⁇ source was used. did.
- Reference Example A2-2 the product of Reference Example A2-2 was synthesized in the same manner as Reference Example A2-1b except that the amounts of lithium carbonate and sodium carbonate were changed as described in Table 17.
- Reference Example A2-3 the product of Reference Example A2-3 was synthesized in the same manner as Reference Example A2-1b except that the starting materials shown in Table 17 were used.
- Reference Examples A2-4 to A2-5 the synthesis method of Reference Examples A2-4 and A2-5 is the same as that of Example A2-1 except that the composition described in Non-Patent Document 2 is used as the target composition.
- the respective products were synthesized.
- the target composition, starting materials and molar ratio were as described in Table 17 above.
- Example A2-14 had an oxygen subscript of 13.5 in the composition formula. That is, the product of Example A2-14 had a slight oxygen deficiency relative to Example A2-5.
- Powder X-ray diffraction measurement was performed on the products of Examples A2-1 to A2-14 and the products of Reference Examples A2-1 to A2-5 according to the procedure described above.
- the surface index corresponding to the most intense diffraction line L20 appearing in the range of 17 ° ⁇ 2 ⁇ ⁇ 18.5 ° and the value of 2 ⁇ of this diffraction line L 2 ⁇ L20 , the plane index corresponding to the most intense diffraction line H appearing in the range of 18.5 ° ⁇ 2 ⁇ ⁇ 19.5 °, the value 2 ⁇ H20 of 2 ⁇ of this diffraction line H20, and the intensity ratio I of these diffraction lines L20 / I H20 is shown in Table 19 below.
- the products obtained in Examples A-1 to 14 are orthorhombic crystals having the symmetry of space group Fmmm shown in FIG. It turned out to be a compound.
- the crystal phases and space groups of each product are summarized in Table 19 below.
- FIG. 17 shows X-ray charts of Example A2-2, Example A2-4, Example A2-5, and Example A2-6 as representative X-ray charts.
- Example A2-15 In Example A2-15, the product of Example A2-15 was synthesized by the following procedure.
- Example A2-5 a portion of the product of Example A2-5 was immersed in an aqueous sucrose solution adjusted to a concentration of 10 wt%. The sucrose solution was then filtered. The filter residue was then heated at 700 ° C. for 2 hours in a nitrogen atmosphere. The product obtained by this heating was made the product of Example A2-15.
- Example A2-15 The product of Example A2-15 is analyzed by TEM-EDX (Transmission Electron Microscopy and Energy Dispersive X-ray Spectroscopy), as a result of Example A2-5. It was found that the surface of the particles of the product was coated with carbon.
- TEM-EDX Transmission Electron Microscopy and Energy Dispersive X-ray Spectroscopy
- Example A2-16 In Example A2-16, the surface of the product of Example A2-5 is coated with lithium titanate Li 4 Ti 5 O 12 using a tumbling fluidized bed apparatus according to the following procedure; Example A2-16 The product of was synthesized.
- Example A2-16 The product of Example A2-16 was analyzed by TEM-EDX (transmission electron microscopy and energy dispersive X-ray spectroscopy) and electron beam diffraction to show that the spinel type was on the surface of the particles of the product of Example A2-5. It was found that a layer of lithium titanate Li 4 Ti 5 O 12 was coated.
- Example B2 In Example B2-1 to B2-8, Examples A2-1 to A2-13 were used except that the starting materials shown in Table 20 were used to obtain products of the target compositions shown in Table 20 below. Similarly, the products of Examples B2-1 to B2-8 were obtained. The molar ratio of the starting materials was made to be the ratio shown in Table 20 below.
- Example B2-1 to B2-8 were subjected to compositional analysis and powder X-ray diffraction measurement in the same manner as in Example A2 series. The results are shown in Tables 21 and 22 below, respectively.
- Example C2 In Examples C2-1 to C2-10, Examples A2-1 to A2-12 were used except that the starting materials shown in Table 23 were used in order to obtain products of the target compositions shown in Table 23 below. Similarly, the products of Examples C2-1 to C2-10 were obtained. The molar ratios of the starting materials were made to be the ratios shown in Table 23 below.
- Reference Example C2 In Reference Examples C2-1 and C2-2, in order to obtain products of the target composition shown in Table 23 below, synthesis is carried out by the method described in Patent Document 3 to produce Reference Examples C2-1 and C2-2. I got a thing. The molar ratio of the starting materials was made to be the ratio described in Table 23 below.
- Example C2-1 to C2-7 and Reference Examples C2-1 and C2-2 were subjected to compositional analysis and powder X-ray diffraction measurement in the same manner as in Example A2. The results are shown in Table 24 and Table 25 below, respectively.
- Example D2 In Examples D2-1 to D2-18, Examples A2-1 to A2-12 were used except that starting materials shown in Table 26 were used to obtain products of the target compositions shown in Table 26 below. The products of Examples D2-1 to D2-18 were obtained in the same manner as in. The molar ratios of the starting materials were made to be the ratios shown in Table 26 below.
- Example D2-1 to D2-18 were subjected to compositional analysis and powder X-ray diffraction measurement in the same manner as in Example A2 series. The results are shown in Table 27 and Table 28 below, respectively.
- particles of the product of Example A2-1 were pulverized to an average particle size of 5 ⁇ m or less to obtain a pulverized product.
- acetylene black was mixed as a conductive agent at a ratio of 10 parts by mass with respect to the active material to obtain a mixture.
- this mixture was dispersed in NMP (N-methyl-2-pyrrolidone) to obtain a dispersion.
- NMP N-methyl-2-pyrrolidone
- PVdF polyvinylidene fluoride
- This slurry was applied onto a current collector made of aluminum foil using a blade. After drying this at 130 ° C. under vacuum for 12 hours, rolling was performed so that the density of the electrode layer (excluding the current collector) was 2.2 g / cm 3 , to obtain an electrode.
