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Secondary battery, battery module, battery pack and vehicle — Kabushiki Kaisha Toshiba (US10727540B2)

ABSTRACT

Abstract

According to one embodiment, a secondary battery including a positive electrode, a negative electrode, and an electrolyte is provided. The negative electrode includes titanium-containing oxide and at least one kind of element selected from the group consisting of B, P, Al, La, Zr, Ge, Zn, Sn, Ga, Pb, In, Bi, and Tl. The electrolyte includes lithium ions and a solvent containing water.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation application of PCT Application No. PCT/JP2017/003666, filed Feb. 1, 2017, and based upon and claiming the benefit of priority from Japanese Patent Application No. 2016-017249, filed Feb. 1, 2016, and Japanese Patent Application No. 2016-184794, filed Sep. 21, 2016, the entire contents of all of which are incorporated herein by reference.

FIELD

Embodiments of the present invention relate to a secondary battery, a battery module, a battery pack and a vehicle.

BACKGROUND

A nonaqueous electrolyte battery in which a lithium metal, a lithium alloy, a lithium compound or a carbonaceous material is used for a negative electrode is expected as a high energy density battery, and active research and development have been conducted. A lithium ion secondary battery including a positive electrode containing LiCoO 2 or LiMn 2 O 4 as an active material and a negative electrode containing a carbonaceous material that allows lithium ions to be inserted in and extracted from has been widely put to practical use for a portable device.

In the case of installing the battery in a vehicle such as an automobile or a train, it is desirable that the positive and negative electrodes include a material excellent in chemical and electrochemical stability, in durability, and in corrosion resistance for obtaining a storage performance in high-temperature environments (e.g., at not less than 60° C.), cycle performance, and reliability of high power over a long time. Further, high performance in cold climates, high-output performance in a low-temperature environment (−40° C.), and long life performance are required. On the other hand, although a nonvolatile and noncombustible electrolytic solution has been developed as a nonaqueous electrolyte for enhancing safety performance, a battery including the electrolytic solution has not yet been put to practical use because output characteristics, low-temperature performance, and long life performance are reduced.

As described above, when the lithium ion secondary battery is installed in a vehicle or the like, there is a problem with the high-temperature durability and low-temperature output performance. Thus, it is difficult to install the lithium ion secondary battery in an engine room of the vehicle in place of a lead storage battery.

Since an electrolytic solution of the lithium ion secondary battery is used at a high voltage of 2 V to 4.5 V, an aqueous solution-based electrolytic solution is not used in the lithium ion secondary battery, and a nonaqueous electrolytic solution in which lithium salt is dissolved in an organic solvent is used. It has been considered to improve a composition of the nonaqueous electrolytic solution in order to improve large current discharge performance and cycle life performance. However, since ion conductivity of the nonaqueous electrolytic solution is lower than that of the aqueous solution-based electrolytic solution, it is difficult to lower the resistance of a battery. Since an organic solvent is used in the nonaqueous electrolyte, high temperature decomposition of the nonaqueous electrolyte is likely to occur. And since heat stability of the nonaqueous electrolyte is poor, high-temperature cycle life performance is lowered. Also, although a solid electrolyte has been considered as a nonaqueous electrolyte, since the ion conductivity of the nonaqueous electrolyte is further lowered, it is difficult to enhance large current discharge performance.

In a nonaqueous electrolyte battery charged and discharged by movement of Li ions between a negative electrode and a positive electrode, a nonaqueous electrolyte containing a nonaqueous solvent is used as an electrolytic solution. Since the nonaqueous solvent has wide potential stability, in the nonaqueous electrolyte battery, a high cell voltage of approximately 3 to 4 V can be exhibited. Thus, the nonaqueous electrolyte battery is excellent in energy density as compared with conventional storage batteries. Therefore, in recent years, the use of nonaqueous electrolyte batteries has been progressing in a wide range of applications including on-vehicle application such as μHEV (micro-hybrid electric vehicle) and an idling stop system, and for stationary use.

However, since a nonaqueous solvent contained in a nonaqueous electrolyte is an organic solvent, the nonaqueous solvent is highly volatile and inflammable. Thus, a nonaqueous electrolyte battery has risks such as a possibility of ignition associated with over-charge, temperature increase, or impact. To prevent such risks, the use of an aqueous solvent in a lithium ion battery has been proposed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a partially cutout cross-sectional view of a secondary battery of an embodiment;

FIG. 2 is a side view of the battery of FIG. 1 ;

FIG. 3 is a partially cutout perspective view of the secondary battery of the embodiment;

FIG. 4 is an enlarged cross-sectional view of an A portion of FIG. 3 ;

FIG. 5 is a perspective view of an example of a battery module of the embodiment;

FIG. 6 is a perspective view of an example of a battery pack of the embodiment;

FIG. 7 is an exploded perspective view of another example of a battery pack of the embodiment;

FIG. 8 is a block diagram showing an electric circuit of the battery pack of FIG. 7 ;

FIG. 9 is a schematic cross-sectional view of an example of a coin-type secondary battery according to an embodiment;

FIG. 10 is a schematic cross-sectional view of an example of a square-type secondary battery according to an embodiment;

FIG. 11 is a schematic cross-sectional view of a side surface of the square-type secondary battery in FIG. 10 ;

FIG. 12 is a perspective view of an example of a battery module according to an embodiment;

FIG. 13 is a schematic view of an example of a vehicle including a battery pack according to the embodiment; and

FIG. 14 is a schematic view showing an aspect of a vehicle including the secondary battery according to embodiments.

DETAILED DESCRIPTION

According to one embodiment, a secondary battery including a positive electrode, a negative electrode, and an electrolyte is provided. The negative electrode includes titanium-containing oxide and at least one kind of element selected from the group consisting of B, P, Al, La, Zr, Ge, Zn, Sn, Ga, Pb, In, Bi, and Tl. The electrolyte includes lithium ions and a solvent containing water.

Furthermore, according to one embodiment, a battery module includes the secondary battery according to the embodiment.

Yet further, according to one embodiment, a battery pack includes the secondary battery according to the embodiment.

In addition, according to one embodiment, a vehicle includes the battery pack according to the embodiment.

According to another embodiment, a secondary battery is provided. The secondary battery includes a positive electrode, a negative electrode, and an electrolytic solution. The negative electrode includes a current collector and a negative electrode active material including titanium-containing oxide. At least one of the current collector and the negative electrode active material includes on at least a portion of a surface thereof, a covering layer including at least one kind of element selected from the group consisting of Zn, In, Sn, Pb, Hg, Cu, Cd, Ag, and Bi. The electrolytic solution includes an aqueous solvent and an electrolyte.

Furthermore, according to another embodiment, a battery module is provided. The battery module includes the secondary battery according to the other embodiment.

According to one embodiment, a battery pack is provided. The battery pack includes the secondary battery according to the other embodiment

According to still another embodiment, a vehicle is provided. The vehicle includes the battery pack according to the other embodiment.

First Embodiment

According to a first embodiment, a secondary battery including a positive electrode, a negative electrode, and an electrolyte is provided. The negative electrode contains particles of titanium-containing oxide and at least one kind of element (hereinafter referred to as an additive element) selected from the group consisting of B, P, Al, La, Zr, Ge, Zn, Sn, Ga, Pb, In, Bi, and TI. The electrolyte contains lithium ions and a solvent containing water. In this electrolyte, the ion conductivity can be increased by 10 times or more as compared with a nonaqueous electrolytic solution. When such an aqueous electrolyte is combined with a negative electrode containing particles of titanium-containing oxide as a negative electrode active material, generation of hydrogen gas inhibits insertion and extraction of lithium ions. The present inventors have for the first time found that when a negative electrode contains an additive element, a hydrogen generation rate in titanium-containing oxide is reduced to reduce generation of hydrogen, so that lithium ions can be efficiently inserted in and extracted from the negative electrode, whereby cycle life performance, storage performance, and large current discharge performance of a secondary battery are enhanced.

