JP2015046308A - Active material and secondary battery arranged by use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an active material by which the worsening of discharge capacity owing to the repetition of charge and discharge can be made smaller, and a superior cycle characteristic can be achieved; and a secondary battery arranged by use thereof.SOLUTION: An active material comprises a complex oxide of sodium and manganese including at least one of NaMnO, NaMnOand NaMnO; in the active material, calcium is substituted for the sodium and solid-dissolved in the complex oxide so that the quantity of the calcium is 10 atom% or less to that of the sodium. The active material is to be used as a positive electrode active material. Using the active material, a secondary battery which is small in the worsening of discharge capacity owing to the repetition of charge and discharge, and superior in cycle characteristic can be arranged. The secondary battery comprises a positive electrode 1, an electrolytic layer 2 and a negative electrode 3, which is shown in a schematic sectional view of FIG. 1.

Description

  The present invention relates to an active material and a secondary battery using the active material.

  In recent years, secondary batteries have been used not only for mobile phones and notebook PCs but also as batteries for electric vehicles.

  A secondary battery is generally composed of a positive electrode, a negative electrode, and an electrolyte (quality). The positive electrode includes, for example, transition metal and alkali metal oxides, and the negative electrode includes, for example, carbon-based materials and alloys such as graphite and hard carbon. System materials, oxide materials, and organic solvents are used for the electrolyte. A typical example of such a battery is a lithium ion battery, and since it has a high energy density, it will be used not only for storage batteries for electric vehicles and households but also for large-scale applications such as voltage stabilization for wind power and solar power generation. Is also expected. However, rare metals such as Li, Co, and Ni are used for the positive electrode material of the lithium ion battery, and the amount existing on the earth, the so-called Clark number, is small. If the demand for Li ion batteries increases in the future, there is a concern that the unit price will rise further. Is done.

In recent years, therefore, sodium ion batteries that charge and discharge with sodium ions have been researched and developed in place of lithium ion batteries. A feature of the sodium ion battery is that a manganese composite oxide (LiMnO ₂ ), which is a layered compound unstable with lithium, can be synthesized relatively easily. For example, Patent Document 1 proposes an oxide containing sodium and manganese as an active material for the positive electrode. On the other hand, in Patent Document 2, it is proposed to use nanowires of single crystal sodium manganate (Na _0.44 MnO ₂ ) as an active material for the positive electrode.

Japanese Patent No. 4793770 JP 2008-226798 A

However, the active material having a structure of Na _x MnO _2-y (where 0 <x ≦ 1, −0.1 <y <0.1) described in Patent Documents 1 and 2 is capacity degradation due to charge / discharge. For example, in the example of Patent Document 2, it is disclosed that, in repeated charge / discharge evaluation (cycle characteristic evaluation), significant capacity deterioration occurs up to 20 cycles in the initial stage of the test.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an active material having a small deterioration in discharge capacity due to repeated charge and discharge and excellent cycle characteristics, and a secondary battery using the active material. .

  The active material of the present invention is composed of a composite oxide containing Na, Mn and Ca, and the content of Ca is 10 atomic% or less with respect to Na.

  The secondary battery of the present invention has a positive electrode, a negative electrode, and an electrolyte, and the positive electrode includes the above active material.

  ADVANTAGE OF THE INVENTION According to this invention, the active material excellent in cycling characteristics with little deterioration of the discharge capacity by repetition of charging / discharging, and a secondary battery using the same can be provided.

It is a schematic sectional drawing of the secondary battery which is one Embodiment of this invention. It is a perspective view which shows the external appearance of a secondary battery.

  A secondary battery according to an embodiment of the present invention will be described with reference to FIG. The secondary battery of this embodiment has an electrolyte layer 2 between the positive electrode 1 and the negative electrode 3, and these constitute a power generation element 4. Further, on the surface opposite to the side facing the electrolyte layer 2 of the positive electrode 1 and the negative electrode 3, a positive electrode side current collecting layer 5P and a negative electrode side current collecting layer 5N are provided, respectively. A secondary battery is formed by housing the power generation element 4 shown in FIG. 1 in a battery case as shown in FIG. There are various battery case forms such as a laminate type, a tube type, and a coin type, but any form may be used. 6N and 6P shown in FIG. 2 are a negative electrode terminal and a positive electrode terminal, respectively, for electrically connecting the external circuit to the negative electrode and the positive electrode, and 7 is a laminate film.