- the electrochemical measurement cell of Example was produced using this electrode, metallic lithium foil as a counter electrode, and a non-aqueous electrolyte.
- a non-aqueous electrolyte one in which lithium hexafluorophosphate (LiPF 6 ) was dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) was used.
- Example A2-1 For the electrochemical measurement cell of Example A2-1, a charge and discharge test was performed at room temperature. The charge and discharge test was performed with a charge and discharge current value of 0.2 C (time discharge rate) in a potential range of 1.0 V to 3.0 V based on the metal lithium electrode. The initial Li insertion amount in this test was taken as the initial charge capacity, and the Li release amount was taken as the initial discharge capacity. At this time, the value obtained by dividing the initial discharge capacity by the initial charge capacity and multiplying by 100 (initial discharge capacity / initial charge capacity ⁇ 100) was defined as the initial charge / discharge efficiency.
- Example A2-1 the electrochemical measurement cell of Example A2-1 was repeatedly subjected to 50 cycles of charging and discharging.
- One cycle consisted of one charge and one discharge.
- the charge and discharge were performed at room temperature with a current value of 1 C (hourly discharge rate) in a potential range of 1.0 V to 3.0 V based on the metal lithium electrode.
- the electrochemical measurement cell of the example was charged and discharged again at 0.2 C (time discharge rate), and the capacity retention rate was calculated with the initial discharge capacity as 100%.
- Example A2-1 With respect to the electrochemical measurement cell of Example A2-1, the 0.2 C discharge capacity and the 10.0 C discharge capacity were each measured.
- the discharge rate as an index of rate performance was calculated by dividing the 10.0 C discharge capacity obtained by the measurement by the 0.2 C capacity obtained by the measurement as well.
- the solid curve labeled (4) shows the potential change of the electrode containing the orthorhombic complex oxide of Example A2-9.
- the dotted curve with the symbol (5) indicates the potential change of the electrode containing the orthorhombic complex oxide of Reference Example A2-1b.
- the effective potential range of the negative electrode is in the range of 1.0 V (vs. Li / Li + ) to 2.0 V (vs. Li / Li + ).
- the charge / discharge curve of Reference Example A2-1b has a potential flat portion in which the amount of change in potential accompanying the change in capacitance is small over a wide range of capacitance.
- the product of Reference Example A2-1b exhibiting such a charge / discharge curve is not preferable for practical use because it is difficult to grasp the correlation between the charge capacity and the battery voltage as described above.
- the electrode of Reference Example A2-1b has a capacity of about 90 mAh / g and a low capacity.
- the charge-discharge curves of Examples A2-4, A2-5, A2-6 and A2-9, as shown in FIG. 18, are 1.0 V (vs. Li / Li + ) to 2.0 V. Over the range of (vs. Li / Li + ), it has a large continuous potential gradient with the amount of change in potential accompanying change in charge and discharge capacity.
- the state of charge (remaining capacity) of the battery For rechargeable batteries, by examining the battery voltage, it is possible to estimate the state of charge (remaining capacity) of the battery. That is, the continuous potential gradient that the products of Examples A2-4, A2-5, A2-6 and A2-9 can exhibit is useful for charge and discharge control of the battery.
- the electrode capacity of Examples A2-4, A2-5, A2-6 and A2-9 is higher than that of Reference Example A-1 b.
- the products of Examples A2-4, A2-5, A2-6 and A2-9 can provide batteries with high energy density.
- Table 18 by changing the value of the general formula Li 2 + w Na 2-x2 M ⁇ y2 Ti 6-z2 M ⁇ z2 O 14 + ⁇ 2 in subscript x2 for composite oxide, a battery It can be seen that the battery voltage can be adjusted arbitrarily depending on the application. For example, when using as an assembled battery for motor vehicles whose operating voltage range is fixed, a desired battery voltage can be obtained by changing the negative electrode potential as shown in the embodiment by the combined positive electrode.
- Examples A2-1 to A2-3, A2-7, A2-8, A2-10 to A2-16, B2-1 to B2-8, C2-1 to C2-10 and D2 are electrochemical measurement cells in the range of 1.0 V to 2.0 V as in Examples A2-4 to 6 and A2-9.
- the amount of change in potential accompanying the change in capacity during charge and discharge was larger than that in Reference Example A2-1b, and had a continuous potential gradient corresponding to the charge and discharge capacity.
- the electrode capacity of these examples was also higher than that of Reference Example A2-1b.
- the potential at SOC 50% was 50% charge (Li insertion) of the capacity at 0.2 C from the electrode potential in the open circuit state with respect to metal Li in a half charge state (complete discharge (Li desorption) state And the potential after one hour from the open circuit state).
- the potential difference ⁇ V of SOC 20-80% is a potential difference between the electrode potential at 20% of the 0.2 C discharge capacity (vs lithium metal) and the electrode potential at 80%.
- FIG. 19 shows a discharge (Li release) curve of Li 2 Na 1.5 Ti 5.5 Nb 0.5 O 14 as an example.
- the electrode is then subjected to a discharge (Li release) to 2.0 V (versus metallic lithium) at 0.2C.
- a discharge curve as shown in FIG. 19 is obtained.
- the difference between the potential at the capacity C 20 corresponding to 20% (relative to metallic lithium) and the potential at the capacity C 80 corresponding to 80% (relative to metallic lithium) is as described above. Calculated from the discharge curve obtained. In Figure 19, located in 1.445V (vs.Li/Li +) at SOC 80%, it is in SOC20% 1.264V (vs.Li/Li +). Therefore, the difference, that is, the potential difference ⁇ V, is 181 mV. As the numerical value is larger, the electrode potential changes more greatly with the change of the capacity in charge and discharge. An electrode having a high numerical value can easily understand the correlation between the charge and discharge capacity and the battery voltage, and can estimate that the electrode is easy to perform charge and discharge management.