When the electrolyte further contains zinc ions, the capacity of the secondary battery can be improved in addition to the cycle life performance, the storage performance, and the large current discharge performance. It is assumed that this is due to the mechanism to be described as follows. Zinc ions in an electrolytic solution may be deposited as zinc as metal or a compound of zinc (for example, zinc oxide or zinc hydroxide) on a surface of particles of titanium-containing oxide by charging such as initial charging. Thus, at least a portion of the surface of the particles of the titanium-containing oxide can be covered with a covering member containing Zn as a zinc element. Since the Zn (zinc element) in the covering member functions as an additive element to increase a hydrogen generation overvoltage of a negative electrode, hydrogen generation is suppressed, so that lithium ions are smoothly inserted in and extracted from the negative electrode. Since the zinc element in the covering member also functions as a negative electrode active material, a negative electrode capacity is enhanced. When the zinc element in a metal state is contained in the negative electrode, electron conductivity of the negative electrode is enhanced. From these results, it is possible to achieve a secondary battery being excellent in cycle life performance, storage performance, and large current discharge performance and having a high capacity.

When the covering member containing an additive element covers at least a portion of the surface of the particles of the titanium-containing oxide, the hydrogen generation overvoltage in the negative electrode can be further increased, and therefore, the cycle life performance and the storage performance of the secondary battery can be further improved.

When the electrolyte contains an anion including at least one kind selected from the group consisting of a chlorine ion (Cl − ), a hydroxide ion (OH − ), a sulfate ion (SO 4 − ), and a nitrate ion (NO 3 − ), the ion conductivity of the electrolyte is enhanced, whereby large current discharge performance of the secondary battery can be improved.

When the titanium-containing oxide includes at least one kind selected from titanium oxide represented by a general formula Li x TiO 2 (0≤x≤1) and lithium titanium oxide represented by a general formula Li 4+x Ti 5 O 12 (x is −1≤x≤3), the hydrogen generation overvoltage in the negative electrode is further increased, so that the cycle life performance and the storage performance of the secondary battery can be further improved.

As described above, the secondary battery of each embodiment includes the electrolyte, the negative electrode, and the positive electrode, and a separator can be interposed between the negative electrode and the positive electrode. Further, the secondary battery of each embodiment can further include a container storing the electrolyte, the negative electrode, and the positive electrode.

Hereinafter, the electrolyte, the negative electrode, the positive electrode, the separator, and the container will be described.

1) Electrolyte

The electrolyte is a first electrolyte, which contains a solvent containing lithium ions and water. Examples of the electrolyte include a solution containing lithium ions, and a gel-like electrolyte including a composite of the solution and a polymer material. The solution containing lithium ions is prepared by, for example, dissolving a lithium salt in a solvent containing water. Examples of the polymer material include polyvinylidene fluoride (PVdF), polyacrilonitrile (PAN), and polyethyleneoxide (PEO)

It is preferable to use water as a solvent. This is because an electrolyte having a high ion conductivity can be obtained. An aqueous solution may have a lithium ion concentration in the range of not less than 2 mol/L and not more than 10 mol/L. It is considered that when the lithium ion concentration is high, free water molecules are reduced, and a hydrogen generation suppression effect can be enhanced. Thus, the concentration is more preferably in the range of not less than 4 mol/L and not more than 10 mol/L and still more preferably in the range of not less than 6 mol/L and not more than 10 mol/L.

Examples of lithium salt include LiCl, LiBr, LiOH, Li 2 SO 4 , LiNO 3 , Li 2 C 2 O 4 , and LiB[(OCO) 2 ] 2 . One or plural kinds of lithium ions may be used. It is preferable because an electrolyte containing LiCl can have a high lithium ion concentration of not less than 4 mol/L or not less than 6 mol/L.

It is preferable that an electrolyte contains anion species including at least one kind selected from the group consisting of a chlorine ion (Cl − ), a hydroxide ion (OH − ), a sulfate ion (SO 4 2− ), and a nitrate ion (NO 3 − ). Those anion species can be obtained by, for example, dissolving lithium salt, such as LiCl, LiOH, Li 2 SO 4 , or LiNO 3 , in a solvent.

The electrolyte may contain salt of an additive element. One or plural kinds of additive elements may be contained in the salt. It is preferable that this salt can be dissolved in a solvent containing water. Examples of the salt include ZnSO 4 . When the electrolyte contains ZnSO 4 , zinc ions exist in the electrolyte (for example, in a solvent). As a result, metallic zinc or a compound of zinc is deposited on a surface of titanium-containing oxide particles by charging such as initial charging, whereby at least a portion of the surface of the titanium-containing oxide particles can be covered with a zinc-containing covering member. Thus, the capacity of the secondary battery can be improved in addition to the cycle life performance, the storage performance, and the large current discharge performance.

<div id="p-0044" num="0043" class="descrip

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation application of PCT Application No. PCT/JP2017/003666, filed Feb. 1, 2017, and based upon and claiming the benefit of priority from Japanese Patent Application No. 2016-017249, filed Feb. 1, 2016, and Japanese Patent Application No. 2016-184794, filed Sep. 21, 2016, the entire contents of all of which are incorporated herein by reference.

FIELD

Embodiments of the present invention relate to a secondary battery, a battery module, a battery pack and a vehicle.

BACKGROUND

A nonaqueous electrolyte battery in which a lithium metal, a lithium alloy, a lithium compound or a carbonaceous material is used for a negative electrode is expected as a high energy density battery, and active research and development have been conducted. A lithium ion secondary battery including a positive electrode containing LiCoO 2 or LiMn 2 O 4 as an active material and a negative electrode containing a carbonaceous material that allows lithium ions to be inserted in and extracted from has been widely put to practical use for a portable device.

In the case of installing the battery in a vehicle such as an automobile or a train, it is desirable that the positive and negative electrodes include a material excellent in chemical and electrochemical stability, in durability, and in corrosion resistance for obtaining a storage performance in high-temperature environments (e.g., at not less than 60° C.), cycle performance, and reliability of high power over a long time. Further, high performance in cold climates, high-output performance in a low-temperature environment (−40° C.), and long life performance are required. On the other hand, although a nonvolatile and noncombustible electrolytic solution has been developed as a nonaqueous electrolyte for enhancing safety performance, a battery including the electrolytic solution has not yet been put to practical use because output characteristics, low-temperature performance, and long life performance are reduced.

As described above, when the lithium ion secondary battery is installed in a vehicle or the like, there is a problem with the high-temperature durability and low-temperature output performance. Thus, it is difficult to install the lithium ion secondary battery in an engine room of the vehicle in place of a lead storage battery.

Since an electrolytic solution of the lithium ion secondary battery is used at a high voltage of 2 V to 4.5 V, an aqueous solution-based electrolytic solution is not used in the lithium ion secondary battery, and a nonaqueous electrolytic solution in which lithium salt is dissolved in an organic solvent is used. It has been considered to improve a composition of the nonaqueous electrolytic solution in order to improve large current discharge performance and cycle life performance. However, since ion conductivity of the nonaqueous electrolytic solution is lower than that of the aqueous solution-based electrolytic solution, it is difficult to lower the resistance of a battery. Since an organic solvent is used in the nonaqueous electrolyte, high temperature decomposition of the nonaqueous electrolyte is likely to occur. And since heat stability of the nonaqueous electrolyte is poor, high-temperature cycle life performance is lowered. Also, although a solid electrolyte has been considered as a nonaqueous electrolyte, since the ion conductivity of the nonaqueous electrolyte is further lowered, it is difficult to enhance large current discharge performance.