For the positive electrode 1, a composite oxide containing Na, Mn, and Ca (hereinafter sometimes simply referred to as a composite oxide) is used as an active material. This is a solution in which Ca is dissolved in a complex oxide of Na and Mn, and Ca is substituted with Na to form a compound represented by the composition formula Na _x Ca _y MnO _{2 + z} . When Ca is dissolved in a complex oxide of Na and Mn, the activity as an active material is slightly reduced and the capacity of the electrode is reduced, but the rate of decrease in capacity after repeated charge and discharge is reduced, and charge and discharge are reduced. The capacity of the active material in which Ca is dissolved and the capacity of the active material in which Ca is not dissolved are reversed in several cycles, and the capacity of the active material in which Ca is dissolved is compared. growing.

At this time, when the content of Ca is 10 atomic% or less with respect to Na, that is, when a composite oxide containing Na, Mn and Ca is expressed by a composition formula Na _x Ca _y MnO _{2 + z} , y / x ≦ 0. It is important to be in the range of 1. With such a range, it is possible to suppress the capacity reduction due to a decrease in appearance and Na of the crystalline phases, such as CaO or CaCO ₃ is not dissolved in the composite oxide of Na and Mn. In addition, it is preferable to set the Ca content to 1 atomic% or more with respect to Na, that is, y / x ≧ 0.01 because generation of heterogeneous phases can be suppressed and cycle characteristics are further improved.

Further, x is preferably in the range of 0.4 ≦ x ≦ 1.0 and z is in the range of 0 ≦ z ≦ 1. With such a range of x, decrease in capacity of the composite oxide, does not contribute to charging and discharging, such as _Mn 2 _{O 3} and sodium carbonate monohydrate _{(Na 2 CO 3 · H 2} O) crystals Appearance of phases can be suppressed. In addition, when z is in such a range and the crystal contains more oxygen, the crystallinity of the composite oxide can be increased, and a decrease in capacity can be suppressed.

As a composite oxide of Na and Mn having a composition in such a range and having high activity as a positive electrode active material of a secondary battery, for example, Na _0.5 MnO ₂ , Na _0.7 MnO _2.05 , Na _0.7 MnO ₂ , NaMnO ₂ , Na ₄ Mn ₉ O ₁₈ , Na ₂ Mn ₃ O _{7 and the} like can be mentioned, and these composite oxides can dissolve Ca, so that it has excellent cycle characteristics. Become a substance. Among these, NaMnO ₂ , Na _0.7 MnO _2.05 , Na _0.7 MnO ₂ and Na ₄ Mn ₉ O ₁₈ have particularly high activity. Therefore, in the present embodiment, at least one of the group consisting of these is used. It preferably contains a seed crystal phase.

In addition, as described above, crystal phases such as CaO, Mn ₂ O ₃ and Na ₂ CO ₃ .H ₂ O do not contribute to charge / discharge, and the presence of these different phases may cause a reduction in capacity. It is preferable that the active material does not substantially contain these crystal phases. Note that the active material does not substantially contain these crystal phases, and in the X-ray diffraction (XRD) measurement of the active material, different phases such as CaO, Mn ₂ O ₃ and Na ₂ CO ₃ .H ₂ O are confirmed. Say what you can't do.

  Note that the composition of the composite oxide that is an active material may be confirmed by elemental analysis. For example, fluorescent X-ray analysis, wavelength dispersive X-ray spectroscopic analysis (WDS), ICP emission spectroscopic analysis, or the like may be used. The crystal phase contained in the active material can be confirmed by identifying a diffraction pattern obtained by X-ray diffraction (XRD) measurement of the active material. The fact that Ca is dissolved in the complex oxide of Na and Mn, for example, is confirmed by elemental analysis that Ca is contained, and other than the complex oxide of Na and Mn by X-ray diffraction. It can be confirmed from the fact that a heterogeneous phase containing Ca such as CaO cannot be confirmed, and that the lattice constant changes depending on the Ca content.