- Example E2 In Example E2, a non-aqueous electrolyte battery was produced by the following procedure.
- a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) was prepared as a mixed solvent.
- Lithium hexafluorophosphate (LiPF 6 ) was dissolved in this solvent at a concentration of 1M.
- a non-aqueous electrolyte was prepared.
- the non-aqueous electrolyte battery of Example E2 was produced using the electrode group produced as described above and the non-aqueous electrolyte.
- FIG. 20 shows the charge / discharge curve of the non-aqueous electrolyte battery of Example E2.
- the voltage fluctuated gently in the voltage range of 2.3 V to 3.0 V. That is, by using the product of Example A2-5, it was possible to obtain a non-aqueous electrolyte battery in which the voltage fluctuates gently in the voltage range of 2.3 V to 3.0 V.
- the operating voltage range is higher than in the case of using spinel type lithium titanate (Li 4 Ti 5 O 12 ) for the negative electrode, ie, 15.1 V to 11.5 V
- spinel type lithium titanate Li 4 Ti 5 O 12
- Example F2 In Example F2, the assembled batteries of Examples F2-1 to F2-4 were manufactured according to the following procedure.
- Example F2-1 In Example F2-1, the particles of the product of Example A2-4 were used in place of the particles of the product of Example A2-5 in the preparation of the negative electrode, but the particles of the product of Example A2-4 were used and described in Example E2. Five non-aqueous electrolyte batteries of Example F2-1 were produced in the same manner as the procedure.
- Example F2-1 Five manufactured non-aqueous electrolyte batteries were electrically connected in series with one another.
- the assembled battery thus obtained was used as the assembled battery of Example F2-1.
- Examples F2-2 to F2-4 In Examples F2-2 to F2-4, the procedure is the same as that of Example F2-1 except that each of the nonaqueous electrolyte batteries of Examples F2-2 to F2-4 manufactured in the following procedures is used. The assembled batteries of Examples F2-2 to F2-4 were produced.
- Example F2-2 five non-aqueous electrolyte batteries similar to the non-aqueous electrolyte battery of Example E2 were produced by the same procedure as the procedure described in Example E2. These were used as the non-aqueous electrolyte battery of Example F2-2.
- Example F2-3 the particles of the product of Example A2-6 were used in place of the particles of the product of Example A2-5 in the production of the negative electrode, but the particles of the product of Example A2-6 were used and described in Example E2.
- Five non-aqueous electrolyte batteries of Example F2-3 were produced in the same manner as the procedure.
- Example F2-4 the particles of the product of Example A2-9 are used in place of the particles of the product of Example A2-5 in the preparation of the negative electrode, but the particles of the product of Example A2-9 are used.
- Five non-aqueous electrolyte batteries of Example F2-4 were produced in the same manner as the procedure.
- FIG. 21 shows discharge curves of the battery packs of Examples F2-1 to F2-4.
- the dashed-dotted curve indicated by symbol (1) is a discharge curve of the assembled battery of Example F2-1.
- the solid curve with the symbol (2) is the discharge curve of the assembled battery of Example F2-2.
- the dashed curve labeled (3) is the discharge curve of the assembled battery of Example F2-3.
- the solid curve labeled (4) is the discharge curve of the assembled battery of Example F2-4.
- the average operating voltage is about 12.5 V to about 13.5 V. It can be seen that an assembled battery within the range of Also, it can be seen that the respective discharge curves have different voltage gradients. By changing the average operating voltage and the voltage gradient in this manner, it is possible to design the operating voltage of the assembled battery according to the application. For example, when constructing a motor assist type hybrid car or an idling stop system in combination with a 12 V lead storage battery for automobiles, a battery pack voltage according to the overdischarge prevention of the lead storage battery at high load and the voltage fluctuation at the regenerative input. Design is possible.
- non-aqueous electrolyte batteries using spinel type lithium titanate (Li 4 Ti 5 O 12 ) as the negative electrode have a low average operating voltage, and it is necessary to set 6 in series to obtain a voltage compatible with automotive lead storage batteries There is.
- the average operating voltage of the non-aqueous electrolyte battery can be increased. can do.
- Example A2 series can be used for a battery pack. Therefore, by using the products of Example A2 series, Example B2 series, Example C2 series, and Example D2 series, even if the number of series of nonaqueous electrolyte batteries is set to 5 series, it is compatible with 12V lead acid battery for automobile It is possible to construct an assembled battery capable of indicating a voltage that can be made, and thus a battery pack. Therefore, the products of Example A2 series, Example B2 series, Example C2 series and Example D2 series can realize a small battery pack capable of exhibiting low resistance and high energy density at low cost. .
- an assembled battery includes a negative electrode containing an active material containing a titanium composite oxide.
- This titanium composite oxide contains Na and the metal element M in the crystal structure.
- the metal element M is at least one selected from the group consisting of Zr, Sn, V, Nb, Ta, Mo, W, Fe, Co, Mn and Al.
- This battery assembly can exhibit an average operating voltage similar to that of a 12V battery assembly including a lead storage battery. Therefore, this battery pack can exhibit excellent voltage compatibility with a battery pack including a lead-acid battery.