In a nonaqueous electrolyte battery charged and discharged by movement of Li ions between a negative electrode and a positive electrode, a nonaqueous electrolyte containing a nonaqueous solvent is used as an electrolytic solution. Since the nonaqueous solvent has wide potential stability, in the nonaqueous electrolyte battery, a high cell voltage of approximately 3 to 4 V can be exhibited. Thus, the nonaqueous electrolyte battery is excellent in energy density as compared with conventional storage batteries. Therefore, in recent years, the use of nonaqueous electrolyte batteries has been progressing in a wide range of applications including on-vehicle application such as μHEV (micro-hybrid electric vehicle) and an idling stop system, and for stationary use.

However, since a nonaqueous solvent contained in a nonaqueous electrolyte is an organic solvent, the nonaqueous solvent is highly volatile and inflammable. Thus, a nonaqueous electrolyte battery has risks such as a possibility of ignition associated with over-charge, temperature increase, or impact. To prevent such risks, the use of an aqueous solvent in a lithium ion battery has been proposed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a partially cutout cross-sectional view of a secondary battery of an embodiment;

FIG. 2 is a side view of the battery of FIG. 1 ;

FIG. 3 is a partially cutout perspective view of the secondary battery of the embodiment;

FIG. 4 is an enlarged cross-sectional view of an A portion of FIG. 3 ;

FIG. 5 is a perspective view of an example of a battery module of the embodiment;

FIG. 6 is a perspective view of an example of a battery pack of the embodiment;

FIG. 7 is an exploded perspective view of another example of a battery pack of the embodiment;

FIG. 8 is a block diagram showing an electric circuit of the battery pack of FIG. 7 ;

FIG. 9 is a schematic cross-sectional view of an example of a coin-type secondary battery according to an embodiment;

FIG. 10 is a schematic cross-sectional view of an example of a square-type secondary battery according to an embodiment;

FIG. 11 is a schematic cross-sectional view of a side surface of the square-type secondary battery in FIG. 10 ;

FIG. 12 is a perspective view of an example of a battery module according to an embodiment;

FIG. 13 is a schematic view of an example of a vehicle including a battery pack according to the embodiment; and

FIG. 14 is a schematic view showing an aspect of a vehicle including the secondary battery according to embodiments.

DETAILED DESCRIPTION

According to one embodiment, a secondary battery including a positive electrode, a negative electrode, and an electrolyte is provided. The negative electrode includes titanium-containing oxide and at least one kind of element selected from the group consisting of B, P, Al, La, Zr, Ge, Zn, Sn, Ga, Pb, In, Bi, and Tl. The electrolyte includes lithium ions and a solvent containing water.

Furthermore, according to one embodiment, a battery module includes the secondary battery according to the embodiment.

Yet further, according to one embodiment, a battery pack includes the secondary battery according to the embodiment.

In addition, according to one embodiment, a vehicle includes the battery pack according to the embodiment.

According to another embodiment, a secondary battery is provided. The secondary battery includes a positive electrode, a negative electrode, and an electrolytic solution. The negative electrode includes a current collector and a negative electrode active material including titanium-containing oxide. At least one of the current collector and the negative electrode active material includes on at least a portion of a surface thereof, a covering layer including at least one kind of element selected from the group consisting of Zn, In, Sn, Pb, Hg, Cu, Cd, Ag, and Bi. The electrolytic solution includes an aqueous solvent and an electrolyte.

Furthermore, according to another embodiment, a battery module is provided. The battery module includes the secondary battery according to the other embodiment.

According to one embodiment, a battery pack is provided. The battery pack includes the secondary battery according to the other embodiment

According to still another embodiment, a vehicle is provided. The vehicle includes the battery pack according to the other embodiment.

First Embodiment

According to a first embodiment, a secondary battery including a positive electrode, a negative electrode, and an electrolyte is provided. The negative electrode contains particles of titanium-containing oxide and at least one kind of element (hereinafter referred to as an additive element) selected from the group consisting of B, P, Al, La, Zr, Ge, Zn, Sn, Ga, Pb, In, Bi, and TI. The electrolyte contains lithium ions and a solvent containing water. In this electrolyte, the ion conductivity can be increased by 10 times or more as compared with a nonaqueous electrolytic solution. When such an aqueous electrolyte is combined with a negative electrode containing particles of titanium-containing oxide as a negative electrode active material, generation of hydrogen gas inhibits insertion and extraction of lithium ions. The present inventors have for the first time found that when a negative electrode contains an additive element, a hydrogen generation rate in titanium-containing oxide is reduced to reduce generation of hydrogen, so that lithium ions can be efficiently inserted in and extracted from the negative electrode, whereby cycle life performance, storage performance, and large current discharge performance of a secondary battery are enhanced.

When the electrolyte further contains zinc ions, the capacity of the secondary battery can be improved in addition to the cycle life performance, the storage performance, and the large current discharge performance. It is assumed that this is due to the mechanism to be described as follows. Zinc ions in an electrolytic solution may be deposited as zinc as metal or a compound of zinc (for example, zinc oxide or zinc hydroxide) on a surface of particles of titanium-containing oxide by charging such as initial charging. Thus, at least a portion of the surface of the particles of the titanium-containing oxide can be covered with a covering member containing Zn as a zinc element. Since the Zn (zinc element) in the covering member functions as an additive element to increase a hydrogen generation overvoltage of a negative electrode, hydrogen generation is suppressed, so that lithium ions are smoothly inserted in and extracted from the negative electrode. Since the zinc element in the covering member also functions as a negative electrode active material, a negative electrode capacity is enhanced. When the zinc element in a metal state is contained in the negative electrode, electron conductivity of the negative electrode is enhanced. From these results, it is possible to achieve a secondary battery being excellent in cycle life performance, storage performance, and large current discharge performance and having a high capacity.

When the covering member containing an additive element covers at least a portion of the surface of the particles of the titanium-containing oxide, the hydrogen generation overvoltage in the negative electrode can be further increased, and therefore, the cycle life performance and the storage performance of the secondary battery can be further improved.

When the electrolyte contains an anion including at least one kind selected from the group consisting of a chlorine ion (Cl − ), a hydroxide ion (OH − ), a sulfate ion (SO 4 − ), and a nitrate ion (NO 3 − ), the ion conductivity of the electrolyte is enhanced, whereby large current discharge performance of the secondary battery can be improved.

When the titanium-containing oxide includes at least one kind selected from titanium oxide represented by a general formula Li x TiO 2 (0≤x≤1) and lithium titanium oxide represented by a general formula Li 4+x Ti 5 O 12 (x is −1≤x≤3), the hydrogen generation overvoltage in the negative electrode is further increased, so that the cycle life performance and the storage performance of the secondary battery can be further improved.

As described above, the secondary battery of each embodiment includes the electrolyte, the negative electrode, and the positive electrode, and a separator can be interposed between the negative electrode and the positive electrode. Further, the secondary battery of each embodiment can further include a container storing the electrolyte, the negative electrode, and the positive electrode.

Hereinafter, the electrolyte, the negative electrode, the positive electrode, the separator, and the container will be described.