  In this embodiment, the positive electrode may contain a positive electrode active material other than the composite oxide containing Na, Mn and Ca. Further, as an inevitable impurity in the process, for example, Al, Zr, Mg, Ti, Fe and the like may be contained in a proportion of 0.5% by mass or less.

As an example of a method for producing such an active material, synthesis by a solid phase method will be described. As the Na source, for example, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide and the like can be used. As the Mn source, manganese trioxide (III), manganese dioxide (IV), manganese carbonate (II) and the like can be used. As the Ca source, calcium oxide, calcium carbonate, calcium nitrate, calcium acetate and the like can be used. These raw material powders are blended in a predetermined amount, mixed in a solvent such as alcohol, dried, and then heat-treated in a temperature range of 500 to 800 ° C., preferably 550 to 700 ° C., so that Na, Mn And a composite oxide containing Ca can be obtained. By dissolving Ca, a crystal phase of Na _0.7 MnO _2.05 is formed at a relatively low firing temperature of 500 to 700 ° C., and Na ₄ Mn ₉ O ₁₈ is heated at a high temperature of 700 to 800 ° C. A crystalline phase mainly forms. Note that the method used for the synthesis of the active material is not limited to the solid phase method, and other than that, a complex oxide containing Na, Mn, and Ca can be formed using any of known synthesis methods such as a hydrothermal method and a sol-gel method. You may synthesize. Further, Ca may be dissolved later in a commercially available or synthesized complex oxide of Na and Mn.

  The obtained composite oxide may be subjected to particle size adjustment by pulverization by a technique such as a ball mill or a bead mill, if necessary. When adjusting the particle size, the average particle size of the composite oxide powder may be adjusted to an appropriate range according to the use conditions of the secondary battery using the composite oxide and the method for producing the electrode, for example, 0.1 to 50 μm. An appropriate range corresponding to the purpose may be selected and adjusted from the range. The average particle size of the powder can be confirmed by, for example, particle size distribution measurement by a diffraction scattering method.

  An electrode is produced using the obtained complex oxide. For example, 80% by mass of this composite oxide as an active material, 10% by mass of acetylene black as a conductive assistant, 10% by mass of polyvinylidene fluoride as a binder, and 15% by mass of NMP (N-methylpyrrolidone) as a solvent Is added to make a slurry. The prepared slurry is applied on an Al foil, for example, by a well-known sheet forming method such as a doctor blade method, and the solvent is dried. Thus, an active material that is a composite oxide containing Na, Mn, and Ca and a conductive auxiliary agent are used. An electrode containing a binder can be manufactured.

In addition to polyvinylidene fluoride, a binder selected according to the application, such as polytetrafluoroethylene (PTFE), fluorine rubber, styrene butadiene rubber, polyimide resin (PI), polyamide resin, polyamideimide resin, etc. is used. it can. In addition, the conductive auxiliary agent is ketjen black, carbon nanotube, graphite, hard carbon, metal (aluminum, gold, platinum, etc.) powder instead of acetylene black, inorganic conductive oxide (indium tin oxide (ITO) glass, Any material may be used as long as it is chemically stable and exhibits conductivity in the operating voltage range, such as tin oxide.

  Alternatively, an electrode may be formed using the obtained composite oxide powder by forming a green compact by a molding method such as extrusion molding or a roll compaction method. Alternatively, the composite oxide powder may be fired and used as a sintered body that does not contain a conductive additive or a binder.

  The average particle diameter of the active material particles in the electrode is adjusted by selecting an appropriate range from, for example, a range of 0.1 to 50 μm, depending on the use conditions such as the voltage range and temperature of the secondary battery using the active material do it. For example, when used in a secondary battery application that requires high output, the average particle size of the active material particles is preferably in a relatively small range of 0.5 to 1.0 μm.