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Abstract
Description
第1の実施形態によると、組電池が提供される。この組電池は、互いに電気的に直列に接続された5個の非水電解質電池を具備する。5個の非水電解質電池の各々は、正極と、負極と、非水電解質とを具備する。負極は、チタン複合酸化物を含む活物質を含む。チタン複合酸化物は、結晶構造中にNa及び金属元素Mを含む。金属元素Mは、Zr、Sn、V、Nb、Ta、Mo、W、Fe、Co、Mn及びAlからなる群より選択される少なくとも1種である。
負極は、集電体と、負極層(負極活物質含有層)とを含むことができる。負極層は、集電体の片面又は両面に形成され得る。負極層は、負極活物質と、任意に導電剤及び結着剤とを含むことができる。
正極は、集電体と、正極層(正極活物質含有層)とを含むことができる。正極層は、集電体の片面若しくは両面に形成され得る。正極層は、正極活物質と、任意に導電剤及び結着剤を含むことができる。
非水電解質は、例えば、電解質を有機溶媒に溶解することにより調製される液状非水電解質、又は、液状電解質と高分子材料とを複合化したゲル状非水電解質であってよい。
無機固体電解質は、リチウムイオン伝導性を有する固体物質である。
セパレータは、例えば、ポリエチレン、ポリプロピレン、セルロース、若しくはポリフッ化ビニリデン(PVdF)を含む多孔質フィルム、又は合成樹脂製不織布から形成されてよい。中でも、ポリエチレン又はポリプロピレンから形成された多孔質フィルムは、一定温度において溶融し、電流を遮断することが可能であるため、安全性を向上できる。
外装部材としては、例えば、厚さが0.5mm以下であるラミネートフィルム又は厚さが1mm以下である金属製容器が用いることができる。ラミネートフィルムの厚さは、0.2mm以下であることがより好ましい。金属製容器は、厚さが0.5mm以下であることがより好ましく、厚さが0.2mm以下であることがさらに好ましい。
正極端子は、例えば、リチウムの酸化還元電位に対する電位が3V以上5V以下の範囲における電気的安定性と導電性とを有する材料から形成されることができる。具体的には、正極端子は、アルミニウム、又はMg、Ti、Zn、Mn、Fe、Cu、Si等の元素を含むアルミニウム合金から形成される。正極端子は、正極集電体との接触抵抗を低減するために、正極集電体と同様の材料から形成されることが好ましい。
第1の例の活物質は、斜方晶型の結晶構造を有し且つ一般式LixM11-yM2yTi6-zM3zO14+δで表される複合酸化物を含む活物質である。ここで、M1は、Sr、Ba、Ca、及びMgからなる群より選択される少なくとも1種である。M2は、Naであるか、又はNaとCs及びKからなる群より選択される少なくとも1種とを含む。M3は、Al、Fe、Zr、Sn、V、Nb、Ta及びMoからなる群より選択される少なくとも1種である。xは2≦x≦6の範囲内にある。yは0<y<1の範囲内にある。zは0<z<6の範囲内にある。δは-0.5≦δ≦0.5の範囲内にある。
x+{2×(1-y)}+y+{4×(6-z)}+{(z3×3)+(z4×4)+(z5×5)+(z6×6)}-28=0 (1)
(1)式を整理すると、以下の(2)式になる:
x-y-4z+(3z3+4z4+5z5+6z6)=2 (2)
式(2)の条件を満たすことにより、複合酸化物の結晶構造中の電荷的中性が保たれる。電荷的中性が保たれている複合酸化物は、一般式LixM1Ti6O14+δで表される複合酸化物の結晶構造において、M1サイトの一部が金属カチオンM2で正しく置換され、Tiサイトの一部が金属カチオンM3で正しく置換された置換酸化物である。一般式LixM1Ti6O14+δで表される複合酸化物の結晶構造内でM2及びM3が正しく置換されている置換酸化物を含むことにより、第1の例の活物質は、リチウムイオンが挿入される空隙サイトに対する酸化物イオンの配位環境を均一にすることができる。これが、第1の例の活物質が含むことができる複合酸化物が1.0V~1.45V(vs.Li/Li+)の電位範囲においてなだらかな電位変化を示すことができる理由である。一方、空隙サイトに対する酸化物イオンの配位環境の均一性が低いと、複合酸化物の充放電カーブは電位の段差部分を示すようになる。
第1の例の活物質が含む複合酸化物のBET比表面積は特に制限されないが、5m2/g以上200m2/g未満であることが好ましい。より好ましくは、5m2/g以上30m2/g以下である。
第1の例の活物質は、以下に説明するような、固相反応法によって合成することができる。まず、原料の酸化物や化合物、塩等を適切な化学量論比で混合して、混合物を得る。上記の塩は、炭酸塩及び硝酸塩のような、比較的低温で分解して酸化物を生じる塩であることが好ましい。次に、得られた混合物を粉砕し、できるだけ均一になるように混合する。次に、この混合物を仮焼成する。仮焼成は、大気中で600~850℃の温度範囲で、延べ1~3時間行う。次に、焼成温度を高くし、大気中で900~1500℃の範囲で本焼成を行う。このとき、軽元素であるリチウムは900℃以上の温度で焼成すると蒸散することがある。この場合、焼成条件下におけるリチウムの蒸散量を調べ、その分、リチウム原料を過剰量含ませることで、蒸散分を補って正しい組成の試料を得るようにする。更に、酸素欠損等による格子欠陥を防止することがより好ましい。例えば、本焼成前に原料粉を加圧成型してペレット状またはロッド状に加工することで、大気と触れる面積を少なくし、且つ粒子同士の接触面積を増やして焼成することで、格子欠陥の生成を抑制できる。工業的な量産の場合には、原料粉を焼成する際に酸素雰囲気下など高い酸素分圧下で焼成するか、又は通常の大気中焼成後に400~1000℃の温度範囲で熱処理(アニール)をして、酸素欠損を修復することが好ましい。このように格子欠陥の生成を抑制しないと、結晶性が低くなる可能性がある。