1) Electrolyte

The electrolyte is a first electrolyte, which contains a solvent containing lithium ions and water. Examples of the electrolyte include a solution containing lithium ions, and a gel-like electrolyte including a composite of the solution and a polymer material. The solution containing lithium ions is prepared by, for example, dissolving a lithium salt in a solvent containing water. Examples of the polymer material include polyvinylidene fluoride (PVdF), polyacrilonitrile (PAN), and polyethyleneoxide (PEO)

It is preferable to use water as a solvent. This is because an electrolyte having a high ion conductivity can be obtained. An aqueous solution may have a lithium ion concentration in the range of not less than 2 mol/L and not more than 10 mol/L. It is considered that when the lithium ion concentration is high, free water molecules are reduced, and a hydrogen generation suppression effect can be enhanced. Thus, the concentration is more preferably in the range of not less than 4 mol/L and not more than 10 mol/L and still more preferably in the range of not less than 6 mol/L and not more than 10 mol/L.

Examples of lithium salt include LiCl, LiBr, LiOH, Li 2 SO 4 , LiNO 3 , Li 2 C 2 O 4 , and LiB[(OCO) 2 ] 2 . One or plural kinds of lithium ions may be used. It is preferable because an electrolyte containing LiCl can have a high lithium ion concentration of not less than 4 mol/L or not less than 6 mol/L.

It is preferable that an electrolyte contains anion species including at least one kind selected from the group consisting of a chlorine ion (Cl − ), a hydroxide ion (OH − ), a sulfate ion (SO 4 2− ), and a nitrate ion (NO 3 − ). Those anion species can be obtained by, for example, dissolving lithium salt, such as LiCl, LiOH, Li 2 SO 4 , or LiNO 3 , in a solvent.

The electrolyte may contain salt of an additive element. One or plural kinds of additive elements may be contained in the salt. It is preferable that this salt can be dissolved in a solvent containing water. Examples of the salt include ZnSO 4 . When the electrolyte contains ZnSO 4 , zinc ions exist in the electrolyte (for example, in a solvent). As a result, metallic zinc or a compound of zinc is deposited on a surface of titanium-containing oxide particles by charging such as initial charging, whereby at least a portion of the surface of the titanium-containing oxide particles can be covered with a zinc-containing covering member. Thus, the capacity of the secondary battery can be improved in addition to the cycle life performance, the storage performance, and the large current discharge performance.

A pH value of an aqueous solution containing lithium ions is preferably in the range of not less than 3 and not more than 13. If the pH value is in this range, hydrogen generation can be reduced. Consequently, the cycle life performance and the storage performance can be enhanced. More preferable ranges are not less than pH 4 and not more than pH 6.5 in an acidic region and not less than pH 7.5 and not more than pH 12 in an alkaline region. When the pH value is in the acidic region or the alkaline region, corrosion reaction of an additive element such as zinc can be suppressed while improving the ion conductivity of an electrolyte. The pH value of the electrolyte can be adjusted into a range in the acidic region by adding sulfuric acid to the electrolyte. On the other hand, the pH value of the electrolyte can be adjusted into a range in the alkaline region by adding LiOH to the electrolyte.

2) Negative Electrode

The negative electrode includes a negative electrode current collector and a negative electrode active material-containing layer provided on one side or both sides of the current collector and including an active material, an electro-conductive agent, and a binder.

Examples of the negative electrode current collector include a foil, a porous body, and a mesh. Examples of materials forming the negative electrode current collector include electrically conductive materials such as metals and alloys. Examples of metals include nickel, stainless steel, iron, copper, aluminum, and zinc. It is preferable for the negative electrode current collector to include a metal plate whose surface is covered with a layer or film of metal oxide by oxidation treatment. The negative electrode current collector may be made of one or more kinds of materials.

A negative electrode active material-containing layer further contains at least one kind of element (hereinafter referred to as an additive element) selected from the group consisting of B, P, Al, La, Zr, Ge, Zn, Sn, Ga, Pb, In, Bi, and Tl. Each additive element may take any form including a simple substance, a compound, and an alloy. Each additive element may be present in a negative electrode in a plurality of forms such as a simple substance and a compound.

Examples of compounds of each additive element include oxide, hydroxide, and an oxide solid electrolyte. Examples of oxides of the additive element include boron oxide (B 2 O 3 ), alumina (Al 2 O 3 ), zirconia oxide (ZrO 2 ), germanium oxide (GeO 2 ), zinc oxide (ZnO), and lead oxide (PbO). Examples of hydroxides of the additive element include zinc hydroxide (Zn(OH) 2 ). On the other hand, it is preferable to use an oxide solid electrolyte having high stability in an alkali aqueous solution and having lithium ion conductivity. In particular, an oxide solid electrolyte having a garnet crystal structure, a perovskite crystal structure, or a NASICON-type crystal structure has advantages of chemical stability in an alkaline aqueous solution, a high reduction resistance, and a wide potential window. Examples of the oxide solid electrolyte having the garnet crystal structure include Li 5+x A x La 3−x M 2 O 12 (A is at least one kind of element selected from the group consisting of Ca, Sr, and Ba, M is Nb and/or Ta, and x is 0≤x≤2), Li 3 M 2−x L 2 O 12 (M is Ta and/or Nb, L is Zr, and x is 0≤x≤2), Li 7−3x Al x La 3 Zr 2 O 12 (x is 0≤x≤0.3), and Li 7 La 3 Zr 2 O 12 . Among them, since Li 6.25 Al 0.25 La 3 Zr 2 O 12 and Li 7 La 3 Zr 2 O 12 each have a high ion conductivity and are each electrochemically stable, the large current discharge performance and the cycle life performance of the secondary battery are improved. As the oxide solid electrolyte having the perovskite crystal structure, Li 3x La 2/3−x TiO 3 (0.05≤x≤0.15) is preferably used. As the oxide solid electrolyte having the NASICON-type crystal structure, Li 1.3 Ti 1.7 Al 0.3 (PO 4 ) 3 is preferably used. As an oxide solid electrolyte having a γ-Li 3 PO 4 crystal structure, Li 14 ZnGe 4 O 16 or Li 3.6 Ge 0.6 V 0.4 O 4 is preferably used.

Preferred examples of oxides include zirconia oxide (ZrO 2 ), alumina (Al 2 O 3 ), zinc oxide (ZnO), and germanium oxide (GeO 2 ). Those oxides have a high suppression effect for hydrogen generation. When Al 2 O 3 is used, hydrogen generation is suppressed, and the cycle life performance and the storage performance are enhanced.

Since zinc as metal or a compound of zinc (for example, zinc oxide or zinc hydroxide) has a high hydrogen overvoltage and functions as a negative electrode active material, hydrogen generation is suppressed, and a high capacity negative electrode can be achieved. Since zinc as metal is excellent in electron conductivity, it can serve as an electro-conductive agent, so that the electron conductivity of a negative electrode can be enhanced.

Composite particles in which at least a portion of a surface of particles of an additive element is covered with a layer or film including oxide of the additive element may be used. The hydrogen generation overvoltage on a surface of metal oxide can be increased as compared with a surface of a metal simple substance. In particular, a composite in which at least a portion of a surface of Al particles is covered with a layer or a film including alumina (Al 2 O 3 ) and a composite in which at least a portion of a surface of Zn particles is covered with a layer or a film including zinc oxide (ZnO) each have a high hydrogen overvoltage, and thus it is preferable. It is preferable that alumina is formed by applying alumite treatment to Al body.

Examples of alloys containing an additive element include a Zn alloy, a Bi—In—Pb-based alloy, a Bi—In—Ca-based alloy, and a Bi—In—Al alloy. Those alloys can increase the hydrogen generation overvoltage.

The additive element allows containing of a negative electrode active material-containing layer by mixing particles containing the additive element with titanium-containing oxide particles. Although the shape of particles containing this additive element is not limited particularly, the particles may have a spherical shape, an elliptical shape, a flat shape, a fibrous shape, or the like.