  The average particle size of the active material particles in the electrode can be controlled by adjusting the particle size of the composite oxide powder when the electrode is formed by sheet molding or green compact. In the case of forming the electrode, it can be performed by adjusting the particle size of the composite oxide powder and adjusting the firing temperature. The average particle diameter of the active material particles in the electrode is determined by, for example, distinguishing the active material particles in the cross section of the electrode using a scanning electron microscope (SEM) and wavelength dispersive X-ray analysis (WDS), and taking a photograph. It can be obtained by analyzing and calculating.

The type of active material used for the negative electrode 3 differs depending on whether an aqueous or non-aqueous electrolyte is used. In the case of a water-based electrolyte, activated carbon, NaTi ₂ (PO ₄ ) ₃ or the like can be used. In the case of a non-aqueous electrolyte, in addition to an active material that can be used in a water-based electrolyte, Sn—Sb composite glass is used. Or oxide materials such as hard carbon, sodium metal, and Na ₂ Ti ₃ O ₇ can be used.

  As the electrolyte layer 2, any one of an aqueous electrolyte, a non-aqueous electrolyte such as an organic electrolyte or an ionic liquid impregnated in a separator, a polymer solid electrolyte, an inorganic solid electrolyte, or a molten salt may be used. it can.

  The separator impregnated with the aqueous electrolyte solution or the non-aqueous electrolyte solution is required to pass ions and prevent the positive and negative electrodes from being short-circuited. Specifically, a polyolefin fiber nonwoven fabric, a polyolefin microporous film, a glass filter, a ceramic porous material, or the like can be used. Here, examples of the polyolefin include polyethylene and polypropylene, and a separator generally used for a secondary battery such as a lithium ion battery is applicable.

  As the aqueous electrolyte, for example, an aqueous solution of 1 to 3 mol / L sodium sulfate can be used. Such an aqueous electrolyte solution can change the electrolysis potential of water by adjusting the pH, and thus can change the charging potential of the secondary battery.

The organic electrolyte is composed of an organic solvent and an electrolyte salt, and an additive for the purpose of forming a film on the electrode surface, preventing overcharge, imparting flame retardancy, or the like may be added as necessary. As the organic solvent, those having a high dielectric constant, low viscosity and low vapor pressure are preferably used. Examples of such materials include ethylene carbonate (EC), propylene carbonate, butylene carbonate, and γ-butyrolactone. , Sulfolane, 1,2-dimethoxyethane, 1,3-dimethoxypropane, dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, or a mixture of two or more thereof. It is done. Examples of the electrolyte salt include sodium perchlorate (NaClO ₄ ), sodium tetrafluoroborate (NaBF ₄ ), sodium hexafluorophosphate (NaPF ₆ ), NaN (SO ₂ F) ₂ , NaN (CF ₃ SO _{2) 2, NaN} (sodium salt such as _C 2 F 5 _{SO 2) 2} and the like. Among these, NaN (SO ₂ F) ₂ , NaN (CF ₃ SO ₂ ) _2, and NaN (C ₂ F ₅ SO ₂ ) ₂ are mixed with other alkali metal salts and used in an environment at a certain temperature or higher. Therefore, it can also be used as a molten salt.

  When a polymer solid electrolyte or an inorganic solid electrolyte is used as the electrolyte layer 2, the thickness can be reduced to, for example, 10 μm or less, and further 3 μm or less, and more active materials can be used compared to a secondary battery having the same volume. Since packing can be performed, the capacity can be increased, and as a result, the energy density can be improved. However, in order to prevent a short circuit, the solid electrolyte needs to have a necessary minimum thickness that does not cause a dielectric breakdown or a short circuit due to a pinhole.