第2の例の活物質は、斜方晶型の結晶構造を有し且つ一般式Li2+wNa2-x2Mαy2Ti6-z2Mβz2O14+δ2で表される複合酸化物を含む活物質である。ここで、Mαは、Cs及びKからなる群より選択される少なくとも1種である。Mβは、Zr、Sn、V、Nb、Ta、Mo、W、Fe、Co、Mn及びAlからなる群より選択される少なくとも1種である。wは0≦w≦4の範囲内にある。x2は0<x2<2の範囲内にある。y2は0≦y2<2の範囲内にある。z2は0<z2<6の範囲内にある。δ2は-0.5≦δ≦0.5の範囲内にある。
(2+w)+(2-x2)+y2+{4×(6-z2)}+{(z3×3)+(z4×4)+(z5×5)+(z6×6)}-28=0 (1)
(1)式を整理すると、以下の(2)式になる:
w-x2+y2-4z2+(3z3+4z4+5z5+6z6)=0 (2)
式(2)の条件を満たすことにより、複合酸化物の結晶構造中の電荷的中性が保たれる。電荷的中性が保たれている複合酸化物Li2+wNa2-x2Mαy2Ti6-z2Mβz2O14+δ2は、一般式Li2+wNa2Ti6O14+δ2で表される複合酸化物の結晶構造におけるTiサイトの一部がカチオンMβで正しく置換された置換酸化物である。また、電荷的中性が保たれており且つyが0より大きな複合酸化物Li2+wNa2-x2Mαy2Ti6-z2Mβz2O14+δ2は、一般式Li2+wNa2Ti6O14+δ2で表される複合酸化物の結晶構造におけるNaサイトの一部がカチオンMαで正しく置換された置換酸化物である。また、電荷的中性が保たれた複合酸化物Li2+wNa2-x2Mαy2Ti6-z2Mβz2O14+δ2は、一般式Li2+wNa2Ti6O14+δ2で表される複合酸化物の結晶構造におけるNaサイトの一部に対応する部分が結晶構造において安定的に空孔として存在することができる。このように一般式Li2+wNa2Ti6O14+δ2で表される複合酸化物の結晶構造内でカチオンM2が正しく置換されており、一般式Li2+wNa2Ti6O14+δ2で表される複合酸化物の結晶構造内で正しく置換されたカチオンMα及び/又は安定に存在することができる空孔を含んだ置換酸化物を含むことにより、第2の例の活物質は、リチウムイオンが挿入される空隙サイトに対する酸化物イオンの配位環境を均一にすることができる。これが、第2の例の活物質が含むことができる複合酸化物が1.0V~1.45V(vs.Li/Li+)の電位範囲において連続的な電位変化を示すことができる理由である。一方、空隙サイトに対する酸化物イオンの配位環境の均一性が低い複合酸化物は、充放電カーブが電位の段差部分、すなわち電位変化が急峻な部分を示すようになる。
第2の例の活物質が含む複合酸化物のBET比表面積は特に制限されないが、5m2/g以上200m2/g未満であることが好ましい。より好ましくは、5m2/g以上30m2/g以下である。
第2の例の活物質は、例えば、以下に説明するような、固相反応法によって合成することができる。まず、原料の酸化物や化合物、塩等を適切な化学量論比で混合して、混合物を得る。上記の塩は、炭酸塩及び硝酸塩のような、比較的低温で分解して酸化物を生じる塩であることが好ましい。次に、得られた混合物を粉砕し、できるだけ均一になるように混合する。次に、この混合物を仮焼成する。仮焼成は、大気中で600~850℃の温度範囲で、延べ1~3時間行う。次に、焼成温度を高くし、大気中で900~1500℃の範囲で本焼成を行う。このとき、軽元素であるリチウムは900℃以上の温度で焼成すると蒸散することがある。この場合、焼成条件下におけるリチウムの蒸散量を調べ、その分、リチウム原料を過剰量含ませることで、蒸散分を補って正しい組成の試料を得るようにする。更に、酸素欠損等による格子欠陥を防止することがより好ましい。例えば、本焼成前に原料粉を加圧成型してペレット状またはロッド状に加工することで、大気と触れる面積を少なくし、且つ粒子同士の接触面積を増やして焼成することで、格子欠陥の生成を抑制できる。また焼成用の匣鉢に蓋を付けて軽元素の蒸散を防ぐことも有効である。工業的な量産の場合には、原料粉を焼成する際に酸素雰囲気下など高い酸素分圧下で焼成するか、又は通常の大気中焼成後に400~1000℃の温度範囲で熱処理(アニール)をして、酸素欠損を修復することが好ましい。このように格子欠陥の生成を抑制しないと、結晶性が低くなる可能性がある。
活物質の粉末X線回折測定は、次のように行う。
活物質の組成は、例えば、誘導結合プラズマ(Inductively Coupled Plasma:ICP)発光分光法を用いて分析することができる。この際、各元素の存在比は、使用する分析装置の感度に依存する。従って、例えば、第1の例の活物質の組成をICP発光分光法を用いて分析した際、先に説明した元素比から測定装置の誤差分だけ数値が逸脱することがある。しかしながら、分析装置の誤差範囲で測定結果が上記のように逸脱したとしても、第1の例の活物質は先に説明した効果を十分に発揮することができる。
第2の実施形態によると、電池パックが提供される。この電池パックは、第1の実施形態に係る組電池を具備する。
以下、実施例に基づいて上記実施形態をさらに詳細に説明する。なお、合成した斜方晶型複合酸化物の結晶相の同定及び結晶構造の推定は、Cu-Kα線を用いた粉末X線回折法によって行った。また、生成物の組成をICP法により分析し、目的物が得られていることを確認した。
[実施例A]
<実施例A-1~A-12>
実施例A-1~A-12では、以下の手順により、実施例A-1~A-12の生成物を合成した。実施例A-1~A-12のそれぞれの目的組成を、以下の表1に示す。
実施例A-13では、電気炉内を3%の水素を含む窒素ガスでフローしながら還元雰囲気下で焼成を行ったこと以外は、実施例A-6と同様の手順で、実施例A-13の生成物を合成した。
参考例A-1では、非特許文献1に記載された固相反応法で、化合物Li2SrTi6O14を合成した。出発原料及びモル比は、上記表1に記載した通りとした。