When additive element-containing particles are mixed with negative electrode active material particles, it is desirable that a mixing ratio satisfies the following formula (1):

2% by weight≤{ W 1 /W 2 }×100≤50% by weight  (1)

In the formula (1), W 1 represents the weight of the additive element-containing particles, and W 2 is the weight of the negative electrode active material particles. When a surface of the titanium-containing oxide particles is covered with a covering member, W 2 is the total weight of the titanium-containing oxide particles and the covering member.

When the weight ratio of an additive element is not less than 2% by weight and not more than 50% by weight, the electron conductivity in a negative electrode is enhanced, and hydrogen generation is significantly suppressed. Therefore, lithium ions can be smoothly inserted in and extracted from the negative electrode active material, whereby the large current discharge performance of a battery can be enhanced. A more preferable range of the weight ratio is not less than 3% by weight and not more than 30% by weight.

The weight ratio of the additive element is measured by the following method. A secondary battery is disassembled in a glove box filled with argon to take out a negative electrode therefrom. A negative electrode active material-containing layer is separated from a negative electrode current collector of the taken out negative electrode. The negative electrode active material-containing layer is washed with water or cleaned with a neutral aqueous solution and then dried. Thereafter, the additive element and the negative electrode active material are separated using a specific gravity difference between the additive element and the negative electrode active material. The separation is performed by a method of putting a mixed powder in an organic solvent and separating the additive element and the negative electrode active material based on a difference in settling velocity or a method of separating the additive element and the negative electrode active material by using a dry type gravity sorting/separator device. The weights of the additive element and the negative electrode active material are measured to calculate the weight ratio of the additive element from the formula (1).

At least a portion of the surface of titanium-containing oxide particles can be covered with a covering member containing the additive element. Examples of the covering method include, in addition to plating and evaporation, a method of allowing an electrolytic solution of a secondary battery to contain the additive element and allowing the additive element in the electrolytic solution to be deposited on titanium-containing oxide particles by charging. A thickness of the covering member including the additive element is preferably not less than 0.01 μm and not more than 1 μm. If the thickness is less than this range, hydrogen generation increases, and the life performance may be reduced. On the other hand, if the thickness is more than this range, resistance increases, and the large current discharge performance may be reduced. A more preferable range is not less than 0.01 μm and not more than 0.5 μm. Although the covering member containing the additive element may have a granular shape, a fibrous shape, a layered shape, or the like, the shape is not limited particularly. The thickness of the covering member can be measured by observation using a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

The negative electrode active material-containing layer may further contain titanium oxide (TiO, TiO 2 ) in addition to the additive element.

The negative electrode active material contains one or plural kinds of titanium-containing oxides. Examples of the titanium-containing oxides include lithium titanium oxide, titanium oxide, niobium titanium oxide, and sodium niobium titanium oxide. The Li insertion potential of the titanium-containing oxide is desirably in a range of not less than 1V (vs. Li/Li + ) and not more than 3V (vs. Li/Li + ).

Examples of lithium titanium oxides include spinel structure lithium titanium oxide (for example, a general formula Li 4+x Ti 5 O 12 (x is −1≤x≤3)), lithium titanium oxide having a ramsdellite structure (for example, Li 2+x Ti 3 O 7 (−1≤x≤3)), Li 1+x Ti 2 O 4 (0≤x≤1), Li 1.1+x Ti 1.8 O 4 (0≤x≤1), Li 1.07+x Ti 1.86 O 4 (0≤x≤1), and LiTiO 2 (0&lt;x≤1).

Examples of titanium oxides include titanium oxide having a monoclinic structure, titanium oxide having a rutile structure, and titanium oxide having an anatase structure. In the titanium oxide having each crystal structure, the composition before charging can be represented by TiO 2 , and the composition after charging can be represented by Li x TiO 2 (x is 0≤x≤1). In the titanium oxide having a monoclinic structure, the structure before charging can be represented as TiO 2 (B).

Examples of niobium oxides include niobium oxide represented by Li a TiM b Nb 2±β O 7±σ (0≤a≤5, 0≤b≤0.3, 0≤β≤0.3, 0≤σ≤0.3, and M is at least one kind of element selected from the group consisting of Fe, V, Mo, and Ta).

Examples of sodium niobium titanium oxides include orthorhombic Na-containing niobium titanium composite oxide represented by a general formula Li 2+v Na 2−w M1 x Ti 6−y−z Nb y M2 z O 14+δ (0≤v≤4, 0&lt;w&lt;2, 0≤x&lt;2, 0&lt;y≤6, 0≤z&lt;3, −0.5≤δ≤0.5, M1 includes at least one selected from Cs, K, Sr, Ba, and Ca, and M2 includes at least one selected from Zr, Sn, V, Ta, Mo, W, Fe, Co, Mn, and Al).

Preferable examples of titanium-containing oxides include titanium oxide having an anatase structure, titanium oxide having a monoclinic structure, and lithium titanium oxide having a spinel structure. In each titanium-containing oxide and the lithium titanium oxide, since the Li insertion potential is in a range of not less than 1.4 V (vs. Li/Li + ) and not more than 2 V (vs. Li/Li + ), the hydrogen generation suppression effect can be enhanced by combining the titanium-containing oxide with an electrolytic solution being an aqueous solution containing lithium ions.

Consequently, a negative electrode can allow lithium ions to be efficiently inserted in and extracted from. Titanium oxide having an anatase structure has the most excellent hydrogen generation suppression effect, followed by titanium oxide having a monoclinic structure, lithium titanium oxide having a spinel structure, and niobium titanium oxide. By virtue of the use of those titanium-containing oxides, an aluminum foil or an aluminum alloy foil used as a positive electrode current collector can be used like a negative electrode current collector, instead of a copper foil, so that weight reduction and cost reduction can be achieved. This is advantageous for an electrode structure as a bipolar structure. The lithium titanium oxide having a spinel structure can reduce a change in volume due to a charge/discharge reaction.

A negative electrode active material is contained in the form of particles in a negative electrode active material-containing layer. Negative electrode active material particles may be independent primary particles, secondary particles as agglomerates of primary particles, or a mixture of the independent primary particles and the secondary particles. The shape of particles is not limited particularly and may be, for example, a spherical shape, an elliptical shape, a flat shape, or a fibrous shape.

An average particle size (diameter) of secondary particles of a negative electrode active material is preferably not less than 5 μm and more preferably not less than 7 μm and not more than 20 μm. If the average particle size is in this range, the hydrogen generation suppression effect can be enhanced.

A negative electrode active material in which the average particle size of secondary particles is not less than 5 μm is obtained by the following method, for example. An active-material raw material is reacted and synthesized to produce an active material precursor having an average particle size of not more than 1 μm. After that, the precursor is baked as a heat treatment and then ground using a grinder such as a ball mill and a jet mill. Then, in the heat treatment, an active material precursor is aggregated to be grown to secondary particles having a large particle size.

An average particle size of primary particles of a negative electrode active material is desirably not more than 1 μm. Consequently, a diffusion distance of lithium ions inside active material particles is reduced, and a specific surface area increases. Thus, excellent high input performance (i.e., rapid charge performance) is obtained. On the other hand, if an average particle size is small, particles are likely to aggregate, and most of an electrolyte may be distributed in a negative electrode to cause depletion of the electrolyte in a positive electrode. Therefore, the lower limit value of the average particle size is desirably 0.001 μm. A more preferable average particle size is not less than 0.1 μm and not more than 0.8 μm.

In negative electrode active material particles, it is desirable that the specific surface area according to a BET method using N 2 absorption is in a range of not less than 3 m 2 /g and not more than 200 m 2 /g. Consequently, an affinity with an electrolyte of a negative electrode can be further enhanced.