  A material having corrosion resistance that does not cause a reaction such as dissolution at the potential of the positive electrode may be used for the positive current collecting layer 5P. Examples of such materials include metal materials and alloys including aluminum, tantalum, niobium, titanium, gold, platinum, etc., carbonaceous materials such as graphite, hard carbon, and glassy carbon, inorganic materials such as ITO glass and tin oxide. A conductive oxide material or the like can be used. Among these, aluminum, gold, and platinum are preferable because they are excellent in corrosion resistance and easily available. Aluminum is particularly preferable because it is passivated by forming an oxide film on the surface and excellent in corrosion resistance even at a high potential.

  A material that does not cause side reactions such as alloying with Na at the potential of the negative electrode may be used for the negative current collecting layer 5N. Examples of such materials include metal materials and alloys including copper, nickel, brass, zinc, aluminum, stainless steel, tungsten, gold, platinum, carbonaceous materials such as graphite, hard carbon, and glassy carbon, ITO glass. An inorganic conductive oxide material such as tin oxide can be used. In particular, it is preferable to use aluminum or nickel from the viewpoint of high conductivity and relatively low cost. Aluminum, in particular, has high conductivity and is relatively inexpensive, like copper and nickel, and cannot be used because it forms an alloy with lithium, but is inactive with sodium. Also, it can be used as a current collector.

  The positive electrode side current collecting layer 5P and the negative electrode side current collecting layer 5N may use a metal foil or mesh made of these metal materials, or an inorganic conductive oxide such as a metal material, a carbonaceous material, ITO glass or tin oxide. A conductive ink or the like using a material material as a filler may be applied to the electrode material surface and dried. Moreover, what vapor-deposited metals, such as platinum, aluminum, and titanium, on the electrode material surface may be used.

  In addition, when using metal foil or a mesh, it is preferable that the thickness shall be 5-20 micrometers. Moreover, when using metal foil, you may use what roughened the surface of metal foil in order to improve the adhesive force with electrode material. In this case, the surface roughness of the metal foil is preferably 0.5 to 2 μm in terms of arithmetic average roughness (Ra). The surface roughness of the metal foil is measured using a surface roughness meter such as a stylus type or a light interference type, a laser microscope, an atomic force microscope (AFM), or the like. When using a stylus-type surface roughness meter that is generally used, based on JIS B0601, for example, on the condition that the stylus tip diameter is 2 μm, the measurement length is 4.8 mm, and the cutoff value is 0.8 mm Just measure.

  The secondary battery of the present embodiment has been described above, but the present invention is not limited to the present embodiment, and can be applied to various modifications without departing from the present invention.

  Hereinafter, the secondary battery of this invention is demonstrated in detail based on an Example.

First, a composite oxide containing Na, Mn, and Ca to be a positive electrode active material was synthesized. Sodium carbonate powder (Kanto Chemical Co., Ltd .: reagent grade), manganese trioxide (III) powder (high purity chemistry: 3N) and calcium oxide powder (Kanto Chemical Co., Ltd .: reagent 3N) were used as raw materials. These raw materials, x and y are blended so that the value shown in Table 1 when expressed in a composition formula _{Na x Ca y MnO 2 + z} , slurried with isopropyl alcohol (IPA) as a solvent, a ZrO ₂ ball And mixed for 20 hours in a ball mill. After drying the mixed slurry, heat treatment was performed at the temperature shown in Table 1 for 10 hours to synthesize a composite oxide. The synthesized composite oxide was subjected to X-ray diffraction (XRD) measurement using CuKα rays, and the crystal phase contained in the composite oxide was confirmed by analyzing the diffraction pattern. Table 1 shows the crystal phases contained in each composite oxide. For example, sample No. 3, the presence of a crystal phase of hexagonal Na _0.70 MnO _2.05 was confirmed. The composition of the composite oxide was confirmed by ICP emission spectroscopic analysis, and it was confirmed that there was no change from the composition at the time of preparation.