実施例A-1~A-13の生成物及び参考例A-1~A-7の生成物の組成を、先に説明したICP法により分析した。その結果を、以下の表2に示す。
実施例A-1~A-13の生成物及び参考例A-1~A-7の生成物について、先に説明した手順で粉末X線回折測定を行った。
実施例A-14では、以下の手順により、実施例A-14の生成物を合成した。
実施例A-15では、以下の手順により、実施例A-6の生成物の表面に転動流動層装置を用いてチタン酸リチウムLi4Ti5O12を被覆して、実施例A-15の生成物を合成した。
実施例B-1~B-11では、以下の表4に示す目的組成の生成物を得るために、表4に示した出発原料を用いたこと以外は実施例A-1~A-12と同様にして、実施例B-1~B-11の生成物を得た。出発原料のモル比は、以下の表4に示した比となるようにした。
参考例C-1~C-4、実施例C-5及びC―6、並びに参考例C-7では、以下の表7に示す目的組成の生成物を得るために、表7に示した出発原料を用いたこと以外は実施例A-1~A-12と同様にして、参考例C-1~C-4、実施例C-5及びC-6、並びに参考例C-7の生成物を得た。出発原料のモル比は、以下の表7に示した比となるようにした。
実施例D-1~D-16では、以下の表10に示す目的組成の生成物を得るために、表10に示した出発原料を用いたこと以外は、実施例A-1~A-12と同様にして、実施例D-1~D-16の生成物を得た。出発原料のモル比は、以下の表10に示した比となるようにした。
上記実施例及び参考例で得られた各生成物について、以下の手順で電気化学測定を行った。なお、以下では実施例A-1の生成物を用いた例を説明するが、他の実施例及び参考例の各生成物についても、実施例A-1の生成物と同様に電気化学測定を行った。
実施例A-4、A-5及びA-6の電気化学測定セル並びに参考例A-1及びA-6の電気化学測定セルの電気化学測定により得られた初回充放電曲線を図13に示す。図13において、符号(1)を付した実線の曲線が、実施例A-4の斜方晶型酸化物を含む電極の電位変化を示している。また、符号(2)を付した実線の曲線が、実施例A-5の斜方晶型酸化物を含む電極の電位変化を示している。更に、符号(3)を付した実線の曲線が、実施例A-6の斜方晶型酸化物を含む電極の電位変化を示している。また、符号(4)を付した点線の曲線が、参考例A-1の斜方晶型酸化物を含む電極の電位変化を示している。更に、符号(5)を付した点線の曲線が、参考例A-6の斜方晶型酸化物を含む電極の電位変化を示している。
実施例Eでは、以下の手順により、非水電解質電池を作製した。
まず、実施例A-5の生成物の粒子を、平均粒子径が5μm以下となるように粉砕して、粉砕物を得た。次に、導電剤としてアセチレンブラックを、該生成物に対して6質量部の割合で混合して、混合物を得た。次に、この混合物をNMP(N-メチル-2-ピロリドン)中に分散して、分散液を得た。この分散液に、結着剤としてのポリフッ化ビニリデン(PVdF)を実施例A-5の生成物に対して10質量部の割合で混合し、負極スラリーを調製した。このスラリーを、ブレードを用いて、アルミ箔からなる集電体上に塗布した。これを真空下130℃で12時間乾燥したのち、電極層(集電体を除く)の密度が2.2g/cm3となるように圧延して負極を得た。
市販のリン酸鉄リチウム(LiFePO4)に、導電助剤としてアセチレンブラックを5重量部の割合で混合して、混合物を得た。次に、この混合物をNMP中に分散して、分散液を得た。この分散液に、結着剤としてのPVdFをリン酸鉄リチウムに対して5重量部の割合で混合し、正極スラリーを調製した。このスラリーを、ブレードを用いて、アルミ箔からなる集電体上に塗布した。これを真空下130℃で12時間乾燥したのち、電極層(集電体を除く)の密度が2.1g/cm3となるように圧延して正極を得た。
以上のようにして作製した正極と負極とを、間にポリエチレン製セパレータを挟んで積層し、積層体を得た。次いで、この積層体を捲回し、更にプレスすることにより、扁平形状の捲回型電極群を得た。この電極群に正極端子及び負極端子を接続した。
混合溶媒として、エチレンカーボネート及びジエチルカーボネートの混合溶媒(体積比1:1)を準備した。この溶媒中に、六フッ化リン酸リチウム(LiPF6)を1Mの濃度で溶解させた。かくして、非水電解質を調製した。
以上のようにして作製した電極群と非水電解質とを用いて、実施例Eの非水電解質電池を作製した。
この実施例Eの非水電解質電池に対して、室温で充放電試験を行った。充放電試験は、電池電圧で1.5V~2.6Vの電圧範囲で、充放電電流値を0.2C(時間放電率)として行なった。
実施例Fでは、以下の手順により、実施例Fの組電池を作製した。
実施例Fの組電池に対して、室温で充放電試験を行った。充放電試験は、組電池の電圧として、7.5V~13.0Vの電圧範囲で、充放電電流値を0.2C(時間放電率)として行った。
参考例Gでは、以下の手順により、参考例Gの組電池を作製した。
参考例Gの組電池に対して、室温で充放電試験を行った。充放電試験は、組電池の電圧として、9.0V~15.6Vの電圧範囲で、充放電電流値を0.2C(時間放電率)として行った。
[実施例A2]
<実施例A2-1~A2-13>
実施例A2-1~A2-13では、以下の手順により、実施例A2-1~A2-13の生成物を合成した。実施例A2-1~A2-13のそれぞれの目的組成を、以下の表17に示す。
実施例A2-14では、電気炉内を3%の水素を含む窒素ガスでフローしながら還元雰囲気下で焼成を行ったこと以外は、実施例A2-5と同様の手順で、実施例A2-14の生成物を合成した。