A specific surface area of a negative electrode active material-containing layer (except for a current collector) is desirably in a range of not less than 3 m 2 /g and not more than 50 m 2 /g. A more preferable range of the specific surface area is not less than 5 m 2 /g and not more than 50 m 2 /g. The negative electrode active material-containing layer may be a porous layer provided on a current collector, and including a negative electrode active material, an electro-conductive agent, and a binder.

A porosity of a negative electrode (except for a current collector) is desirably in a range of 20 to 50%. Consequently, it is possible to obtain a high-density negative electrode excellent in affinity with an electrolyte. A more preferable range of the porosity is 25 to 40%.

Examples of the electro-conductive agent include carbon materials, such as acetylene black, carbon black, coke, carbon fibers, or graphite, and metal powders such as nickel or zinc. One or plural kinds of electro-conductive agents may be used. Since hydrogen is generated from a carbon material, it is desirable to use a metal powder as an electro-conductive agent. When zinc particles are used in an additive element, since the zinc particles serve as an electro-conductive agent, another electro-conductive agent is not required. The zinc particles further serve as a negative electrode active material. Thus, when the zinc particles are used in the additive element, hydrogen generation is suppressed, and a high capacity negative electrode excellent in electron conductivity can be achieved.

Examples of the binder include polytetrafluoroethylene (PTFE), fluororubbers, styrene butadiene rubbers, and core/shell binder. One or plural kinds of binders may be used.

The mixing ratio of the negative electrode active material, the electro-conductive agent, and the binder is preferably set in the range of 80% by weight to 95% by weight for the negative electrode active material, 3% by weight to 18% by weight for the electro-conductive agent, and 2% by weight to 7% by weight for the binder.

The negative electrode is produced by, for example, suspending the negative electrode active material, the electro-conductive agent, and the binder in an appropriate solvent, applying the suspended matter on a current collector, drying, and pressing the current collector by, for example, heat-pressing.

3) Positive Electrode

The positive electrode has a positive electrode current collector and a positive electrode active material-containing layer provided on one side or both sides of the current collector and including an active material, an electro-conductive agent, and a binder.

As the positive electrode active material, a positive electrode active material capable of allowing Li to be inserted and extracted may be used. Examples of the positive electrode active material include lithium manganese composite oxide, lithium nickel composite oxide, lithium cobalt aluminum composite oxide, lithium nickel cobalt manganese composite oxide, spinel-type lithium manganese nickel composite oxide, lithium manganese cobalt composite oxide, lithium iron oxide, lithium fluorinated iron sulfate, and a phosphate compound having an olivine crystal structure (such as Li x FePO 4 (0≤x≤1) and Li x MnPO 4 (0≤x≤1)). The phosphate compound having an olivine crystal structure is excellent in heat stability.

Examples of a positive electrode active material capable of obtaining a high positive electrode potential include lithium manganese composite oxides such as LiMn 2 O 4 (0&lt;x≤1) and Li x MnO 2 (0&lt;x≤1), lithium nickel aluminum composite oxides such as Li x Ni 1−y Al y O2 (0&lt;x≤1, 0&lt;y≤1), lithium cobalt composite oxides such as Li x CoO 2 (0&lt;x≤1), lithium nickel cobalt composite oxides such as Li x Ni 1−y−z Co y Mn z O 2 (0&lt;x≤1, 0&lt;y≤1, 0≤z≤1), lithium manganese cobalt composite oxides such as Li x Mn y Co 1−y O 2 (0&lt;x≤1, 0&lt;y≤1), spinel-type lithium manganese nickel composite oxides such as Li x Mn 2−y Ni y O 4 (0&lt;x≤1, 0&lt;y&lt;2), lithium phosphorus oxides having an olivine crystal structure, such as Li x FePO 4 (0&lt;x≤1), Li x Fe 1−y Mn y PO 4 (0&lt;x≤1, 0≤y≤1) and Li x CoPO 4 (0&lt;x≤1), and fluorinated iron sulfate (such as Li x FeSO 4 F (0&lt;x≤1)).

According to lithium nickel aluminum composite oxides, lithium nickel cobalt manganese composite oxides, and lithium manganese cobalt composite oxides, reaction with an electrolyte under a high temperature environment can be suppressed, so that a battery life can be significantly increased. Composite oxide represented by Li x Ni 1−y−z Co y Mn z O 2 (0≤x≤1.1, 0≤y≤0.5, and 0≤z≤0.5, more preferably 0&lt;x≤1.1, 0&lt;y≤0.5, and 0&lt;z≤0.5) is advantageous for a high temperature durability life.

Particles of a positive electrode active material may include independent primary particles, secondary particles as agglomerates of primary particles, or both the independent primary particles and the secondary particles.

An average particle size (average particle diameter) of primary particles of the positive electrode active material is preferably not more than 1 μm and more preferably 0.05 to 0.5 μm. It is preferable that at least a portion of surfaces of the particles of the positive electrode active material is covered with a carbon material. The carbon material may take the form of a layer structure, a particle structure, or an aggregate of particles.

When the positive electrode active material particles take the form where the secondary particles and the independent primary particles are mixed, the average particle size of the positive electrode active material particles is preferably not less than 0.8 μm and not more than 15 μm.

As a positive electrode current collector, a foil, a porous body, or a mesh is preferably used. Examples of electrically conductive materials contained in the positive electrode current collector include aluminum alloy, and metals such as nickel, stainless steel, iron, copper, or aluminum.

Examples of an electro-conductive agent used for enhancing electron conductivity and suppressing contact resistance with a current collector include acetylene black, carbon black, graphite, and carbon fiber having an average fiber diameter of not more than 1 μm. One or plural kinds of electro-conductive agents may be used.

Examples of a binder for binding an active material and the electro-conductive agent include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluororubbers. One or plural kinds of binders may be used.

The mixing ratio of the positive electrode active material, the electro-conductive agent, and the binder is preferably set in the range of not less than 80% by weight and not more than 95% by weight for the positive electrode active material, not less than 3% by weight and not more than 18% by weight for the electro-conductive agent, and not less than 2% by weight and not more than 7% by weight for the binder. When the mixing ratio of the electro-conductive agent is not less than 3% by weight, the above effect can be exercised, and when the mixing ratio of the electro-conductive agent is not more than 18% by weight, decomposition of an electrolyte on a surface of the electro-conductive agent under high temperature preservation can be reduced. When the mixing ration of the binder is not less than 2% by weight, sufficient electrode strength is obtained, and when the mixing ration of the binder is not more than 7% by weight, an insulating portion of an electrode can be decreased.

The positive electrode is produced by, for example, suspending the positive electrode active material, the electro-conductive agent, and the binder in an appropriate solvent, applying the suspended matter on a positive electrode current collector, drying, and pressing the current collector. A positive electrode pressing pressure is preferably in the range of 0.15 ton/mm to 0.3 ton/mm. If the positive electrode pressing pressure is in this range, it is preferable because adhesion (i.e., peel strength) between the positive electrode active material-containing layer and the positive electrode current collector is enhanced, and, at the same time, the elongation percentage of the positive electrode current collector is not more than 20%.

4) Separator

A separator may be disposed between a positive electrode and a negative electrode. Examples of the separator include nonwoven fabrics, films, and paper. Examples of materials contained in the separator include polyolefin, such as polyethylene or polypropylene, and cellulose. Preferable examples of the separator include nonwoven fabrics containing cellulose fibers and porous films containing polyolefin fibers. The porosity of the separator is preferably not less than 60%. A fiber diameter is preferably not more than 10 μm. When the fiber diameter is not more than 10 μm, an affinity with an electrolyte of the separator is enhanced, so that battery resistance can be reduced. A more preferable range of the fiber diameter is not more than 3 μm. In a cellulose fiber containing nonwoven fabric having a porosity of not less than 60%, impregnation of an electrolyte is good, and high output performance can be exhibited from low temperature to high temperature. The separator does not react with a negative electrode in long term storage after charging, float charging, and over-charge, and a short-circuit between the negative electrode and a positive electrode due to dendrite precipitation of lithium metal does not occur. A more preferable range is 62% to 80%.