  Next, a positive electrode was produced using the synthesized composite oxide as an active material. 80% by mass of composite oxide powder synthesized as a positive electrode active material, 10% by mass of acetylene black as a conductive additive, 10% by mass of polyvinylidene fluoride as a binder, and 15% by mass of NMP (N -Methylpyrrolidone) was used to prepare a slurry. This slurry was applied onto an aluminum foil serving as a positive current collecting layer by a doctor blade method, and the solvent was dried to form a positive active material layer having a thickness of 50 μm. The obtained positive electrode active material layer was cut into a 10 × 10 cm square shape together with an aluminum foil serving as a positive electrode side current collecting layer to produce a positive electrode. Furthermore, the aluminum foil used as a positive electrode terminal was attached to the edge part of the surface by which the positive electrode active material layer of aluminum foil was not formed by spot welding.

  Sodium metal was used as the negative electrode active material. A sodium foil serving as a negative electrode active material layer was press-bonded onto an aluminum foil serving as a negative electrode side current collecting layer by pressing, and this was cut into a 10 × 10 cm square shape to produce a negative electrode. Furthermore, the aluminum foil used as a negative electrode terminal was attached by spot welding to the edge part of the surface which has not pressure-bonded the sodium foil of aluminum foil.

  Between the produced positive electrode and negative electrode, a separator of a porous membrane made of polypropylene / polyethylene containing an electrolytic solution was arranged to produce a power generation element. As the electrolytic solution, one obtained by dissolving NaTFSI at 1 mol / L in propylene carbonate (PC), which is an organic solvent, was used.

  The produced power generation element is housed in a bag-shaped aluminum laminate film that is an exterior body, an electrolyte is injected, and the opening of the exterior body is exposed with the ends of the positive electrode terminal and the negative electrode terminal exposed from the opening of the exterior body. The part was sealed by heat welding to obtain a secondary battery.

The manufactured secondary battery was subjected to a charge / discharge test under the following conditions to confirm the battery characteristics.
Charging / discharging voltage range: upper limit 4.0V, lower limit 1.5V
Charging / discharging current value: 1 mA / cm ² (constant current charging / discharging)
Measurement temperature: 30 ° C
Cycle: 100 cycles with one discharge-charge cycle

  Sample No. 2, 3, 5, 7, and 8 are complex oxides of Na and Mn containing 10 atomic% or less of Ca with respect to Na. Therefore, the initial discharge capacity is 100 mAh / g or more, and 100 cycles of charge and discharge Even after the test, the cycle characteristics showing a capacity retention rate of 80% or more were excellent. It can also be seen that the cycle characteristics are improved by the solid solution of Ca regardless of the crystal phase of the composite oxide. On the other hand, sample no. 1 has a capacity retention rate of 60% or less and sample No. 1 containing 14 atomic% of Ca. In No. 4, the initial discharge capacity was reduced to 85 mAh / g.

  Sample No. In No. 6, since the firing temperature was as high as 900 ° C., a lot of different phases were precipitated, and the initial discharge capacity was as low as 78 mAh / g.

DESCRIPTION OF SYMBOLS 1 .... Positive electrode 2 .... Electrolyte layer 3 .... Negative electrode 4 .... Electric power generation element 5N ... Negative electrode side current collecting layer 5P ... Positive electrode side current collecting layer 6N ... Negative electrode terminal 6P ... Positive terminal 7 ... Laminate film

Claims (6)

  An active material comprising a complex oxide containing Na, Mn and Ca, wherein the Ca content is 10 atomic% or less with respect to Na.   The active material according to claim 1, wherein a content of the Ca is 1 atomic% or more with respect to the Na. 3. The composition according to claim 1, comprising at least one crystal phase selected from the group consisting of NaMnO ₂ , Na _0.7 MnO _2.05 , Na _0.7 MnO ₂ and Na ₄ Mn ₉ O _18. The active material as described in. 4. The active material according to claim 1, wherein substantially no crystal phases of CaO, CaCO ₃ , Mn ₂ O ₃ and Na ₂ CO ₃ .H ₂ O are contained.   A secondary battery comprising: a positive electrode; a negative electrode; and an electrolyte, wherein the positive electrode includes the active material according to claim 1.   The secondary battery according to claim 5, wherein charging and discharging are performed by exchanging sodium ions between the positive electrode and the negative electrode.

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