参考例A2-1では、合成条件により粉末X線回折図の強度比が異なることを示すため、異なる2つの条件で、化合物Li2Na2Ti6O14を目的組成として、参考例A2-1a及びA2-1bの生成物をそれぞれ合成した。参考例A2-1aでは、表17に示したようにMβソースを含まない出発原料を用いたこと、及び焼成中のLi蒸散量を考慮せずに、1000℃で連続24時間焼成したこと以外は実施例A2-1と同様の方法で、参考例A2-1aの生成物を合成した。一方、参考例A2-1bでは、表17に示したようにMβソースを含まない出発原料を用いたこと以外は実施例A2-1と同様の方法で、参考例A2-1bの生成物を合成した。
実施例A2-1~A2-14の生成物及び参考例A2-1~A2-5の生成物の組成を、先に説明したICP法により分析した。その結果を、以下の表18に示す。
実施例A2-1~A2-14の生成物及び参考例A2-1~A2-5の生成物について、先に説明した手順で粉末X線回折測定を行った。
実施例A2-15では、以下の手順により、実施例A2-15の生成物を合成した。
実施例A2-16では、以下の手順により、実施例A2-5の生成物の表面に転動流動層装置を用いてチタン酸リチウムLi4Ti5O12を被覆して、実施例A2-16の生成物を合成した。
実施例B2-1~B2-8では、以下の表20に示す目的組成の生成物を得るために、表20に示した出発原料を用いたこと以外は実施例A2-1~A2-13と同様にして、実施例B2-1~B2-8の生成物を得た。出発原料のモル比は、以下の表20に示した比となるようにした。
実施例C2-1~C2-10では、以下の表23に示す目的組成の生成物を得るために、表23に示した出発原料を用いたこと以外は実施例A2-1~A2-12と同様にして、実施例C2-1~C2-10の生成物を得た。出発原料のモル比は、以下の表23に示した比となるようにした。
参考例C2-1及びC2-2では、以下の表23に示す目的組成の生成物を得るために、特許文献3に記載の方法で合成を行い、参考例C2-1及びC2-2の生成物を得た。出発原料のモル比は、以下の表23に記した比となるようにした。
実施例D2-1~D2-18では、以下の表26に示す目的組成の生成物を得るために、表26に示した出発原料を用いたこと以外は、実施例A2-1~A2-12と同様にして、実施例D2-1~D2-18の生成物を得た。出発原料のモル比は、以下の表26に示した比となるようにした。
上記実施例及び参考例で得られた各生成物について、以下の手順で電気化学測定を行った。なお、以下では実施例A2-1の生成物を用いた例を説明するが、他の実施例及び参考例の各生成物についても、実施例A2-1の生成物と同様に電気化学測定を行った。
実施例A2-4、A2-5、A2-6及びA2-9の電気化学測定セル並びに参考例A-1bの電気化学測定セルの電気化学測定により得られた初回充放電曲線を図18に示す。図18において、符号(1)を付した一点鎖線の曲線が、実施例A2-4の斜方晶型複合酸化物を含む電極の電位変化を示している。また、符号(2)を付した実線の曲線が、実施例A2-5の斜方晶型複合酸化物を含む電極の電位変化を示している。符号(3)を付した破線の曲線が、実施例A2-6の斜方晶型複合酸化物を含む電極の電位変化を示している。更に、符号(4)を付した実線の曲線が、実施例A2-9の斜方晶型複合酸化物を含む電極の電位変化を示している。また、符号(5)を付した点線の曲線が、参考例A2-1bの斜方晶型複合酸化物を含む電極の電位変化を示している。
実施例E2では、以下の手順により、非水電解質電池を作製した。
まず、実施例A2-5の生成物の粒子を、平均粒子径が5μm以下となるように粉砕して、粉砕物を得た。次に、導電剤としてアセチレンブラックを、該生成物に対して6質量部の割合で混合して、混合物を得た。次に、この混合物をNMP(N-メチル-2-ピロリドン)中に分散して、分散液を得た。この分散液に、結着剤としてのポリフッ化ビニリデン(PVdF)を実施例A-5の生成物に対して10質量部の割合で混合し、負極スラリーを調製した。このスラリーを、ブレードを用いて、アルミ箔からなる集電体上に塗布した。これを真空下130℃で12時間乾燥したのち、電極層(集電体を除く)の密度が2.2g/cm3となるように圧延して負極を得た。
市販のスピネル型リチウムマンガン酸化物(LiMn2O4)に、導電助剤としてアセチレンブラックを5重量部の割合で混合して、混合物を得た。次に、この混合物をNMP中に分散して、分散液を得た。この分散液に、結着剤としてのPVdFをリチウムマンガン酸化物に対して5重量部の割合で混合し、正極スラリーを調製した。このスラリーを、ブレードを用いて、アルミ箔からなる集電体上に塗布した。これを真空下130℃で12時間乾燥したのち、電極層(集電体を除く)の密度が2.1g/cm3となるように圧延して正極を得た。
以上のようにして作製した正極と負極とを、間にポリエチレン製セパレータを挟んで積層し、積層体を得た。次いで、この積層体を捲回し、更にプレスすることにより、扁平形状の捲回型電極群を得た。この電極群に正極端子及び負極端子を接続した。
混合溶媒として、エチレンカーボネート及びジエチルカーボネートの混合溶媒(体積比1:1)を準備した。この溶媒中に、六フッ化リン酸リチウム(LiPF6)を1Mの濃度で溶解させた。かくして、非水電解質を調製した。
以上のようにして作製した電極群と非水電解質とを用いて、実施例E2の非水電解質電池を作製した。
この実施例E2の非水電解質電池に対して、室温で充放電試験を行った。充放電試験は、電池電圧で1.8V~3.1Vの電圧範囲で、充放電電流値を0.2C(時間放電率)として行なった。
実施例F2では、以下の手順で、実施例F2-1~F2-4の組電池を作製した。
実施例F2-1では、負極の作製の際に、実施例A2-5の生成物の粒子に代えて、実施例A2-4の生成物の粒子を用いたこと以外は実施例E2で説明した手順と同様の手順により、実施例F2-1の5個の非水電解質電池を作製した。
実施例F2-2~F2-4では、以下の手順で作製した実施例F2-2~F2-4のそれぞれの非水電解質電池を用いたこと以外は実施例F2-1と同様の手順で、実施例F2-2~F2-4の組電池を作製した。