It is preferable that the separator has a thickness of not less than 20 μm and not more than 100 μm and a density of not less than 0.2 g/cm 3 and not more than 0.9 g/cm 3 . If the thickness and the density of the separator are in these ranges, mechanical strength and a reduction in battery resistance can be balanced, so that a high output secondary battery in which an internal short-circuit is suppressed can be provided. Heat shrinkage of the separator under a high temperature environment is small, and good high temperature storage performance can be exhibited.

5) Container

As a container containing a positive electrode, a negative electrode, and an electrolyte, a metal container, a laminate film container, or a resin container, such as a polyethylene container or a polypropylene container, may be used.

As the metal container, a rectangular or cylindrical metal can made of nickel, iron, stainless steel, or the like may be used.

Each plate thickness of the resin container and the metal container is preferably not more than 1 mm and more preferably not more than 0.5 mm. A more preferable range is not more than 0.3 mm. The lower limit value of the plate thickness is desirably 0.05 mm.

Examples of laminate films include a multilayer film in which a metal layer is covered with a resin layer. Examples of the metal layer include a stainless steel foil, an aluminum foil, and an aluminum alloy foil. As the resin layer, a polymer such as polypropylene (PP), polyethylene (PE), nylon, or polyethylene terephthalate (PET) may be used. A preferable range of a thickness of the laminate film is not more than 0.5 mm. A more preferable range is not more than 0.2 mm. The lower limit value of the thickness of the laminate film is desirably 0.01 mm.

The secondary battery according to the embodiments is applicable to secondary batteries in various forms such as a rectangular form, a cylindrical form, a flat form, a thin form, or a coin form. The secondary battery according to the embodiments is preferably a secondary battery having a bipolar structure. Consequently, it is advantageous in terms of enabling production of a plural of series cells as one cell.

An example of the secondary battery according to the embodiments will be described with reference to FIGS. 1 to 4 .

FIGS. 1 and 2 show an example of a secondary battery using a metal container.

An electrode group 1 is stored in a rectangular cylindrical metal container 2 . The electrode group 1 has a structure in which a positive electrode 3 and a negative electrode 4 are spirally wound to provide a flat shape while a separator 5 is interposed between the positive electrode 3 and the negative electrode 4 . An electrolyte (not shown) is held by the electrode group 1 . As shown in FIG. 2 , belt-like positive electrode leads 6 are electrically connected to a plural of portions of an end of the positive electrode 3 located on an end surface of the electrode group 1 . On the other hand, belt-like negative electrode leads 7 are electrically connected to a plural of portions of an end of the negative electrode 4 located on the end surface of the electrode group 1 . The positive electrode leads 6 are bundled to be electrically connected to a positive electrode conductive tab 8 . A positive electrode terminal is constituted of the positive electrode leads 6 and the positive electrode conductive tab 8 . The negative electrode leads 7 are bundled to be electrically connected to a negative electrode conductive tab 9 . A negative electrode terminal is constituted of the negative electrode leads 7 and the negative electrode conductive tab 9 . A metal sealing plate 10 is fixed to an opening of the metal container 2 by welding or the like. The positive electrode conductive tab 8 and the negative electrode conductive tab 9 are drawn to the outside through a take-out hole formed in the sealing plate 10 . An inner peripheral surface of each take-out hole of the sealing plate 10 is covered with an insulating member 11 in order to avoid a short-circuit due to contact between the positive electrode conductive tab 8 and the negative electrode conductive tab 9 .

FIGS. 3 and 4 show an example of a secondary battery using a container member made of a laminate film.

The laminate type electrode group 1 is stored in a bag- like container 2 made from a laminate film in which a metal layer is interposed between two resin films. The laminate type electrode group 1 has a structure in which the positive electrode 3 and the <figure-callout id="4" label="negative electrode

CLAIMS

Claims ( 34 )

What is claimed is:

1. A secondary battery comprising:

a positive electrode;

a negative electrode comprising a titanium-containing oxide and zinc as metal, at least one compound of additive element, or both the zinc as metal and the compound of additive element, the titanium-containing oxide comprising one or more selected from the group consisting of titanium oxide represented by a general formula Li x TiO 2 where 0≤x≤1, lithium titanium oxide represented by a general formula Li 4+x Ti 5 O 12 where −1≤x≤3, lithium titanium oxide represented by Li 2+x Ti 3 O 7 where −1≤x≤3, lithium titanium oxide represented by Li 1+x Ti 2 O 4 where 0≤x≤1, lithium titanium oxide represented by Li 1.1+x Ti 1.8 O 4 where 0≤x≤1, lithium titanium oxide represented by Li 1.07+x Ti 1.86 O 4 where 0≤x≤1, niobium oxide represented by Li a TiM b Nb 2±β O 7±σ where 0≤a≤5, 0≤b≤0.3, 0≤β≤0.3, 0≤σ≤0.3, and M is at least one selected from the group consisting of Fe, V, Mo, and Ta, and sodium niobium titanium oxide represented by a general formula Li 2+y Na 2−w M1 x Ti 6−y−z Nb y M2 z O 14+δ where 0≤v≤4, 0&lt;w&lt;2, 0≤x&lt;2, 0&lt;y≤6, 0≤z&lt;3, −0.5≤δ≤0.5, M1 includes at least one selected from Cs, K, Sr, Ba, and Ca, and M2 includes at least one selected from Zr, Sn, V, Ta, Mo, W, Fe, Co, Mn, and Al, and the compound of additive element being at least one selected from the group consisting of boron oxide, alumina, zirconium oxide, germanium oxide, zinc oxide, lead oxide, zinc hydroxide, Li 5+x A x La 3−x M 2 O 12 where A is at least one element selected from the group consisting of Ca, Sr, and Ba, M is Nb and/or Ta, and x is 0≤x≤2, Li 3 M 2−x L 2 O 12 where M is Ta and/or Nb, L is Zr, and x is 0≤x≤2, Li 7−3x Al x La 3 Zr 2 O 12 where x is 0≤x≤0.3, Li 7 La 3 Zr 2 O 12 , Li 3x La 2/3−x TiO 3 where 0.05≤x≤0.15, Li 1.3 Ti 1.7 Al 0.3 (PO 4 ) 3 , an oxide solid electrolyte having a γ-Li 3 PO 4 crystal structure, a Zn alloy, a Bi—In—Pb-based alloy, a Bi—In—Ca-based alloy, and a Bi—In—Al alloy; and

an electrolyte comprising lithium ions and water as a solvent.

2. The secondary battery according to claim 1 ,

wherein the electrolyte further comprises zinc ions.

3. The secondary battery according to claim 1 ,

wherein the negative electrode comprises particles of the titanium-containing oxide and a covering member covering at least a portion of surfaces of the particles and comprising the at least one kind of element.

4. The secondary battery according to claim 1 ,

wherein the electrolyte further comprises an anion comprising at least one selected from the group consisting of a chlorine ion (Cl − ), a hydroxide ion (OH − ), a sulfate ion (SO 4 2− ), and a nitrate ion (NO 3 − ).

5. The secondary battery according to claim 1 ,

wherein the titanium-containing oxide comprises at least one of the titanium oxide represented by the general formula Li x TiO 2 (0≤x≤1) and the lithium titanium oxide represented by the general formula Li 4+x Ti 5 O 12 (x is −1≤x≤3).