実施例F2-1~F2-4の組電池に対して、室温で充放電試験を行った。充放電試験は、組電池の電圧として、9.0V~15.5Vの電圧範囲で、充放電電流値を0.2C(時間放電率)として行なった。
Claims (7)
- 互いに電気的に直列に接続された5個の非水電解質電池を具備し、
前記5個の非水電解質電池の各々は、
正極と、
負極と、
非水電解質と
を具備し、
前記負極は、結晶構造中にNa及び金属元素Mを含んだチタン複合酸化物を含む活物質を含み、前記金属元素Mは、Zr、Sn、V、Nb、Ta、Mo、W、Fe、Co、Mn及びAlからなる群より選択される少なくとも1種である組電池。 - 前記金属元素MがNbを含む請求項1に記載の組電池。
- 前記チタン複合酸化物の前記結晶構造は空間群Cmca又はFmmmに属する対称性を有する請求項1又は2に記載の組電池。
- 前記チタン複合酸化物は、一般式Li2+aM(I)2-bTi6-cM(II)dO14+σで表される複合酸化物である請求項1又は3に記載の組電池:
ここで、
前記M(I)は、Naであるか、又はNaと、Sr、Ba、Ca、Mg、Cs及びKからなる群より選択される少なくとも1種とを含み、
前記M(II)は、Zr、Sn、V、Nb、Ta、Mo、W、Fe、Co、Mn及びAlからなる群より選択される少なくとも1種であり、
aは0≦a≦6の範囲内にあり、bは0≦b<2の範囲内にあり、cは0<c<6の範囲内にあり、dは0<d≦6の範囲内にあり、σは-0.5≦σ≦0.5の範囲内にある。 - 前記チタン複合酸化物は、斜方晶型の結晶構造を有し且つ一般式LixM11-yM2yTi6-zM3zO14+δで表される複合酸化物である請求項1又は2に記載の組電池:
ここで、
前記M1は、Sr、Ba、Ca、及びMgからなる群より選択される少なくとも1種であり、
前記M2は、Naであるか、又はNaとCs及びKからなる群より選択される少なくとも1種とを含み、
前記M3は、Al、Fe、Zr、Sn、V、Nb、Ta及びMoからなる群より選択される少なくとも1種であり、
xは2≦x≦6の範囲内にあり、yは0<y<1の範囲内にあり、zは0<z<6の範囲内にある。δは-0.5≦δ≦0.5の範囲内にある。 - 前記チタン複合酸化物は、斜方晶型の結晶構造を有し且つ一般式Li2+wNa2-x2Mαy2Ti6-z2Mβz2O14+δ2で表される複合酸化物である請求項1又は2に記載の組電池:
ここで、Mαは、Cs及びKからなる群より選択される少なくとも1種である。Mβは、Zr、Sn、V、Nb、Ta、Mo、W、Fe、Co、Mn及びAlからなる群より選択される少なくとも1種である。wは0≦w≦4の範囲内にある。x2は0<x2<2の範囲内にある。y2は0≦y2<2の範囲内にある。z2は0<z2<6の範囲内にある。δ2は-0.5≦δ≦0.5の範囲内にある。 - 請求項1~6の何れか1項に記載の組電池を具備する電池パック。
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CN107845830A (zh) * | 2016-09-20 | 2018-03-27 | 株式会社东芝 | 固体电解质、锂电池、电池包、及车辆 |
US10707523B2 (en) | 2016-09-20 | 2020-07-07 | Kabushiki Kaisha Toshiba | Solid electrolyte, lithium battery, battery pack, and vehicle |
US20180269539A1 (en) * | 2017-03-17 | 2018-09-20 | Kabushiki Kaisha Toshiba | Electrode for secondary battery, secondary battery, battery pack, and vehicle |
US10886574B2 (en) * | 2017-03-17 | 2021-01-05 | Kabushiki Kaisha Toshiba | Porous electrode including titanium-containing oxide, secondary battery, battery pack, and vehicle |
US10439218B2 (en) | 2017-03-24 | 2019-10-08 | Kabushiki Kaisha Toshiba | Active material, electrode, secondary battery, battery pack, and vehicle |
JP2018190554A (ja) * | 2017-04-28 | 2018-11-29 | Tdk株式会社 | リチウムイオン二次電池用負極活物質、リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
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EP3147974A4 (en) | 2017-08-02 |
KR20180128527A (ko) | 2018-12-03 |
EP3364484A1 (en) | 2018-08-22 |
EP3147974B1 (en) | 2019-02-27 |
CN106104866B (zh) | 2020-01-21 |
US20170005322A1 (en) | 2017-01-05 |
US10511014B2 (en) | 2019-12-17 |
KR101987611B1 (ko) | 2019-06-10 |
KR20170032453A (ko) | 2017-03-22 |
EP3147974A1 (en) | 2017-03-29 |
CN106104866A (zh) | 2016-11-09 |
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