6. A battery module comprising the secondary battery according to claim 1 .

7. A battery pack comprising the secondary battery according to claim 1 .

8. The battery pack according to claim 7 , further comprising an external power distribution terminal and a protective circuit.

9. The battery pack according to claim 7 , comprising a plural of the secondary batteries, the secondary batteries being electrically connected in series, in parallel, or in combination thereof.

10. A vehicle comprising the battery pack according to claim 7 .

11. The vehicle according to claim 10 ,

wherein the battery pack is configured to recover a regenerative energy of power of the vehicle.

12. A secondary battery comprising:

a positive electrode;

a negative electrode comprising a current collector and a negative electrode active material containing a titanium-containing oxide, at least one of the current collector and the negative electrode active material including, on at least a portion of a surface thereof, a covering layer including at least one kind of element selected from the group consisting of Zn, In, Sn, Pb, Hg, Cu, Cd, Ag, and Bi, the titanium-containing oxide comprising at least one kind of compound selected from the group consisting of oxide of titanium represented by Li x TiO 2 wherein x is 0≤x≤1, lithium titanium oxide having a spinel structure, lithium-titanium oxide having a ramsdellite structure, niobium-titanium oxide represented by Li a TiM b Nb 2±β O 7±σ wherein 0≤a≤5, 0≤b≤0.3, 0≤β≤0.3, 0≤σ≤0.3, and M is at least one element selected from the group consisting of Fe, V, Mo, and Ta, niobium titanium composite oxide represented by a general formula Ti 1−x M x+y Nb 2−y O 7−δ , wherein 0≤x&lt;1, 0≤y&lt;1, and M includes at least one selected from the group consisting of Mg, Fe, Ni, Co, W, Ta, and Mo, and orthorhombic Na-containing niobium titanium composite oxide represented by a general formula Li 2+v Na 2−w M1 x Ti 6−y−z Nb y M2 z O 14+δ wherein 0≤v≤4, 0&lt;w&lt;2, 0≤x&lt;2, 0&lt;y&lt;6, 0≤z&lt;3, y+z&lt;6, −0.5≤δ≤0.5, M1 is at least one element selected from the group consisting of Cs, K, Sr, Ba, and Ca, and M2 is at least one element selected from the group consisting of Zr, Sn, V, Ta, Mo, W, Fe, Co, Mn, and Al; and

an electrolytic solution comprising an aqueous solvent and an electrolyte.

13. The secondary battery according to claim 12 , wherein the negative electrode active material includes the covering layer on at least a portion of the surface thereof.

14. The secondary battery according to claim 12 , wherein the negative electrode further comprises an electro-conductive agent, and the current collector, the negative electrode active material, and the electro-conductive agent each include the covering layer on at least a portion of a surface thereof.

15. The secondary battery according to claim 14 , wherein for each of the current collector, the negative electrode active material, and the electro-conductive agent, 10% or more to 100% or less of a surface area thereof is covered with the covering layer.

16. The secondary battery according to claim 12 , wherein the covering layer has a thickness of 2 nm or more and 5 μm or less and comprises at least one phase selected from the group consisting of: a phase of metal comprising at least one kind of element selected from the group consisting of Zn, In, Sn, Pb Hg, Cu, Cd, Ag, and Bi; a phase of alloy comprising the at least one kind of element; a phase of oxide of the at least one kind of element; and a phase of hydroxide of the at least one kind of element.

17. The secondary battery according to claim 12 , wherein the negative electrode active material comprises at least one kind of compound selected from the group consisting of the oxide of titanium, the lithium titanium oxide having the spinel structure, the niobium titanium composite oxide represented by the general formula Ti 1−x M x+y Nb 2−y O 7−δ , wherein 0≤x&lt;1, 0≤y&lt;1, and M includes at least one selected from Mg, Fe, Ni, Co, W, Ta, and Mo, and the orthorhombic type Na-containing niobium titanium composite oxide represented by the general formula Li 2+v Na 2−w M1 x Ti 6−y−z Nb y M2 z O 14+δ wherein 0≤v≤4, 0&lt;w&lt;2, 0≤x&lt;2, 0&lt;y&lt;6, 0≤z&lt;3, y+z&lt;6, −0.5≤δ≤0.5, M1 is at least one element selected from the group consisting of Cs, K, Sr, Ba, and Ca, and M2 is at least one element selected from the group consisting of Zr, Sn, V, Ta, Mo, W, Fe, Co, Mn, and Al.

18. The secondary battery according to claim 12 , wherein the electrolytic solution includes at least one kind of anion selected from the group consisting of NO 3 − , Cl − , LiSO 4 − , SO 4 2− , OH − , [N(SO 2 CF 3 ) 2 ] − , [N(SO 2 F) 2 ] − , and [B(C 2 O 4 ) 2 ] − .

19. The secondary battery according to claim 12 , wherein the positive electrode includes a positive electrode active material comprising at least one kind of compound selected from the group consisting of a phosphate compound having an olivine structure and represented by a general formula Li x FePO 4 wherein 0≤x≤1, a lithium manganese composite oxide represented by a general formula Li x Mn 2 O 4 wherein 0&lt;x≤1, and a lithium cobalt composite oxide represented by a general formula Li x CoO 2 wherein 0&lt;x≤1.

20. A battery module comprising the secondary battery according to claim 12 .

21. A battery pack comprising the secondary battery according to of claim 12 .

22. The battery pack according to claim 21 , further comprising an external power distribution terminal and a protective circuit.

23. The battery pack according to claim 21 , comprising a plural of the secondary batteries, the secondary batteries being electrically connected in series, in parallel, or in combination thereof.

24. A vehicle comprising the battery pack according to claim 21 .

25. The vehicle according to claim 24 ,

wherein the battery pack is configured to recover a regenerative energy of power of the vehicle.

26. The secondary battery according to claim 1 , wherein

the electrolyte is an aqueous electrolyte.

27. The secondary battery according to claim 1 , wherein

the electrolyte further comprises a lithium salt, the lithium salt is comprised of anion species and the lithium ions, and the electrolyte comprises the water in an amount of 1 mol or more relative to 1 mol of the lithium salt.

28. The secondary battery according to claim 12 , wherein

the electrolytic solution comprises water, and the electrolytic solution comprises the water in an amount of 1 mol or more relative to 1 mol of the electrolyte.

29. The secondary battery according to claim 27 ,

wherein the electrolyte comprises an aqueous solution having a lithium ion concentration in the range of not less than 2 mol/L and not more than 10 mol/L.

30. The secondary battery according to claim 28 ,

wherein the electrolyte comprises a lithium salt that dissociates into Li ions and anions, and the anions have a concentration of 1 M to 10 M in the electrolyte.

31. The secondary battery according to claim 12 ,

wherein the electrolytic solution further comprises zinc ions, and the electrolyte comprises a lithium salt that dissociates into Li ions and anions.

32. The secondary battery according to claim 1 ,

wherein the compound of additive element is selected from the group consisting of alumina, zirconium oxide, zinc oxide, Li 7 La 3 Zr 2 O 12 , Li 1.3 Ti 1.7 Al 0.3 (PO 4 ) 3 , Li 3.6 Ge 0.6 V 0.4 O 4 .

33. The secondary battery according to claim 1 ,

wherein the zinc as metal and the compound of additive element is comprised as particles mixed in the negative electrode or as a covering member covering the titanium-containing oxide.

34. The secondary battery according to claim 12 ,

wherein the covering layer comprises at least one selected from the group consisting of ZnO, In 2 O 3 , Cu, SnO, InO, and PbO 2 .

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US10727540B2

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2016-02-01

2017-03-13

Secondary battery, battery module, battery pack and vehicle

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